EP2841549B1 - Formulations, use of same as or for manufacture of dish-washing agents and their manufacture - Google Patents
Formulations, use of same as or for manufacture of dish-washing agents and their manufacture Download PDFInfo
- Publication number
- EP2841549B1 EP2841549B1 EP13720303.0A EP13720303A EP2841549B1 EP 2841549 B1 EP2841549 B1 EP 2841549B1 EP 13720303 A EP13720303 A EP 13720303A EP 2841549 B1 EP2841549 B1 EP 2841549B1
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- European Patent Office
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- 239000000203 mixture Substances 0.000 title claims description 112
- 238000009472 formulation Methods 0.000 title claims description 92
- 238000004851 dishwashing Methods 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title description 6
- 239000011521 glass Substances 0.000 claims description 46
- 229920002873 Polyethylenimine Polymers 0.000 claims description 37
- 229920000642 polymer Polymers 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 27
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 25
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 9
- PDIZYYQQWUOPPK-UHFFFAOYSA-N acetic acid;2-(methylamino)acetic acid Chemical compound CC(O)=O.CC(O)=O.CNCC(O)=O PDIZYYQQWUOPPK-UHFFFAOYSA-N 0.000 claims description 9
- 229910001385 heavy metal Inorganic materials 0.000 claims description 8
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 7
- 235000013922 glutamic acid Nutrition 0.000 claims description 7
- 239000004220 glutamic acid Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 235000021317 phosphate Nutrition 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229920000388 Polyphosphate Polymers 0.000 claims description 4
- 239000001205 polyphosphate Substances 0.000 claims description 4
- 235000011176 polyphosphates Nutrition 0.000 claims description 4
- 230000035622 drinking Effects 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 238000010411 cooking Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 5
- -1 alkali metal salts Chemical class 0.000 description 37
- 238000005260 corrosion Methods 0.000 description 25
- 230000007797 corrosion Effects 0.000 description 25
- 239000007844 bleaching agent Substances 0.000 description 23
- 229910052783 alkali metal Inorganic materials 0.000 description 19
- 239000002585 base Substances 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 15
- 238000004140 cleaning Methods 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 13
- 229920000962 poly(amidoamine) Polymers 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000011734 sodium 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
- 230000000007 visual effect Effects 0.000 description 8
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000002736 nonionic surfactant Substances 0.000 description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 7
- 239000001509 sodium citrate Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 239000003599 detergent Substances 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 102000004190 Enzymes Human genes 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229940088598 enzyme Drugs 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
- 239000011976 maleic acid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 4
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 235000019993 champagne Nutrition 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 229920005646 polycarboxylate Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 2
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 240000002234 Allium sativum Species 0.000 description 2
- 102000013142 Amylases Human genes 0.000 description 2
- 108010065511 Amylases Proteins 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
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- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
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- 229920002125 Sokalan® Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- GHDBLWVVUWTQCG-UHFFFAOYSA-N acetonitrile;n,n-dimethylmethanamine Chemical class CC#N.CN(C)C GHDBLWVVUWTQCG-UHFFFAOYSA-N 0.000 description 2
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
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- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
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- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 2
- 229940018557 citraconic acid Drugs 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
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- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
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- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
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- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
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- 239000003381 stabilizer Substances 0.000 description 2
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- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000001488 sodium phosphate Substances 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
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229950003937 tolonium Drugs 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
- C11D11/02—Preparation in the form of powder by spray drying
-
- 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
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3723—Polyamines or polyalkyleneimines
-
- 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
- C11D3/33—Amino carboxylic acids
-
- 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
- C11D3/37—Polymers
Definitions
- the present invention relates to a process for the preparation of formulations according to the invention and their use as or for the production of dishwashing agents, in particular dishwasher detergents for automatic dishwashing.
- Dishwashing detergents have many requirements to fulfill. So they have to clean the dishes thoroughly, they should have no harmful or potentially harmful substances in the wastewater, they should allow the draining and drying of the water from the dishes, and they should not cause problems when operating the dishwasher. Finally, they should not lead to aesthetically undesirable consequences on the good to be cleaned. Especially in this context is the glass corrosion.
- Glass corrosion is caused not only by mechanical effects, for example by rubbing glasses or mechanical contact of the glasses with parts of the dishwasher, but is mainly promoted by chemical influences.
- certain ions can be released from the glass by repeated mechanical cleaning, adversely altering the optical and thus the aesthetic properties.
- Glass corrosion has several effects. On the one hand, one can observe the formation of microscopically fine cracks, which are noticeable in the form of lines. On the other hand, one can often observe a general cloudiness, for example a roughening, which makes the glass in question look unaesthetic. Overall, such effects are also subdivided into iridescent discoloration, scoring and surface and annular opacities.
- WO 2006/108857 discloses alkoxylated polyethyleneimines as additives to detergents.
- Detergents containing zeolites or polyaminocarboxylates such as EDTA or triethylenediamine pentaacetate as complexing agents are disclosed by way of example.
- WO 01/96516 suggests formulations containing alkoxylated polyethylenimine for cleaning hard surfaces. For rinsing, purified water is used.
- WO 99/05248 discloses dishwashing compositions comprising polymers of amino group-containing vinyl polymers.
- Dishwashing agents which contain polyethyleneimine. Such dishwashing agents may contain phosphate or be phosphate-free. It is attributed to them a good inhibition of glass corrosion. Zinc and bismuth-containing dishwashing detergents are not recommended. The glass corrosion, in particular the line corrosion and the turbidity, but is not sufficiently delayed or prevented in many cases.
- formulations defined above were found, also called formulations according to the invention.
- Formulations of the invention are heavy metal-free. This is to be understood in the context of the present invention that formulations according to the invention are free of those heavy metal compounds which do not act as bleach catalysts, in particular of compounds of iron and bismuth. In the context of the present invention, "free from” is to be understood in connection with heavy metal compounds as meaning that the content of heavy metal compounds which do not act as bleach catalysts is in the range from 0 to 100 ppm, determined by the Leach method and based on the solids content.
- the formulation according to the invention has a heavy metal content below 0.05 ppm, based on the solids content of the relevant formulation.
- heavy metals are all metals having a specific density of at least 6 g / cm 3 .
- the heavy metals are precious metals and zinc, bismuth, iron, copper, lead, tin, nickel, cadmium and chromium.
- formulation of the invention contains no measurable levels of zinc and bismuth compounds, that is, for example, less than 1 ppm.
- inorganic cations such as ammonium, alkali or alkaline earth metal are suitable, preferably Mg 2+, Ca 2+, Na +, K +, or organic cations, preferably with one or more organic radicals, substituted ammonium, in particular triethanol ammonium, N, N-diethanolammonium, N-mono-C 1 -C 4 -alkyldiethanolammonium, for example N-methyldiethanolammonium or Nn-butyldiethanolammonium, and N, N-di-C 1 -C 4 -alkylethanolammonium.
- inorganic cations such as ammonium, alkali or alkaline earth metal are suitable, preferably Mg 2+, Ca 2+, Na +, K +, or organic cations, preferably with one or more organic radicals, substituted ammonium, in particular triethanol ammonium, N, N-diethanolammonium, N-mono-C 1 -C 4 -alkyl
- Very particularly preferred compounds (A) are the alkali metal salts, in particular the sodium salts of methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA).
- MGDA methylglycine diacetate
- IDS iminodisuccinic acid
- GLDA glutamic acid diacetate
- MGDA methylglycine diacetate
- IDS iminodisuccinic acid
- GLDA glutamic acid diacetate
- modified alkyleneimine polymers are also briefly referred to as modified polyalkyleneimine (B) in the context of the present invention.
- alkyleneimine polymers are to be understood as meaning those polymeric materials which are obtained by homo- or copolymerization of one or more cyclic imines, or by grafting a (co) polymer with at least one cyclic imine.
- examples are polyalkylenepolyamines and polyamidoamines grafted with ethyleneimine.
- polyalkylenepolyamines are preferably understood as meaning those polymers which contain at least six nitrogen atoms and at least five C 2 -C 10 -alkylene units, preferably C 2 -C 3 -alkylene units per molecule, for example pentaethylenehexamine, and in particular polyethyleneimines ,
- the degree of quaternization (alkylation) is preferably 1 to 25, more preferably up to 20 mol%, based on quaternizable (alkylatable) N atoms in alkyleneimine polymer.
- polyamidoamines grafted with ethyleneimine are suitable as alkyleneimine polymers.
- Suitable polyamidoamines are obtainable, for example, by reacting C 4 -C 10 -dicarboxylic acids with polyalkylenepolyamines, which preferably contain 3 to 10 basic nitrogen atoms in the molecule.
- suitable dicarboxylic acids are succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid or terephthalic acid. It is also possible to use mixtures of the abovementioned dicarboxylic acids, for example mixtures of adipic acid and glutaric acid or mixtures of maleic acid and adipic acid.
- Adipic acid is preferably used for the preparation of polyamidoamines.
- Suitable polyalkylenepolyamines which are condensed with the above-mentioned dicarboxylic acids are, for example, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine and bisaminopropylethylenediamine.
- the aforementioned polyalkylenepolyamines can also be used in the form of mixtures in the preparation of polyamidoamine.
- the preparation of polyamidoamine is preferably carried out in bulk, but may also be carried out in inert solvents, if appropriate.
- the condensation of dicarboxylic acid with polyalkylenepolyamine takes place at higher temperatures, for example in the range from 120 to 220.degree.
- the water formed during the reaction is distilled off from the reaction mixture.
- the condensation may optionally be carried out in the presence of lactones or lactams of carboxylic acids having 4 to 8 carbon atoms.
- lactones or lactams of carboxylic acids having 4 to 8 carbon atoms In general, from 0.8 to 1.4 mol of a polyalkylenepolyamine are used per mole of dicarboxylic acid.
- polyamidoamines have primary and secondary NH groups and are soluble in water.
- Ethyleneimine-grafted polyamidoamines can be prepared by allowing ethyleneimine to act on polyamidoamine described above in the presence of Bronsted acids or Lewis acids, for example sulfuric acid, phosphoric acid or boron trifluoride etherate.
- ethyleneimine is grafted onto the relevant polyamidoamine.
- per basic nitrogen atom in the polyamidoamine one can graft 1 to 10 ethyleneimine units, i. H. to 100 parts by weight of polyamidoamine is used about 10 to 500 parts by weight of ethyleneimine.
- Preferred alkyleneimine polymer is polyethyleneimine.
- polyethyleneimines are selected from highly branched polyethyleneimines.
- Highly branched polyethylenimines are characterized by their high degree of branching (DB).
- highly branched polyethyleneimines are polyethyleneimines having DB in the range from 0.1 to 0.95, preferably 0.25 to 0.90, more preferably in the range from 0.30 to 0.80 and very particularly preferably at least 0, 5th
- polyethylenimine is highly branched polyethyleneimines (homopolymers) having an average molecular weight M w in the range from 600 to 20,000 g / mol, preferably in the range from 800 to 15,000 g / mol.
- Alkyleneimine polymer is used in the context of the present invention in covalently modified form, specifically in the range from 2 to 80% by weight, preferably from 5 to 60% by weight, of alkylene oxide side chains, based on the total alkoxylated alkyleneimine Polymer (B).
- alkoxylation one can use epoxides, for example ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide or epichlorohydrin.
- Preferred alkoxylation reagents are ethylene oxide and propylene oxide and mixtures of ethylene oxide and propylene oxide.
- alkoxylated alkyleneimine polymer (B) alkoxylates in the range of 5 to 60 mole percent of the nitrogen atoms of the primary and secondary amino groups of the alkyleneimine polymer.
- modified polyalkyleneimine (B) is selected from polyethyleneimines reacted with ethylene oxide or propylene oxide.
- Modified polyalkyleneimine (B) can have as counter ions high molecular weight or low molecular weight anions, organic or preferably inorganic.
- High molecular weight anions in the context of the present invention have an average molecular weight of 200 g / mol or more, for example up to 2500 g / mol
- low molecular weight anions have a molecular weight of less than 200 g / mol, for example from 17 to 150 g / mol.
- Examples of low molecular weight organic counterions are acetate, propionate and benzoate.
- Examples of low molecular weight inorganic counterions are sulfate, chloride, bromide, hydroxide, carbonate, methanesulfonate and bicarbonate.
- modified polyalkyleneimine (B) has a cationic charge density of at least 5 meq / g to a maximum of 25 meq / g (milliequivalents / g), preferably to 22 meq / g, with an indication in g of modified polyalkyleneimine (B) without taking into account the counterions.
- the cationic charge density can be determined, for example, by titration, for example with polyvinyl sulfate solution.
- modified polyalkyleneimine (B) has a molecular weight distribution M w / M n in the range of 1.1 to 10, preferably 1.5 to 5.
- Contain formulations according to the invention total in the range of 1 to 50% by weight of aminocarboxylate (A), preferably 10 to 25% by weight, in total in the range of 0.001 to 5% by weight of modified polyalkyleneimine (B), preferably 0.02 to 0.5 wt .-%, in each case based on solids content of the relevant formulation.
- A aminocarboxylate
- B modified polyalkyleneimine
- formulation according to the invention contains compound (A) and modified polyalkyleneimine (B) in a weight ratio in the range from 1000 to 1 to 25 to 1.
- formulation according to the invention is free of phosphates and polyphosphates, wherein hydrogen phosphates are subsumed with, for example, free of trisodium phosphate, pentasodium tripolyphosphate and Hexasatriummetaphosphat.
- free from in connection with phosphates and polyphosphates in the context of the present invention should be understood to mean that the total content of phosphate and polyphosphate ranges from 10 ppm to 0.2% by weight, determined by gravimetry.
- formulations according to the invention contain no further components, which are advantageous, for example, for use in dishwashing and / or kitchen utensils, but can easily be formulated with further components and are therefore suitable as starting material.
- formulations according to the invention contain sodium citrate (C).
- sodium citrate includes the mono- and preferably the disodium salt with.
- Sodium citrate can be used as anhydrous salt or as a hydrate, for example as a dihydrate.
- Preferred bleaching agents (D) are selected from sodium perborate, anhydrous or for example as monohydrate or as tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as monohydrate, and sodium persulfate, where the term "persulfate” respectively the salt of peracid H 2 SO 5 and the peroxodisulfate includes.
- the alkali metal salts may each also be alkali metal hydrogencarbonate, alkali metal hydrogen perborate and alkali metal hydrogen persulphate. However, preference is given in each case to the dialkali metal salts.
- formulation according to the invention contains zero to 50% by weight of sodium citrate (C), preferably 1 to 30% by weight, more preferably at least 5% by weight of sodium citrate (C), determined as anhydrous sodium citrate, a total of zero to 15% by weight of bleaching agent (D), preferably at least 0.5% by weight of bleaching agent (D), selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate. in each case based on solids content of the relevant formulation.
- formulation according to the invention is solid at room temperature, for example a powder or a tablet.
- formulation of the invention is liquid at room temperature.
- the formulation according to the invention is a granulate, a liquid preparation or a gel.
- formulation according to the invention may comprise further ingredients (E), for example one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus-free builders, one or more cobuilders, one or more alkali carriers, one or more a plurality of bleaching agents, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers, one or more corrosion inhibitors, one or more builders, buffers, dyes, one or more perfumes, one or more organic solvents, one or more several tableting aids, one or more disintegrating agents, one or more thickeners, or one or more solubilizing agents.
- surfactants for example one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus-free builders, one or more cobuilders, one or more alkali carriers, one or more a plurality of bleaching agents, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers
- surfactants are, in particular, nonionic surfactants and mixtures of anionic or zwitterionic surfactants with nonionic surfactants.
- Preferred nonionic Surfactants are alkoxylated alcohols and alkoxylated fatty alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl glycosides and so-called amine oxides.
- Compounds of the general formula (I) may be block copolymers or random copolymers, preference being given to block copolymers.
- these may be block copolymers or random copolymers, preference being given to block copolymers.
- suitable nonionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide.
- suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters.
- amine oxides or alkyl glycosides are also suitable.
- anionic surfactants are C 8 -C 20 -alkyl sulfates, C 8 -C 20 -alkyl sulfonates and C 8 -C 20 -alkyl ether sulfates having one to six ethylene oxide units per molecule.
- formulation of the invention may contain in the range of from 3 to 20% by weight of surfactant.
- Formulations of the invention may contain one or more enzymes.
- enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.
- Formulations according to the invention may contain, for example, up to 5% by weight of enzyme, preferably from 0.1 to 3% by weight, in each case based on the total solids content of the formulation according to the invention.
- builders of polycarboxylates are selected, for example, alkali metal salts of (meth) acrylic acid homo- or (meth) acrylic acid copolymers.
- Suitable comonomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid.
- a suitable polymer is in particular polyacrylic acid, which preferably has an average molecular weight M w in the range from 2000 to 40,000 g / mol, preferably 2,000 to 10,000 g / mol, in particular 3,000 to 8,000 g / mol.
- copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid.
- copolymers of at least one monomer selected from the group consisting of monoethylenically unsaturated C 3 -C 10 -mono- or C 4 -C 10 -dicarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid with at least one hydrophilic or hydrophobically modified monomers are used as listed below.
- Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins having 10 or more carbon atoms or mixtures thereof, for example 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-hexadecene and 1-octadecene.
- Suitable hydrophilic monomers are monomers having sulfonate or phosphonate groups, as well as nonionic monomers having hydroxy function or alkylene oxide groups. Examples include: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, Ethoxypolypropylengly-kol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate.
- Polyalkylene glycols may contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units per molecule.
- Particularly preferred sulfonic acid-containing monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2 hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and salt
- Particularly preferred phosphonate group-containing monomers are the vinylphosphonic acid and its salts.
- amphoteric polymers can also be used as builders.
- Formulations according to the invention may contain, for example, in the range from 10 to 50% by weight, preferably up to 20% by weight, of builder.
- formulations according to the invention may contain one or more co-builders.
- co-builders are phosphonates, for example hydroxyalkane phosphonates and aminoalkane phosphonates.
- hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder.
- HEDP 1-hydroxyethane-1,1-diphosphonate
- Preferred aminoalkanephosphonates are ethylenediaminetetra-methylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral reacting sodium salts, e.g. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used.
- Formulations of the invention may contain one or more alkali carriers.
- Alkaline carriers for example, provide the pH of at least 9 when an alkaline pH is desired.
- Suitable examples are alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal hydroxides and alkali metal metasilicates.
- Preferred alkali metal is in each case potassium, particularly preferred is sodium.
- Formulations according to the invention may contain, in addition to bleaching agent (D), one or more chlorine-containing bleaching agents.
- Suitable chlorine-containing bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate.
- formulations according to the invention may contain in the range of from 3 to 10% by weight of chlorine-containing bleach.
- Formulations of the invention may contain one or more bleach catalysts.
- Bleach catalysts can be selected from bleach-enhancing transition metal salts or transition metal complexes such as manganese, iron, cobalt, ruthenium or molybdenum-salene complexes or carbonyl complexes. Also, manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and Cobalt, iron, copper and ruthenium amine complexes are useful as bleach catalysts.
- Formulations according to the invention may contain one or more bleach activators, for example N-methylmorpholinium acetonitrile salts ("MMA salts”), trimethylammonium acetonitrile salts, N-acylimides such as N-nonanoylsuccinimide, 1,5-diacetyl-2,2-dioxo-hexahydroxy 1,3,5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).
- MMA salts N-methylmorpholinium acetonitrile salts
- DADHT 1,5-diacetyl-2,2-dioxo-hexahydroxy 1,3,5-triazine
- nitrile quats trimethylammonium acetonitrile salts
- TAED tetraacetylethylenediamine
- TAED tetraacetylhexylenediamine
- Formulations of the invention may contain one or more corrosion inhibitors.
- corrosion inhibitors such compounds that inhibit the corrosion of metal.
- suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, furthermore phenol derivatives such as, for example, hydroquinone, catechol, hydroxyhydroquinone, gallic acid, phloroglucin or pyrogallol.
- formulations according to the invention contain a total of in the range of 0.1 to 1.5 wt .-% corrosion inhibitor.
- Formulations of the invention may contain one or more builders, for example, sodium sulfate.
- Formulations of the invention may contain one or more defoamers selected, for example, from silicone oils and paraffin oils.
- formulations according to the invention contain in total in the range from 0.05 to 0.5% by weight defoamer.
- Formulations according to the invention may contain phosphonic acid or one or more phosphonic acid derivatives, for example hydroxyethane-1,1-diphosphonic acid.
- Another object of the present invention is the use of formulations according to the invention for the automatic cleaning of dishes and kitchen utensils.
- kitchen utensils in the context of the present invention, for example, pots, pans, casseroles to call, and metal objects such as, for example, skimmers, roasters and garlic presses.
- a surface of glass is to be understood as meaning that the object in question has at least one piece of glass which comes into contact with the ambient air and can be contaminated when the object is used.
- the objects in question may be those which are essentially glassware such as drinking glasses or glass bowls. But it can also be, for example, cover that have individual components of a different material, such as pot lid with edging and metal handle.
- Glass surface may be decorated, for example colored or printed, or not decorated.
- glass includes any glass, for example lead glass and in particular soda lime glass, crystal glass and borosilicate glasses.
- Machine cleaning is preferably dishwashing with a dishwasher (English: “automatic dishwashing”).
- At least one formulation according to the invention for automated cleaning of drinking glasses, glass vases and glass jars is used for cooking.
- water having a hardness in the range from 1 to 30 ° dH, preferably from 2 to 25 ° dH, is used for cleaning, German hardness being taken to mean in particular the calcium hardness.
- rinsing water with a hardness in the range of 1 to 30 ° dH preferably 2 to 25 ° dH can be used.
- machine-cleaning formulations according to the invention are used, even with repeated mechanical cleaning of objects which have at least one surface made of glass, there is very little tendency for glass corrosion, even if objects comprising at least one surface made of glass are used have, along with heavily soiled cutlery or dishes cleans. In addition, it is much less harmful to use the formulation of the present invention to clean glass together with metal objects, such as pots, pans or garlic presses.
- formulations according to the invention have a very good bleaching action when used for rinsing dishes and kitchen utensils and glass surfaces.
- Compound (A), modified polyalkyleneimine (B) and bleaching agent (D) are defined above.
- one or more surfactants for formulation according to the invention, for example with one or more surfactants, one or more enzymes, one or more builders, one or more builders a plurality of co-builders, in particular phosphorus-free builders, one or more alkali carriers, one or more bleaches, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers, one or more corrosion inhibitors, one or more builders Buffer or dye.
- one or more surfactants for
- the water is completely or partially removed, for example, to a residual moisture in the range from 0.1 to 10% by weight of the formulation according to the invention by evaporation, in particular by spray drying, spray granulation or compaction ,
- the water is removed, in whole or in part, at a pressure in the range of 0.3 to 2 bar.
- the water is removed, in whole or in part, at temperatures in the range of 60 to 220 ° C.
- the cleaning formulations according to the invention can be provided in liquid or solid form, single- or multiphase, as tablets or in the form of other dosage units, packaged or unpackaged.
- the water content of liquid formulations can vary from 35 to 90% water.
- the invention is illustrated by working examples.
- Base mixtures were prepared from the starting materials according to Table 1. The starting materials were mixed dry.
- Table 1 Basic mixtures for experiments with formulations according to the invention and comparative formulations Base 1
- Base 2 Base 3 protease 2.5 2.5 2.5 amylase 1 1 1 nC 18 H 37 (OCH 2 CH 2 ) 9 OH 5 5
- 10 10
- Sodium percarbonate (D.1) 10.5 10.5 10.5 TAED 4 4 4 Na 2 Si 2 O 5 2 2 2 Na 2 CO 3 19.5 19.5 19.5 Sodium citrate dihydrate 5 22.5 30 All information in g.
- Dishwasher Miele G 1222 SCL Program: 65 ° C (with pre-rinse) ware: 3 champagne glasses “GILDE”, 3 shot glasses, "INTERMEZZO"
- the glasses were placed in the upper dish rack of the dishwasher.
- the dishwashing agent used was in each case 25 g of formulation according to the invention or 25 g of comparison formulation according to Table 3, where Table 3 shows the active components (A.1), base mixture, silicate (C.1 or C.2) and compound (D) or ( E) and (B) of inventive formulation individually specified.
- Rinsing was carried out at a rinse temperature of 55 ° C.
- the water hardness was in each case in the range of zero to 2 ° dH.
- the evaluation was carried out gravimetrically and visually after 100 rinsing cycles.
- the weight of the glasses was determined before the beginning of the first rinse cycle and after drying after the last rinse cycle.
- the weight loss is the difference between the two values.
- the specimens were rinsed in a domestic dishwasher (Bosch SGS5602) with 1 g of surfactant (nC 18 H 37 (OCH 2 CH 2 ) 10 OH) and 20 g of citric acid to remove any impurities.
- the test pieces were dried, their weight determined and fixed on the grid floor insert.
- the dry specimens were weighed. This was followed by the visual assessment of the test specimens. The surface of the test specimens was evaluated for line corrosion (glass scoring) and haze corrosion (areal haze).
- Interim scores (e.g., L3-4) were also allowed on the match.
- formulations according to the invention were also always superior to the corresponding comparative formulations in terms of the inhibition of glass corrosion.
Description
Die vorliegende Erfindung betrifft Formulierungen, enthaltend
- (A) insgesamt im Bereich von 1 bis 50 Gew.-% mindestens eines Aminocarboxylats, gewählt aus Methylglycindiacetat (MGDA), Iminodibernsteinsäure (IDS) und Glutaminsäurediacetat (GLDA) sowie deren Salzen, und
- (B) insgesamt im Bereich von 0,001 bis 2 Gew.-% mindestens eines alkoxylierten Alkylenimin-Polymers mit einem mittleren Molekulargewicht Mw im Bereich von 800 bis 25.000 g/mol, das eine positive Ladungsdichte von mindestens 5 meq/g aufweist und das im Bereich von 2 bis maximal 80 Gew.-% Alkylenoxid-Seitenketten aufweist, bezogen auf gesamtes alkoxyliertes Alkylenimin-Polymer,
- (A) in the range of from 1 to 50% by weight of at least one aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and their salts, and
- (B) generally in the range of 0.001 to 2 wt .-% of at least one alkoxylated alkyleneimine polymer having an average molecular weight M w in the range of 800 to 25,000 g / mol having a positive charge density of at least 5 meq / g and in Having from 2 to at most 80% by weight of alkylene oxide side chains, based on the total alkoxylated alkyleneimine polymer,
Weiterhin betrifft die vorliegende Erfindung ein Verfahren zur Herstellung von erfindungsgemäßen Formulierungen und ihre Verwendung als oder zur Herstellung von Geschirrspülmitteln, insbesondere von Geschirrspülmitteln für das maschinelle Geschirrspülen.Furthermore, the present invention relates to a process for the preparation of formulations according to the invention and their use as or for the production of dishwashing agents, in particular dishwasher detergents for automatic dishwashing.
Geschirrspülmittel haben vielerlei Anforderungen zu erfüllen. So haben sie das Geschirr gründlich zu reinigen, sie sollen im Abwasser keine schädlichen oder potenziell schädlichen Substanzen aufweisen, sie sollen das Ablaufen und Trocknen des Wassers vom Geschirr gestatten, und sie sollen beim Betrieb der Spülmaschine nicht zu Problemen führen. Schließlich sollen sie nicht zu ästhetisch unerwünschten Folgen am zu reinigenden Gut führen. Besonders ist in diesem Zusammenhang die Glaskorrosion zu nennen.Dishwashing detergents have many requirements to fulfill. So they have to clean the dishes thoroughly, they should have no harmful or potentially harmful substances in the wastewater, they should allow the draining and drying of the water from the dishes, and they should not cause problems when operating the dishwasher. Finally, they should not lead to aesthetically undesirable consequences on the good to be cleaned. Especially in this context is the glass corrosion.
Glaskorrosion kommt nicht nur durch mechanische Effekte zustande, beispielsweise durch Aneinanderreiben von Gläsern oder mechanischen Kontakt der Gläser mit Teilen der Spülmaschine, sondern wird hauptsächlich durch chemische Einflüsse gefördert. Beispielsweise können bestimmte Ionen durch wiederholtes maschinelles Reinigen aus dem Glas gelöst werden, was die optischen und somit die ästhetischen Eigenschaften nachteilig verändert.Glass corrosion is caused not only by mechanical effects, for example by rubbing glasses or mechanical contact of the glasses with parts of the dishwasher, but is mainly promoted by chemical influences. For example, certain ions can be released from the glass by repeated mechanical cleaning, adversely altering the optical and thus the aesthetic properties.
Bei der Glaskorrosion beobachtet man mehrere Effekte. Zum einen kann man die Bildung von mikroskopisch feinen Rissen beobachten, die sich in Form von Linien bemerkbar machen. Zum anderen kann man in vielen Fällen eine generelle Eintrübung beobachten, beispielsweise eine Aufrauhung, die das betreffende Glas unästhetisch aussehen lassen. Derartige Effekte werden insgesamt auch unterteilt in irisierende Verfärbung, Riefenbildung sowie flächen- und ringförmige Trübungen.Glass corrosion has several effects. On the one hand, one can observe the formation of microscopically fine cracks, which are noticeable in the form of lines. On the other hand, one can often observe a general cloudiness, for example a roughening, which makes the glass in question look unaesthetic. Overall, such effects are also subdivided into iridescent discoloration, scoring and surface and annular opacities.
Aus
Es bestand also die Aufgabe, Formulierungen bereit zu stellen, die als oder zur Herstellung von Geschirrspülmitteln geeignet sind und die die aus dem Stand der Technik bekannten Nachteile vermeiden und die Glaskorrosion inhibieren oder zumindest besonders gut verringern. Es bestand weiterhin die Aufgabe, ein Verfahren zur Herstellung von Formulierungen bereit zu stellen, die als oder zur Herstellung von Geschirrspülmitteln geeignet sind und die die aus dem Stand der Technik bekannten Nachteile vermeiden. Es bestand weiterhin die Aufgabe, Verwendungen von Formulierungen bereit zu stellen.It was therefore the object to provide formulations which are suitable as or for the production of dishwashing agents and which avoid the disadvantages known from the prior art and inhibit glass corrosion or at least reduce it particularly well. A further object was to provide a process for the preparation of formulations which are suitable as or for the production of dishwasher detergents and which avoid the disadvantages known from the prior art. It was also the task to provide uses of formulations.
Dementsprechend wurden die eingangs definierten Formulierungen gefunden, kurz auch erfindungsgemäße Formulierungen genannt.Accordingly, the formulations defined above were found, also called formulations according to the invention.
Erfindungsgemäße Formulierungen sind Schwermetall-frei. Darunter soll im Rahmen der vorliegenden zu verstehen sei, dass erfindungsgemäße Formulierungen frei sind von solchen Schwermetallverbindungen, die nicht als Bleichkatalysatoren wirken, insbesondere von Verbindungen des Eisens und des Wismut. Unter "frei von" soll im Zusammenhang mit Schwermetallverbindungen im Rahmen der vorliegenden Erfindung verstanden werden, dass der Gehalt an Schwermetallverbindungen, die nicht als Bleichkatalysatoren wirken, in Summe im Bereich von 0 bis 100 ppm liegt, bestimmt nach der Leach-Methode und bezogen auf den Feststoffgehalt. Vorzugsweise weist erfindungsgemäße Formulierung einen Schwermetallgehalt unter 0,05 ppm auf, bezogen auf den Feststoffgehalt der betreffenden Formulierung.Formulations of the invention are heavy metal-free. This is to be understood in the context of the present invention that formulations according to the invention are free of those heavy metal compounds which do not act as bleach catalysts, in particular of compounds of iron and bismuth. In the context of the present invention, "free from" is to be understood in connection with heavy metal compounds as meaning that the content of heavy metal compounds which do not act as bleach catalysts is in the range from 0 to 100 ppm, determined by the Leach method and based on the solids content. Preferably, the formulation according to the invention has a heavy metal content below 0.05 ppm, based on the solids content of the relevant formulation.
Als "Schwermetalle" gelten im Rahmen der vorliegenden Erfindung alle Metalle mit einer spezifischen Dichte von mindestens 6 g/cm3. Insbesondere gelten als Schwermetalle Edelmetalle sowie Zink, Wismut, Eisen, Kupfer, Blei, Zinn, Nickel, Cadmium und Chrom.In the context of the present invention, "heavy metals" are all metals having a specific density of at least 6 g / cm 3 . In particular, the heavy metals are precious metals and zinc, bismuth, iron, copper, lead, tin, nickel, cadmium and chromium.
Vorzugsweise enthält erfindungsgemäße Formulierung keine messbaren Anteile an Zink- und Wismutverbindungen, also beispielsweise weniger als 1 ppm.Preferably, formulation of the invention contains no measurable levels of zinc and bismuth compounds, that is, for example, less than 1 ppm.
Erfindungsgemäße Formulierungen enthalten
- (A) insgesamt im Bereich von 1 bis 50 Gew.-% mindestens eines Aminocarboxylats, gewählt aus Methylglycindiacetat (MGDA), Iminodibernsteinsäure (IDS) und Glutaminsäurediacetat (GLDA) sowie deren Salzen, im Rahmen der vorliegenden Erfindung kurz auch Aminocarboxylat (A) oder auch Verbindung (A) genannt, sowie vorzugsweise deren Salzen.
- (A) in the range of from 1 to 50% by weight of at least one aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and their salts, in the context of the present invention also briefly aminocarboxylate (A) or compound (A) mentioned, and preferably their salts.
Bevorzugt wählt man Verbindung (A) als freie Säure, besonders bevorzugt in partiell oder vollständig neutralisierter Form, also als Salz. Als Gegenionen kommen beispielsweise anorganische Kationen, beispielsweise Ammonium, Alkali oder Erdalkali in Frage, bevorzugt Mg2+, Ca2+, Na+, K+, oder organische Kationen, bevorzugt mit einem oder mehreren organischen Resten substituiertes Ammonium, insbesondere Triethanolammonium, N,N-Diethanolammonium, N-Mono-C1-C4-alkyldiethanolammonium, beispielsweise N-Methyl-diethanolammonium oder N-n-Butyldiethanolammonium, und N,N-Di-C1-C4-alkylethanolammonium.Preference is given to choosing compound (A) as the free acid, particularly preferably in partially or completely neutralized form, ie as salt. As counterions, for example inorganic cations, such as ammonium, alkali or alkaline earth metal are suitable, preferably Mg 2+, Ca 2+, Na +, K +, or organic cations, preferably with one or more organic radicals, substituted ammonium, in particular triethanol ammonium, N, N-diethanolammonium, N-mono-C 1 -C 4 -alkyldiethanolammonium, for example N-methyldiethanolammonium or Nn-butyldiethanolammonium, and N, N-di-C 1 -C 4 -alkylethanolammonium.
Ganz besonders bevorzugte Verbindungen (A) sind die Alkalimetallsalze, insbesondere die Natriumsalze von Methylglycindiacetat (MGDA), Iminodibernsteinsäure (IDS) und Glutaminsäurediacetat (GLDA).Very particularly preferred compounds (A) are the alkali metal salts, in particular the sodium salts of methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA).
Ganz besonders bevorzugt ist Methylglycindiacetat (MGDA), Iminodibernsteinsäure (IDS) bzw. Glutaminsäurediacetat (GLDA) vollständig neutralisiert.Very particular preference is given to fully neutralizing methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) or glutamic acid diacetate (GLDA).
Erfindungsgemäße Formulierungen enthalten weiterhin
- (B) insgesamt im Bereich von 0,001 bis 2 Gew.-% mindestens eines alkoxylierten Alkylenimin-Polymers mit einem mittleren Molekulargewicht Mw im Bereich von 800 bis 25.000 g/mol, das eine positive Ladungsdichte von mindestens 5 meq/g aufweist und das im Bereich von 2 bis maximal 80 Gew.-%, bevorzugt 5 bis 60 Gew.-% Alkylenoxid-Seitenketten aufweist, bezogen auf gesamtes alkoxyliertes Alkylenimin-Polymer.
- (B) generally in the range of 0.001 to 2 wt .-% of at least one alkoxylated alkyleneimine polymer having an average molecular weight M w in the range of 800 to 25,000 g / mol having a positive charge density of at least 5 meq / g and in Range of 2 to at most 80 wt .-%, preferably 5 to 60 wt .-% alkylene oxide side chains, based on the total alkoxylated alkyleneimine polymer.
Derartige modifizierte Alkylenimin-Polymere werden im Rahmen der vorliegenden Erfindung kurz auch modifiziertes Polyalkylenimin (B) genannt.Such modified alkyleneimine polymers are also briefly referred to as modified polyalkyleneimine (B) in the context of the present invention.
Unter Alkylenimin-Polymeren sind im Rahmen der vorliegenden Erfindung solche polymere Materialien zu verstehen, die durch Homo- oder Copolymerisation von einem bzw. mehreren cyclischen Iminen erhalten werden, oder durch Pfropfung eines (Co)polymers mit mindestens einem cyclischen Imin. Beispiele sind Polyalkylenpolyamine und mit Ethylenimin gepfropften Polyamidoamine.In the context of the present invention, alkyleneimine polymers are to be understood as meaning those polymeric materials which are obtained by homo- or copolymerization of one or more cyclic imines, or by grafting a (co) polymer with at least one cyclic imine. Examples are polyalkylenepolyamines and polyamidoamines grafted with ethyleneimine.
Unter Polyalkylenpolyaminen sollen im Rahmen der vorliegenden Erfindung vorzugsweise solche Polymere verstanden werden, die mindestens sechs Stickstoffatome und mindestens fünf C2-C10-Alkyleneinheiten, bevorzugt C2-C3-Alkylen-einheiten pro Molekül enthalten, zum Beispiel Pentaethylenhexamin, und insbesondere Polyethylenimine.For the purposes of the present invention, polyalkylenepolyamines are preferably understood as meaning those polymers which contain at least six nitrogen atoms and at least five C 2 -C 10 -alkylene units, preferably C 2 -C 3 -alkylene units per molecule, for example pentaethylenehexamine, and in particular polyethyleneimines ,
Alkylenimin-Polymer und insbesondere Polyethylenimin kann beispielsweise ein mittleres Molekulargewicht (Mw) von mindestens 300 g/mol haben, bevorzugt liegt das mittlere Molekulargewicht von Polyethylenimin im Bereich von 800 bis 20.000 g/mol, ermittelt durch Lichtstreuung.Alkyleneimine polymer and especially polyethyleneimine may have, for example, an average molecular weight (M w ) of at least 300 g / mol, preferably the average molecular weight of polyethylenimine is in the range from 800 to 20,000 g / mol, determined by light scattering.
Polyalkylenpolyamine können in teilweise quaternierter (alkylierter) Form als Alkylenimin-Polymer kovalent modifiziert werden. Geeignete Quaternierungsmittel (Alkylierungsmittel) sind zum Beispiel Alkylhalogenide, insbesondere C1-C10-Alkylchlorid wie Methylchlorid, Methylbromid, Methyliodid, Ethylchlorid, Ethylbromid, n-Butylchlorid, tert.-Butylchlorid, n-Hexylchlorid, weiterhin Epichlorhydrin, Dimethylsulfat, Diethylsulfat und Benzylchlorid. Falls quaternierte (alkylierte) Polyalkylenpolyamine als Alkylenimin-Polymer kovalent modifiziert werden, beträgt der Grad der Quaternierung (Alkylierung) bevorzugt 1 bis 25, besonders bevorzugt bis zu 20 mol-%, bezogen auf quaternierbare (alkylierbare) N-Atome in Alkylenimin-Polymer.Polyalkylenepolyamines can be covalently modified in partially quaternized (alkylated) form as the alkyleneimine polymer. Suitable quaternizing agents (alkylating agents) are, for example, alkyl halides, in particular C 1 -C 10 -alkyl chloride, such as methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, n-butyl chloride, tert-butyl chloride, n-hexyl chloride, furthermore epichlorohydrin, dimethyl sulfate, diethyl sulfate and benzyl chloride. If quaternized (alkylated) polyalkylenepolyamines are covalently modified as alkyleneimine polymer, the degree of quaternization (alkylation) is preferably 1 to 25, more preferably up to 20 mol%, based on quaternizable (alkylatable) N atoms in alkyleneimine polymer.
Weiterhin sind mit Ethylenimin gepfropften Polyamidoamine als Alkylenimin-Polymere geeignet. Geeignete Polyamidoamine sind zum Beispiel durch Umsetzung von C4-C10-Dicarbonsäuren mit Polyalkylenpolyaminen erhältlich, die vorzugsweise 3 bis 10 basische Stickstoffatome im Molekül enthalten. Geeignete Dicarbonsäuren sind beispielsweise Bernsteinsäure, Maleinsäure, Adipinsäure, Glutarsäure, Korksäure, Sebacinsäure oder Terephthalsäure. Man kann auch Mischungen von vorstehend genannten Dicarbonsäuren einsetzen, zum Beispiel Mischungen von Adipinsäure und Glutarsäure oder Mischungen von Maleinsäure und Adipinsäure. Bevorzugt setzt man Adipinsäure zur Herstellung von Polyamidoaminen ein. Geeignete Polyalkylenpolyamine, die mit vorstehend genannten Dicarbonsäuren kondensiert werden, sind zum Beispiel Diethylentriamin, Triethylentetramin, Dipropylentriamin, Tripropylentetramin, Dihexamethylentriamin, Aminopropylethylendiamin und bis-Aminopropyl-ethylen-diamin. Vorstehend genannte Polyalkylenpolyamine können auch in Form von Mischungen bei der Herstellung von Polyamidoamin eingesetzt werden. Die Herstellung von Polyamidoamin erfolgt vorzugsweise in Substanz, kann jedoch auch gegebenenfalls in inerten Lösungsmitteln vorgenommen werden. Die Kondensation von Dicarbonsäure mit Polyalkylenpolyamin erfolgt bei höheren Temperaturen, zum Beispiel im Bereich von 120 bis 220°C. Das während der Reaktion gebildete Wasser wird aus dem Reaktionsgemisch abdestilliert. Die Kondensation kann gegebenenfalls in Gegenwart von Lactonen oder Lactamen von Carbonsäuren mit 4 bis 8 Kohlenstoffatomen vorgenommen werden. Pro mol Dicarbonsäure verwendet man im Allgemeinen 0,8 bis 1,4 mol eines Polyalkylenpolyamins. So erhältliche Polyamidoamine weisen primäre und sekundäre NH-Gruppen auf und sind in Wasser löslich.Furthermore, polyamidoamines grafted with ethyleneimine are suitable as alkyleneimine polymers. Suitable polyamidoamines are obtainable, for example, by reacting C 4 -C 10 -dicarboxylic acids with polyalkylenepolyamines, which preferably contain 3 to 10 basic nitrogen atoms in the molecule. Examples of suitable dicarboxylic acids are succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid or terephthalic acid. It is also possible to use mixtures of the abovementioned dicarboxylic acids, for example mixtures of adipic acid and glutaric acid or mixtures of maleic acid and adipic acid. Adipic acid is preferably used for the preparation of polyamidoamines. Suitable polyalkylenepolyamines which are condensed with the above-mentioned dicarboxylic acids are, for example, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine and bisaminopropylethylenediamine. The aforementioned polyalkylenepolyamines can also be used in the form of mixtures in the preparation of polyamidoamine. The preparation of polyamidoamine is preferably carried out in bulk, but may also be carried out in inert solvents, if appropriate. The condensation of dicarboxylic acid with polyalkylenepolyamine takes place at higher temperatures, for example in the range from 120 to 220.degree. The water formed during the reaction is distilled off from the reaction mixture. The condensation may optionally be carried out in the presence of lactones or lactams of carboxylic acids having 4 to 8 carbon atoms. In general, from 0.8 to 1.4 mol of a polyalkylenepolyamine are used per mole of dicarboxylic acid. Thus obtainable polyamidoamines have primary and secondary NH groups and are soluble in water.
Mit Ethylenimin gepfropfte Polyamidoamine sind dadurch herstellbar, dass man Ethylenimin in Gegenwart von Brönstedt-Säuren oder Lewis-Säuren, zum Beispiel Schwefelsäure, Phosphorsäure oder Bortrifluoridetherat, auf oben beschriebenes Polyamidoamin einwirken lässt. Dadurch wird Ethylenimin auf das betreffende Polyamidoamin aufgepfropft. Zum Beispiel kann man pro basischem Stickstoffatom im Polyamidoamin 1 bis 10 Ethylenimineinheiten aufpfropfen, d. h. auf 100 Gewichtsteile Polyamidoamin setzt man etwa 10 bis 500 Gewichtsteile Ethylenimin ein.Ethyleneimine-grafted polyamidoamines can be prepared by allowing ethyleneimine to act on polyamidoamine described above in the presence of Bronsted acids or Lewis acids, for example sulfuric acid, phosphoric acid or boron trifluoride etherate. As a result, ethyleneimine is grafted onto the relevant polyamidoamine. For example, per basic nitrogen atom in the polyamidoamine, one can graft 1 to 10 ethyleneimine units, i. H. to 100 parts by weight of polyamidoamine is used about 10 to 500 parts by weight of ethyleneimine.
Bevorzugte Alkylenimin-Polymer ist Polyethylenimin.Preferred alkyleneimine polymer is polyethyleneimine.
In einer Ausführungsform der vorliegenden Erfindung wählt man Polyethylenimine aus hochverzweigten Polyethyleniminen. Hochverzweigte Polyethylenimine werden durch ihren hohen Verzweigungsgrad (Degree of Branching, DB) charakterisiert. Der Verzweigungsgrad lässt sich beispielsweise durch 13C-NMR-Spektroskopie, vorzugsweise in D2O, bestimmen und ist wie folgt definiert:
Als hochverzweigte Polyethylenimine gelten im Rahmen der vorliegen Erfindung Polyethylenimine mit DB im Bereich von 0,1 bis 0,95, bevorzugt 0,25 bis 0,90 besonders bevorzugt im Bereich von 0,30 bis 0,80 und ganz besonders bevorzugt mindestens 0,5.In the context of the present invention, highly branched polyethyleneimines are polyethyleneimines having DB in the range from 0.1 to 0.95, preferably 0.25 to 0.90, more preferably in the range from 0.30 to 0.80 and very particularly preferably at least 0, 5th
In einer Ausführungsform der vorliegenden Erfindung handelt es sich bei Polyethylenimin um hochverzweigte Polyethylenimine (Homopolymere) mit einem mittleren Molekulargewicht Mw im Bereich von 600 bis 20.000 g/mol, bevorzugt im Bereich von 800 bis 15.000 g/mol.In one embodiment of the present invention, polyethylenimine is highly branched polyethyleneimines (homopolymers) having an average molecular weight M w in the range from 600 to 20,000 g / mol, preferably in the range from 800 to 15,000 g / mol.
Alkylenimin-Polymer wird im Rahmen der vorliegenden Erfindung in kovalent modifizierter Form eingesetzt, und zwar so, dass es im Bereich von 2 bis 80 Gew.-%, bevorzugt 5 bis 60 Gew.-% Alkylenoxid-Seitenketten aufweist, bezogen auf gesamtes alkoxyliertes Alkylenimin-Polymer (B). Zum Alkoxylieren kann man Epoxide verwenden, beispielsweise Ethylenoxid, Propylenoxid, 1,2-Butylenoxid, 2,3-Butylenoxid, Styroloxid oder Epichlorhydrin. Bevorzugte Alkoxylierungsreagenzien sind Ethylenoxid und Propylenoxid sowie Mischungen von Ethylenoxid und Propylenoxid.Alkyleneimine polymer is used in the context of the present invention in covalently modified form, specifically in the range from 2 to 80% by weight, preferably from 5 to 60% by weight, of alkylene oxide side chains, based on the total alkoxylated alkyleneimine Polymer (B). For the alkoxylation one can use epoxides, for example ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide or epichlorohydrin. Preferred alkoxylation reagents are ethylene oxide and propylene oxide and mixtures of ethylene oxide and propylene oxide.
In einer Ausführungsform sind in alkoxyliertem Alkylenimin-Polymer (B) im Bereich von 5 bis 60 mol-% der Stickstoff-Atome der primären und sekundären Aminogruppen des Alkylenimin-Polymers alkoxyliert.In one embodiment, alkoxylated alkyleneimine polymer (B) alkoxylates in the range of 5 to 60 mole percent of the nitrogen atoms of the primary and secondary amino groups of the alkyleneimine polymer.
In einer Ausführungsform der vorliegenden Erfindung wählt man modifiziertes Polyalkylenimin (B) aus Polyethyleniminen, die umgesetzt sind mit Ethylenoxid oder Propylenoxid.In one embodiment of the present invention, modified polyalkyleneimine (B) is selected from polyethyleneimines reacted with ethylene oxide or propylene oxide.
Modifiziertes Polyalkylenimin (B) kann als Gegenionen hochmolekulare oder niedermolekulare Anionen aufweisen, organisch oder bevorzugt anorganisch. Hochmolekulare Anionen im Rahmen der vorliegenden Erfindung haben ein mittleres Molekulargewicht von 200 g/mol oder mehr, beispielsweise bis zu 2500 g/mol, niedermolekulare Anionen haben ein Molekulargewicht von weniger als 200 g/mol, beispielsweise von 17 bis 150 g/mol. Beispiele für niedermolekulare organische Gegenionen sind Acetat, Propionat und Benzoat. Beispiele für niedermolekulare anorganische Gegenionen sind Sulfat, Chlorid, Bromid, Hydroxid, Carbonat, Methansulfonat und Hydrogencarbonat.Modified polyalkyleneimine (B) can have as counter ions high molecular weight or low molecular weight anions, organic or preferably inorganic. High molecular weight anions in the context of the present invention have an average molecular weight of 200 g / mol or more, for example up to 2500 g / mol, low molecular weight anions have a molecular weight of less than 200 g / mol, for example from 17 to 150 g / mol. Examples of low molecular weight organic counterions are acetate, propionate and benzoate. Examples of low molecular weight inorganic counterions are sulfate, chloride, bromide, hydroxide, carbonate, methanesulfonate and bicarbonate.
In einer Ausführungsform der vorliegenden Erfindung weist modifiziertes Polyalkylenimin (B) eine kationische Ladungsdichte von mindestens 5 meq/g bis maximal 25 meq/g (Milliäquivalente/g) auf, bevorzugt bis 22 meq/g, wobei sich die Angabe in g auf modifiziertes Polyalkylenimin (B) ohne Berücksichtigung der Gegenionen bezieht. Die kationische Ladungsdichte kann man beispielsweise durch Titration ermitteln, beispielsweise mit Polyvinylsulfatlösung.In one embodiment of the present invention, modified polyalkyleneimine (B) has a cationic charge density of at least 5 meq / g to a maximum of 25 meq / g (milliequivalents / g), preferably to 22 meq / g, with an indication in g of modified polyalkyleneimine (B) without taking into account the counterions. The cationic charge density can be determined, for example, by titration, for example with polyvinyl sulfate solution.
In einer Ausführungsform der vorliegenden Erfindung weist modifiziertes Polyalkylenimin (B) eine Molekulargewichtsverteilung Mw/Mn im Bereich von 1,1 bis 10 auf, bevorzugt 1,5 bis 5.In one embodiment of the present invention, modified polyalkyleneimine (B) has a molecular weight distribution M w / M n in the range of 1.1 to 10, preferably 1.5 to 5.
Erfindungsgemäße Formulierungen enthalten
insgesamt im Bereich von 1 bis 50 Gew.-% Aminocarboxylat (A), bevorzugt 10 bis 25 Gew.-%, insgesamt im Bereich von 0,001 bis 5 Gew.-% modifiziertes Polyalkylenimin (B), bevorzugt 0,02 bis 0,5 Gew.-%,
bezogen jeweils auf Feststoffgehalt der betreffenden Formulierung.Contain formulations according to the invention
total in the range of 1 to 50% by weight of aminocarboxylate (A), preferably 10 to 25% by weight, in total in the range of 0.001 to 5% by weight of modified polyalkyleneimine (B), preferably 0.02 to 0.5 wt .-%,
in each case based on solids content of the relevant formulation.
In einer Variante der vorliegenden Erfindung enthält erfindungsgemäße Formulierung Verbindung (A) und modifiziertes Polyalkylenimin (B) in einem Gewichtsverhältnis im Bereich von 1000 zu 1 bis 25 zu 1.In a variant of the present invention, formulation according to the invention contains compound (A) and modified polyalkyleneimine (B) in a weight ratio in the range from 1000 to 1 to 25 to 1.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung ist erfindungsgemäße Formulierung frei von Phosphaten und Polyphosphaten, wobei Hydrogenphosphate mit subsumiert sind, beispielsweise frei von Trinatriumphosphat, Pentanatriumtripolyphosphat und Hexanatriummetaphosphat. Unter "frei von" soll im Zusammenhang mit Phosphaten und Polyphosphaten im Rahmen der vorliegenden Erfindung verstanden werden, dass der Gehalt an Phosphat und Polyphosphat in Summe im Bereich von 10 ppm bis 0,2 Gew.-% liegt, bestimmt durch Gravimetrie.In a preferred embodiment of the present invention formulation according to the invention is free of phosphates and polyphosphates, wherein hydrogen phosphates are subsumed with, for example, free of trisodium phosphate, pentasodium tripolyphosphate and Hexasatriummetaphosphat. The term "free from" in connection with phosphates and polyphosphates in the context of the present invention should be understood to mean that the total content of phosphate and polyphosphate ranges from 10 ppm to 0.2% by weight, determined by gravimetry.
Erfindungsgemäße Formulierungen können weitere Komponenten enthalten, die beispielsweise für die Verwendung beim Spülen von Geschirr und/oder Küchenutensilien vorteilhaft sind.Formulations of the invention may contain other components which are advantageous, for example, for use in washing dishes and / or kitchen utensils.
In einer anderen Ausführungsform der vorliegenden Erfindung enthalten erfindungsgemäße Formulierungen keine weiteren Komponenten, die beispielsweise für die Verwendung beim Spülen von Geschirr und/oder Küchenutensilien vorteilhaft sind, können aber leicht mit weiteren Komponenten formuliert werden und eignen sich daher als Ausgangsmaterial.In another embodiment of the present invention formulations according to the invention contain no further components, which are advantageous, for example, for use in dishwashing and / or kitchen utensils, but can easily be formulated with further components and are therefore suitable as starting material.
In einer Ausführungsform der vorliegenden Erfindung enthalten erfindungsgemäße Formulierungen Natriumcitrat (C). Dabei umfasst der Begriff Natriumcitrat das Mono- und bevorzugt das Dinatriumsalz mit. Natriumcitrat kann als wasserfreies Salz oder als Hydrat, beispielsweise als Dihydrat eingesetzt werden.In one embodiment of the present invention formulations according to the invention contain sodium citrate (C). The term sodium citrate includes the mono- and preferably the disodium salt with. Sodium citrate can be used as anhydrous salt or as a hydrate, for example as a dihydrate.
In einer Ausführungsform der vorliegenden Erfindung enthalten erfindungsgemäße Formulierungen
- (D) mindestens eine Verbindung, gewählt aus Alkalimetallpercarbonat, Alkalimetallperborat und Alkalimetallpersulfat, im Rahmen der vorliegenden Erfindung auch "Bleichmittel (D)" genannt.
- (D) at least one compound selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate, in the context of the present invention also called "bleaching agent (D)".
Bevorzugte Bleichmittel (D) sind gewählt aus Natriumperborat, wasserfrei oder beispielsweise als Monohydrat oder als Tetrahydrat oder so genanntes Dihydrat, Natriumpercarbonat, wasserfrei oder beispielsweise als Monohydrat, und Natriumpersulfat, wobei der Begriff "Persulfat" jeweils das Salz der Persäure H2SO5 sowie das Peroxodisulfat mit umfasst.Preferred bleaching agents (D) are selected from sodium perborate, anhydrous or for example as monohydrate or as tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as monohydrate, and sodium persulfate, where the term "persulfate" respectively the salt of peracid H 2 SO 5 and the peroxodisulfate includes.
Dabei kann es sich bei den Alkalimetallsalzen jeweils auch um Alkalimetallhydrogencarbonat, Alkalimetallhydrogenperborat und Alkalimetallhydrogenpersulfat handeln. Bevorzugt sind jedoch jeweils die Dialkalimetallsalze.The alkali metal salts may each also be alkali metal hydrogencarbonate, alkali metal hydrogen perborate and alkali metal hydrogen persulphate. However, preference is given in each case to the dialkali metal salts.
In einer Ausführungsform der vorliegenden Erfindung enthält erfindungsgemäße Formulierung null bis 50 Gew.-% Natriumcitrat (C), bevorzugt 1 bis 30 Gew.-%, besonders bevorzugt mindestens 5 Gew.-% Natriumcitrat (C), bestimmt als wasserfreies Natriumcitrat,
insgesamt null bis 15 Gew.-% Bleichmittel (D), bevorzugt mindestens 0,5 Gew.-% Bleichmittel (D), gewählt aus Alkalimetallpercarbonat, Alkalimetallperborat und Alkalimetallpersulfat. bezogen jeweils auf Feststoffgehalt der betreffenden Formulierung.In one embodiment of the present invention formulation according to the invention contains zero to 50% by weight of sodium citrate (C), preferably 1 to 30% by weight, more preferably at least 5% by weight of sodium citrate (C), determined as anhydrous sodium citrate,
a total of zero to 15% by weight of bleaching agent (D), preferably at least 0.5% by weight of bleaching agent (D), selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate. in each case based on solids content of the relevant formulation.
In einer Ausführungsform der vorliegenden Erfindung ist erfindungsgemäße Formulierung bei Zimmertemperatur fest, beispielsweise ein Pulver oder eine Tablette. In einer anderen Ausführungsform der vorliegenden Erfindung ist erfindungsgemäße Formulierung bei Zimmertemperatur flüssig. In einer Ausführungsform der vorliegenden Erfindung ist erfindungsgemäße Formulierung ein Granulat, eine Flüssigzubereitung oder ein Gel.In one embodiment of the present invention, formulation according to the invention is solid at room temperature, for example a powder or a tablet. In another embodiment of the present invention, formulation of the invention is liquid at room temperature. In one embodiment of the present invention, the formulation according to the invention is a granulate, a liquid preparation or a gel.
In einer Ausführungsform der vorliegenden Erfindung enthält erfindungsgemäße Formulierung 0,1 bis 10 Gew.-% Wasser, bezogen auf die Summe aller Feststoffe der betreffenden Formulierung.In one embodiment of the present invention, the formulation according to the invention contains from 0.1 to 10% by weight of water, based on the sum of all solids of the relevant formulation.
In einer Ausführungsform der vorliegenden Erfindung kann erfindungsgemäße Formulierung weitere Inhaltsstoffe (E) aufweisen, beispielsweise ein oder mehrere Tenside, ein oder mehrere Enzyme, einen oder mehrere Builder, insbesondere Phosphor-freie Builder, einen oder mehrere Cobuilder, einen oder mehrere Alkaliträger, ein oder mehrere Bleichmittel, einen oder mehrere Bleichkatalysatoren, einen oder mehrere Bleichaktivatoren, einen oder mehrere Bleichmittelstabilisatoren, einen oder mehrere Entschäumer, einen oder mehrere Korrosionsinhibitoren, einen oder mehrere Gerüststoffe, Puffer, Farbstoffe, einen oder mehrere Duftstoffe, ein oder mehrere organische Lösungsmittel, ein oder mehrere Tablettierhilfsmittel, ein oder mehrere Disintegrationsmittel, einen oder mehrere Verdicker, oder einen oder mehrere Löslichkeitsvermittler.In one embodiment of the present invention, formulation according to the invention may comprise further ingredients (E), for example one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus-free builders, one or more cobuilders, one or more alkali carriers, one or more a plurality of bleaching agents, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers, one or more corrosion inhibitors, one or more builders, buffers, dyes, one or more perfumes, one or more organic solvents, one or more several tableting aids, one or more disintegrating agents, one or more thickeners, or one or more solubilizing agents.
Beispiele für Tenside sind insbesondere nicht-ionische Tenside sowie Mischungen von anionischen oder zwitterionischen Tensiden mit nicht-ionischen Tensiden. Bevorzugte nicht-ionische Tenside sind alkoxylierte Alkohole und alkoxylierte Fettalkohole, Di- und Multiblockcopolymerisate von Ethylenoxid und Propylenoxid und Umsetzungsprodukte von Sorbitan mit Ethylenoxid oder Propylenoxid, Alkylglycoside und sogenannte Aminoxide.Examples of surfactants are, in particular, nonionic surfactants and mixtures of anionic or zwitterionic surfactants with nonionic surfactants. Preferred nonionic Surfactants are alkoxylated alcohols and alkoxylated fatty alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl glycosides and so-called amine oxides.
Bevorzugte Beispiele für alkoxylierte Alkohole und alkoxylierte Fettalkohole sind beispielsweise Verbindungen der allgemeinen Formel (I)
- R1
- gleich oder verschieden und gewählt aus linearem C1-C10-Alkyl, bevorzugt jeweils gleich und Ethyl und besonders bevorzugt Methyl,
- R2
- gewählt aus C8-C22-Alkyl, beispielsweise n-C8H17, n-C10H21, n-C12H25, n-C14H29, n-C16H33 oder n-C18H37,
- R3
- gewählt aus C1-C10-Alkyl, Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl oder iso-Decyl,
- R 1
- identical or different and selected from linear C 1 -C 10 -alkyl, preferably in each case the same and ethyl and particularly preferably methyl,
- R 2
- selected from C 8 -C 22 -alkyl, for example nC 8 H 17 , nC 10 H 21 , nC 12 H 25 , nC 14 H 29 , nC 16 H 33 or nC 18 H 37 ,
- R 3
- selected from C 1 -C 10 -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or isodecyl,
Dabei kann es sich bei Verbindungen der allgemeinen Formel (I) um Blockcopolymere oder statistische Copolymere handeln, bevorzugt sind Blockcopolymere.Compounds of the general formula (I) may be block copolymers or random copolymers, preference being given to block copolymers.
Andere bevorzugte Beispiele für alkoxylierte Alkohole und alkoxylierte Fettalkohole sind beispielsweise Verbindungen der allgemeinen Formel (II)
- R1
- gleich oder verschieden und gewählt aus linearem C1-C10-Alkyl, bevorzugt jeweils gleich und Ethyl und besonders bevorzugt Methyl,
- R4
- gewählt aus C6-C20-Alkyl, insbesondere n-C8H17, n-C10H21, n-C12H25, n-C14H29, n-C16H33, n-C18H37.
- a
- eine Zahl im Bereich von 1 bis 6,
- b
- ist eine Zahl im Bereich von 4 bis 20,
- d
- ist eine Zahl im Bereich von 4 bis 25.
- R 1
- identical or different and selected from linear C 1 -C 10 -alkyl, preferably in each case the same and ethyl and particularly preferably methyl,
- R 4
- selected from C 6 -C 20 -alkyl, in particular nC 8 H 17 , nC 10 H 21 , nC 12 H 25 , nC 14 H 29 , nC 16 H 33 , nC 18 H 37 .
- a
- a number in the range of 1 to 6,
- b
- is a number in the range of 4 to 20,
- d
- is a number in the range of 4 to 25.
Dabei kann es sich bei Verbindungen der allgemeinen Formel (II) um Blockcopolymere oder statistische Copolymere handeln, bevorzugt sind Blockcopolymere.In the case of compounds of the general formula (II), these may be block copolymers or random copolymers, preference being given to block copolymers.
Weitere geeignete nicht-ionische Tenside sind gewählt aus Di- und Multiblockcopolymeren, aufgebaut aus Ethylenoxid und Propylenoxid. Weitere geeignete nicht-ionische Tenside sind gewählt aus ethoxylierten oder propoxylierten Sorbitanestern. Ebenfalls eignen sich Aminoxide oder Alkylglycoside. Eine Übersicht geeigneter weiterer nichtionischer Tenside findet man in
Es können auch Gemische mehrerer verschiedener nicht-ionischer Tenside enthalten sein.It may also contain mixtures of several different nonionic surfactants.
Beispiele für anionische Tenside sind C8-C20-Alkylsulfate, C8-C20-Alkylsulfonate und C8-C20-Alkylethersulfate mit einer bis 6 Ethylenoxideinheiten pro Molekül.Examples of anionic surfactants are C 8 -C 20 -alkyl sulfates, C 8 -C 20 -alkyl sulfonates and C 8 -C 20 -alkyl ether sulfates having one to six ethylene oxide units per molecule.
In einer Ausführungsform der vorliegenden Erfindung kann erfindungsgemäße Formulierung im Bereich von 3 bis 20 Gew.-% Tensid enthalten.In one embodiment of the present invention, formulation of the invention may contain in the range of from 3 to 20% by weight of surfactant.
Erfindungsgemäße Formulierungen können ein oder mehrere Enzyme enthalten. Beispiele für Enzyme sind Lipasen, Hydrolasen, Amylasen, Proteasen, Cellulasen, Esterasen, Pectinasen, Lactasen und Peroxidasen.Formulations of the invention may contain one or more enzymes. Examples of enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.
Erfindungsgemäße Formulierungen können beispielsweise bis 5 Gew.-% Enzym enthalten, bevorzugt sind 0,1 bis 3 Gew.-%, jeweils bezogen auf gesamten Feststoffgehalt der erfindungsgemäßen Formulierung.Formulations according to the invention may contain, for example, up to 5% by weight of enzyme, preferably from 0.1 to 3% by weight, in each case based on the total solids content of the formulation according to the invention.
Erfindungsgemäße Formulierungen können über Natriumcitrat (C) hinaus einen oder mehrere Builder, insbesondere Phosphat-freie Builder, enthalten. Beispiele für geeignete Builder sind Silikate, insbesondere Natriumdisilikat und Natriummetasilikat, Zeolithe, Schichtsilikate, insbesondere solche der Formel α-Na2Si2O5, β-Na2Si2O5 und δ-Na2Si2O5, weiterhin Fettsäuresulfonate, α-Hydroxypropionsäure, Alkalimalonate, Fettsäuresulfonate, Alkyl- und Alkenyldisuccinate, Weinsäurediacetat, Weinsäuremonoacetat, oxidierte Stärke, und polymere Builder, beispielsweise Polycarboxylate und Polyasparaginsäure.Formulations according to the invention may comprise, in addition to sodium citrate (C), one or more builders, in particular phosphate-free builders. Examples of suitable builders are silicates, in particular sodium disilicate and sodium metasilicate, zeolites, phyllosilicates, especially those of the formula α-Na 2 Si 2 O 5 , β-Na 2 Si 2 O 5 and δ-Na 2 Si 2 O 5 , furthermore fatty acid sulfonates, α-hydroxypropionic acid, alkali metal malates, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartaric acid diacetate, tartaric acid monoacetate, oxidized starch, and polymeric builders, for example, polycarboxylates and polyaspartic acid.
In einer Ausführungsform der vorliegenden Erfindung wählt man Builder aus Polycarboxylaten, beispielsweise Alkalimetallsalze von (Meth)acrylsäurehomo- oder (Meth)acrylsäurecopolymeren.In one embodiment of the present invention, builders of polycarboxylates are selected, for example, alkali metal salts of (meth) acrylic acid homo- or (meth) acrylic acid copolymers.
Als Comonomere eignen sich monoethylenisch ungesättigte Dicarbonsäuren wie Maleinsäure, Fumarsäure, Maleinsäureanhydrid, Itaconsäure und Citraconsäure. Ein geeignetes Polymer ist insbesondere Polyacrylsäure, die bevorzugt ein mittleres Molekulargewicht Mw im Bereich von 2000 bis 40.000 g/mol aufweist, bevorzugt 2.000 bis 10.000 g/mol, insbesondere 3.000 bis 8.000 g/mol. Geeignet sind weiterhin copolymere Polycarboxylate, insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure und/oder Fumarsäure.Suitable comonomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid. A suitable polymer is in particular polyacrylic acid, which preferably has an average molecular weight M w in the range from 2000 to 40,000 g / mol, preferably 2,000 to 10,000 g / mol, in particular 3,000 to 8,000 g / mol. Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid.
Es können auch Copolymere aus mindestens einem Monomeren aus der Gruppe bestehend aus monoethylenisch ungesättigten C3-C10-Mono- bzw. C4-C10-Dicarbonsäuren oder deren Anhydriden, wie Maleinsäure, Maleinsäureanhydrid, Acrylsäure, Methacrylsäure, Fumarsäure, Itaconsäure und Citraconsäure mit mindestens einem hydrophil oder hydrophob modifizierten Monomeren wie nachfolgend aufgezählt eingesetzt werden.It is also possible to use copolymers of at least one monomer selected from the group consisting of monoethylenically unsaturated C 3 -C 10 -mono- or C 4 -C 10 -dicarboxylic acids or their anhydrides, such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid with at least one hydrophilic or hydrophobically modified monomers are used as listed below.
Geeignete hydrophobe Monomere sind beispielsweise Isobuten, Diisobuten, Buten, Penten, Hexen und Styrol, Olefine mit 10 oder mehr Kohlenstoffatomen oder deren Gemischen wie beispielsweise 1-Decen, 1-Dodecen, 1-Tetradecen, 1-Hexadecen, 1-Octadecen, 1-Eicosen, 1-Docosen, 1-Tetracosen und 1-Hexacosen, C22-α-Olefin, ein Gemisch aus C20-C24-α-Olefinen und Polyisobuten mit im Mittel 12 bis 100 C-Atomen pro Molekül.Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins having 10 or more carbon atoms or mixtures thereof, for example 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-hexadecene and 1-octadecene. Eicosene, 1-docoses, 1-tetracoses and 1-hexacoses, C 22 -α-olefin, a mixture of C 20 -C 24 -α-olefins and polyisobutene having an average of 12 to 100 carbon atoms per molecule.
Geeignete hydrophile Monomere sind Monomere mit Sulfonat- oder Phosphonatgruppen, sowie nichtionische Monomere mit Hydroxyfunktion oder Alkylenoxidguppen. Beispielsweise seien genannt: Allylalkohol, Isoprenol, Methoxypolyethylenglykol(meth)acrylat, Methoxypolypropy-lenglykol(meth)acrylat, Methoxypolybutylenglykol(meth)acrylat, Methoxypoly(propylenoxid-co-ethylenoxid)(meth)acrylat, Ethoxypolyethylenglykol(meth)acrylat, Ethoxypolypropylengly-kol(meth)acrylat, Ethoxypolybutylenglykol(meth)acrylat und Ethoxypoly(propylenoxid-co-ethylenoxid)(meth)acrylat. Polyalkylenglykole können dabei 3 bis 50, insbesondere 5 bis 40 und vor allem 10 bis 30 Alkylenoxideinheiten pro Molekül enthalten.Suitable hydrophilic monomers are monomers having sulfonate or phosphonate groups, as well as nonionic monomers having hydroxy function or alkylene oxide groups. Examples include: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, Ethoxypolypropylengly-kol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate. Polyalkylene glycols may contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units per molecule.
Besonders bevorzugte Sulfonsäuregruppen-haltige Monomere sind dabei 1-Acryl-amido-1-propansulfonsäure, 2-Acrylamido-2-propansulfonsäure, 2-Acrylamido-2-methylpropansulfonsäure, 2-Methacrylamido-2-methylpropansulfonsäure, 3-Meth-acrylamido-2-hydroxypropansulfonsäure, Allylsulfonsäure, Methallylsulfonsäure, Allyloxybenzolsulfonsäure, Methallyloxybenzolsulfonsäure, 2-Hydroxy-3-(2-propenyloxy)propansulfonsäure, 2-Methyl-2-propen-1-sulfonsäure, Styrolsulfonsäure, Vinylsulfonsäure, 3-Sulfopropylacrylat, 2-Sulfoethylmethacrylat, 3-Sulfopropylmethacrylat, Sulfomethacrylamid, Sulfomethylmethacrylamid sowie Salze der genannten Säuren, wie deren Natrium-, Kalium oder Ammoniumsalze.Particularly preferred sulfonic acid-containing monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2 hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and salts of said acids, such as their sodium, potassium or ammonium salts.
Besonders bevorzugte Phosphonatgruppen-haltige Monomere sind die Vinylphosphonsäure und ihre Salze.Particularly preferred phosphonate group-containing monomers are the vinylphosphonic acid and its salts.
Darüber hinaus können auch amphotere Polymere als Builder eingesetzt werden. Erfindungsgemäße Formulierungen können beispielsweise im Bereich von insgesamt 10 bis 50 Gew.-%, bevorzugt bis 20 Gew.-% Builder enthalten.In addition, amphoteric polymers can also be used as builders. Formulations according to the invention may contain, for example, in the range from 10 to 50% by weight, preferably up to 20% by weight, of builder.
In einer Ausführungsform der vorliegenden Erfindung können erfindungsgemäße Formulierungen einen oder mehrere Cobuilder enthalten.In one embodiment of the present invention, formulations according to the invention may contain one or more co-builders.
Beispiele für Cobuilder sind Phosphonate, beispielsweise Hydroxyalkanphosphonate und 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-Wert 9) reagiert. Als Aminoalkanphosphonate kommen vorzugsweise Ethylendiamintetra-methylenphosphonat (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 des DTPMP, eingesetzt.Examples of co-builders are phosphonates, for example hydroxyalkane phosphonates and aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediaminetetra-methylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral reacting sodium salts, e.g. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used.
Erfindungsgemäße Formulierungen können einen oder mehrere Alkaliträger enthalten. Alkaliträger sorgen beispielsweise für den pH-Wert von mindestens 9, wenn ein alkalischer pH-Wert gewünscht wird. Geeignet sind beispielsweise Alkalimetallcarbonate, Alkalimetallhydrogencarbonate, Alkalimetallhydroxide und Alkalimetallmetasilikate. Bevorzugtes Alkalimetall ist jeweils Kalium, besonders bevorzugt ist Natrium.Formulations of the invention may contain one or more alkali carriers. Alkaline carriers, for example, provide the pH of at least 9 when an alkaline pH is desired. Suitable examples are alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal hydroxides and alkali metal metasilicates. Preferred alkali metal is in each case potassium, particularly preferred is sodium.
Erfindungsgemäße Formulierungen können neben Bleichmittel (D) ein oder mehrere Chlor-haltige Bleichmittel enthalten.Formulations according to the invention may contain, in addition to bleaching agent (D), one or more chlorine-containing bleaching agents.
Geeignete Chlor-haltige Bleichmittel sind beispielsweise 1,3-Dichloro-5,5-dimethylhydantoin, N-Chlorsulfamid, Chloramin T, Chloramin B, Natriumhypochlorit, Calciumhypochlorit, Magnesiumhypochlorit, Kaliumhypochlorit, Kaliumdichloroisocyanurat und Natriumdichloroisocyanurat.Suitable chlorine-containing bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate.
Erfindungsgemäße Formulierungen können beispielsweise im Bereich von 3 bis 10 Gew.-% Chlor-haltiges Bleichmittel enthalten.For example, formulations according to the invention may contain in the range of from 3 to 10% by weight of chlorine-containing bleach.
Erfindungsgemäße Formulierungen können einen oder mehrere Bleichkatalysatoren enthalten. Bleichkatalysatoren kann man wählen aus bleichverstärkenden Übergangsmetallsalzen bzw. Übergangsmetallkomplexen wie beispielsweise Mangan-, Eisen-, Cobalt-, Ruthenium- oder Molybdän-Salenkomplexe oder carbonylkomplexe. Auch Mangan-, Eisen-, Kobalt-, Ruthenium-, Molybdän-, Titan-, Vanadium- und Kupfer-Komplexe mit stickstoffhaltigen Tripod-Liganden sowie Kobalt-, Eisen-, Kupfer- und Ruthenium-Aminkomplexe sind als Bleichkatalysatoren verwendbar.Formulations of the invention may contain one or more bleach catalysts. Bleach catalysts can be selected from bleach-enhancing transition metal salts or transition metal complexes such as manganese, iron, cobalt, ruthenium or molybdenum-salene complexes or carbonyl complexes. Also, manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and Cobalt, iron, copper and ruthenium amine complexes are useful as bleach catalysts.
Erfindungsgemäße Formulierungen können einen oder mehrere Bleichaktivatoren, beispielsweise N-Methylmorpholinium-Acetonitril-Salze ("MMA-Salze"), TrimethylammoniumacetonitrilSalze, N-Acylimide wie beispielsweise N-Nonanoylsuccinimid,, 1,5-Diacetyl-2,2-dioxo-hexahydro-1,3,5-triazin ("DADHT") oder Nitrilquats (Trimethylammoniumacetonitrilsalze) enthalten.Formulations according to the invention may contain one or more bleach activators, for example N-methylmorpholinium acetonitrile salts ("MMA salts"), trimethylammonium acetonitrile salts, N-acylimides such as N-nonanoylsuccinimide, 1,5-diacetyl-2,2-dioxo-hexahydroxy 1,3,5-triazine ("DADHT") or nitrile quats (trimethylammonium acetonitrile salts).
Weitere Beispiele für geeignete Bleichaktivatoren sind Tetraacetylethylendiamin (TAED) und Tetraacetylhexylendiamin.Further examples of suitable bleach activators are tetraacetylethylenediamine (TAED) and tetraacetylhexylenediamine.
Erfindungsgemäße Formulierungen können einen oder mehrere Korrosionsinhibitoren enthalten. Darunter sind im vorliegenden Fall solche Verbindungen zu verstehen, die die Korrosion von Metall inhibieren. Beispiele für geeignete Korrosionsinhibitoren sind Triazole, insbesondere Benzotriazole, Bisbenzotriazole, Aminotriazole, Alkylaminotriazole, weiterhin Phenolderivate wie beispielsweise Hydrochinon, Brenzcatechin, Hydroxyhydrochinon, Gallussäure, Phloroglucin oder Pyrogallol.Formulations of the invention may contain one or more corrosion inhibitors. This is to be understood in the present case, such compounds that inhibit the corrosion of metal. Examples of suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, furthermore phenol derivatives such as, for example, hydroquinone, catechol, hydroxyhydroquinone, gallic acid, phloroglucin or pyrogallol.
In einer Ausführungsform der vorliegenden Erfindung enthalten erfindungsgemäße Formulierungen insgesamt im Bereich von 0,1 bis 1,5 Gew.-% Korrosionsinhibitor.In one embodiment of the present invention, formulations according to the invention contain a total of in the range of 0.1 to 1.5 wt .-% corrosion inhibitor.
Erfindungsgemäße Formulierungen können einen oder mehrere Gerüststoffe enthalten, beispielsweise Natriumsulfat.Formulations of the invention may contain one or more builders, for example, sodium sulfate.
Erfindungsgemäße Formulierungen können einen oder mehrere Entschäumer enthalten, gewählt beispielsweise aus Silikonölen und Paraffinölen.Formulations of the invention may contain one or more defoamers selected, for example, from silicone oils and paraffin oils.
In einer Ausführungsform der vorliegenden Erfindung enthalten erfindungsgemäße Formulierungen insgesamt im Bereich von 0,05 bis 0,5 Gew.-% Entschäumer.In one embodiment of the present invention, formulations according to the invention contain in total in the range from 0.05 to 0.5% by weight defoamer.
Erfindungsgemäße Formulierungen können Phosphonsäure oder ein oder mehrere Phosphonsäurederivate enthalten, beispielsweise Hydroxyethan-1,1-diphosphonsäure.Formulations according to the invention may contain phosphonic acid or one or more phosphonic acid derivatives, for example hydroxyethane-1,1-diphosphonic acid.
Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung von erfindungsgemäßen Formulierungen zur maschinellen Reinigung von Geschirr und Küchenutensilien. Als Küchenutensilien sind im Rahmen der vorliegenden Erfindung beispielsweise Töpfe, Pfannen, Kasserollen zu nennen, weiterhin metallene Gegenstände wie beispielsweise Schaumlöffel, Bratenwender und Knoblauchpressen.Another object of the present invention is the use of formulations according to the invention for the automatic cleaning of dishes and kitchen utensils. As kitchen utensils in the context of the present invention, for example, pots, pans, casseroles to call, and metal objects such as, for example, skimmers, roasters and garlic presses.
Bevorzugt ist die Verwendung von erfindungsgemäßen Formulierungen zur maschinellen Reinigung von Gegenständen, die mindestens eine Oberfläche aus Glas aufweisen, welches dekoriert oder nicht dekoriert sein kann. Dabei ist unter einer Oberfläche aus Glas im Rahmen der vorliegenden Erfindung zu verstehen, dass betreffender Gegenstand mindestens ein Stück aus Glas aufweist, das mit der Umgebungsluft in Berührung kommt und bei Gebrauch des Gegenstands verschmutzt werden kann. So kann es sich bei den betreffenden Gegenständen um solche handeln, die wie Trinkgläser oder Glasschüsseln im Wesentlichen gläsern sind. Es kann sich aber auch beispielsweise um Deckel handeln, die einzelne Komponenten aus einem anderen Material aufweisen, beispielsweise Topfdeckel mit Einfassung und Griff aus Metall.Preference is given to the use of formulations according to the invention for machine cleaning of articles which have at least one surface of glass which is decorated or can not be decorated. In the context of the present invention, a surface of glass is to be understood as meaning that the object in question has at least one piece of glass which comes into contact with the ambient air and can be contaminated when the object is used. Thus, the objects in question may be those which are essentially glassware such as drinking glasses or glass bowls. But it can also be, for example, cover that have individual components of a different material, such as pot lid with edging and metal handle.
Oberfläche aus Glas kann dekoriert, beispielsweise gefärbt oder bedruckt, oder nicht dekoriert sein.Glass surface may be decorated, for example colored or printed, or not decorated.
Unter dem Begriff "Glas" werden beliebige Gläser subsumiert, beispielsweise Bleiglas und insbesondere Kalknatronglas, Kristallglas und Borosilikatgläser.The term "glass" includes any glass, for example lead glass and in particular soda lime glass, crystal glass and borosilicate glasses.
Vorzugsweise handelt es sich bei maschineller Reinigung um ein Spülen mit einer Spülmaschine (englisch: "automatic dishwashing").Machine cleaning is preferably dishwashing with a dishwasher (English: "automatic dishwashing").
In einer Ausführungsform der vorliegenden Erfindung setzt man mindestens eine erfindungsgemäße Formulierung zur maschinellen Reinigung von Trinkgläsern, gläsernen Vasen und Glasgefäßen zum Kochen ein.In one embodiment of the present invention, at least one formulation according to the invention for automated cleaning of drinking glasses, glass vases and glass jars is used for cooking.
In einer Ausführungsform der vorliegenden Erfindung setzt man zum Reinigen Wasser mit einer Härte im Bereich von 1 bis 30 °dH, bevorzugt 2 bis 25 °dH ein, wobei unter deutscher Härte insbesondere die Calcium-Härte zu verstehen ist.In one embodiment of the present invention, water having a hardness in the range from 1 to 30 ° dH, preferably from 2 to 25 ° dH, is used for cleaning, German hardness being taken to mean in particular the calcium hardness.
Auch zum Nachspülen kann man Wasser mit einer Härte im Bereich von 1 bis 30 °dH, bevorzugt 2 bis 25 °dH einsetzen.Also for rinsing water with a hardness in the range of 1 to 30 ° dH, preferably 2 to 25 ° dH can be used.
Setzt man erfindungsgemäße Formulierungen zur maschinellen Reinigung ein, so beobachtet man auch bei wiederholter maschineller Reinigung von Gegenständen, die mindestens eine Oberfläche aus Glas aufweisen, nur sehr geringe Neigung zur Glaskorrosion, und zwar selbst dann, wenn man Gegenstände, die mindestens eine Oberfläche aus Glas aufweisen, zusammen mit stark verschmutztem Besteck oder Geschirr reinigt. Außerdem ist es deutlich weniger schädlich, erfindungsgemäße Formulierung einzusetzen, um Glas zusammen mit Gegenständen aus Metall zu reinigen, beispielsweise zusammen mit Töpfen, Pfannen oder Knoblauchpressen.If machine-cleaning formulations according to the invention are used, even with repeated mechanical cleaning of objects which have at least one surface made of glass, there is very little tendency for glass corrosion, even if objects comprising at least one surface made of glass are used have, along with heavily soiled cutlery or dishes cleans. In addition, it is much less harmful to use the formulation of the present invention to clean glass together with metal objects, such as pots, pans or garlic presses.
Weiterhin kann man beobachten, dass erfindungsgemäße Formulierungen bei der Verwendung zum Spülen von Geschirr und Küchenutensilien und Glasoberflächen eine sehr gute Bleichwirkung aufweisen.Furthermore, it can be observed that formulations according to the invention have a very good bleaching action when used for rinsing dishes and kitchen utensils and glass surfaces.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von erfindungsgemäßen Formulierungen, kurz auch erfindungsgemäßes Herstellungsverfahren genannt. Zur Durchführung des erfindungsgemäßen Herstellungsverfahrens kann man beispielsweise so vorgehen, dass man
- (A) insgesamt im Bereich von 1 bis 50 Gew.-% Aminocarboxylat, gewählt aus Methylglycindiacetat (MGDA), Iminodibernsteinsäure (IDS) und Glutaminsäurediacetat (GLDA) sowie deren Salzen, und
- (B) insgesamt im Bereich von 0,001 bis 2 Gew.-% mindestens eines alkoxylierten Alkylenimin-Polymers mit einem mittleren Molekulargewicht Mw im Bereich von 800 bis 25.000 g/mol, das eine positive Ladungsdichte von mindestens 5 meq/g aufweist und in dem im Bereich von 2 bis maximal 80 Gew.-% Alkylenoxid-Seitenketten aufweist, bezogen auf gesamtes alkoxyliertes Alkylenimin-Polymer,
und gegebenenfalls - (C) Natriumcitrat oder
- (D) mindestens eine Verbindung, gewählt aus Alkalimetallpercarbonat, Alkalimetallperborat und Alkalimetallpersulfat,
- (A) generally in the range of from 1 to 50% by weight of aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and their salts, and
- (B) generally in the range of 0.001 to 2 wt .-% of at least one alkoxylated alkyleneimine polymer having an average molecular weight M w in the range of 800 to 25,000 g / mol, which has a positive charge density of at least 5 meq / g and in the in the range from 2 to a maximum of 80% by weight of alkylene oxide side chains, based on the total alkoxylated alkyleneimine polymer,
and optionally - (C) sodium citrate or
- (D) at least one compound selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate,
Verbindung (A), modifiziertes Polyalkylenimin (B) und Bleichmittel (D) sind vorstehend definiert.Compound (A), modified polyalkyleneimine (B) and bleaching agent (D) are defined above.
In einer Ausführungsform der vorliegenden Erfindung kann man, bevor man das Wasser zumindest teilweise entfernt, mit einem oder mehreren weiteren Inhaltsstoffen (E) für erfindungsgemäße Formulierung vermischen, beispielsweise mit einem oder mehreren Tenside, einem oder mehreren Enzymen, einem oder mehreren Buildern, einem oder mehrere Cobuildern, insbesondere Phosphor-freiem Builder, einem oder mehreren Alkaliträgern, einem oder mehreren Bleichmitteln, einem oder mehreren Bleichkatalysatoren, einem oder mehreren Bleichaktivatoren, einem oder mehreren Bleichmittelstabilisatoren, einem oder mehreren Entschäumern, einem oder mehreren Korrosionsinhibitoren, einem oder mehreren Gerüststoffen, mit Puffer oder Farbstoff.In one embodiment of the present invention, before at least partially removing the water, one may mix with one or more other ingredients (E) for formulation according to the invention, for example with one or more surfactants, one or more enzymes, one or more builders, one or more builders a plurality of co-builders, in particular phosphorus-free builders, one or more alkali carriers, one or more bleaches, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers, one or more corrosion inhibitors, one or more builders Buffer or dye.
In einer Ausführungsform geht man so vor, dass man das Wasser ganz oder teilweise, beispielsweise bis zu einer Restfeuchte im Bereich von 0,1 bis 10 Gew.-% aus erfindungsgemäßer Formulierung entfernt, indem man es verdampft, insbesondere durch Sprühtrocknung, Sprühgranulierung oder Kompaktierung.In one embodiment, the water is completely or partially removed, for example, to a residual moisture in the range from 0.1 to 10% by weight of the formulation according to the invention by evaporation, in particular by spray drying, spray granulation or compaction ,
In einer Ausführungsform der vorliegenden Erfindung entfernt man das Wasser, ganz oder teilweise, bei einem Druck im Bereich von 0,3 bis 2 bar.In one embodiment of the present invention, the water is removed, in whole or in part, at a pressure in the range of 0.3 to 2 bar.
In einer Ausführungsform der vorliegenden Erfindung entfernt man das Wasser, ganz oder teilweise, bei Temperaturen im Bereich von 60 bis 220°C.In one embodiment of the present invention, the water is removed, in whole or in part, at temperatures in the range of 60 to 220 ° C.
Durch das erfindungsgemäße Herstellungsverfahren kann man erfindungsgemäße Formulierungen leicht erhalten.By means of the preparation process according to the invention, it is easy to obtain formulations according to the invention.
Die erfindungsgemäßen Reinigungsformulierungen können in flüssiger oder fester Form, ein- oder mehrphasig, als Tabletten oder in Form anderer Dosiereinheiten, verpackt oder unverpackt bereitgestellt werden. Der Wassergehalt von flüssigen Formulierungen kann variieren von 35 bis 90% Wasser.
Die Erfindung wird durch Arbeitsbeispiele verdeutlicht.The cleaning formulations according to the invention can be provided in liquid or solid form, single- or multiphase, as tablets or in the form of other dosage units, packaged or unpackaged. The water content of liquid formulations can vary from 35 to 90% water.
The invention is illustrated by working examples.
Allgemeines: Es wurde darauf geachtet, dass man nach dem ersten Reinigen der Prüfkörper in der Haushaltsgeschirrspülmaschine bis nach dem Wiegen und visuellen Abmustern der Gläser die Prüfkörper nur mit sauberen Baumwollhandschuhen angefasst wurden, damit das Gewicht bzw. der visuelle Eindruck der Prüfkörper nicht verfälscht wurde.General: Care was taken that after the first cleaning of the specimens in the household dishwasher until after weighing and visual patterning of the glasses, the specimens were only touched with clean cotton gloves, so that the weight or the visual impression of the specimens was not falsified.
Angaben in % sind Gew.-%, wenn nicht ausdrücklich anders angegeben.Data in% are wt .-%, unless expressly stated otherwise.
Die Ladungsdichte von modifizierten Polyethyleniminen (B) wurde stets wie folgt bestimmt (siehe auch:
- Man löste 1 g des betreffenden modifizierten Polyethylenimins (B) in 100 ml vollentsalztem Wasser. Mit einer Pufferlösung und wässriger HCl stellte man einen pH-Wert von 4,0 ein, bestimmt potenziometrisch. Man setzte drei ml einer wässrigen Lösung von Toluidinblau (50 mg/l Wasser) zu und titrierte N/400-KPVS (Kaliumpolyvinylsulfat) Lösung (Fa. Wako) mit einer Konzentration von 0,0004 meq/ml bis zu einem Farbumschlag von blau nach rosa. Man berechnete die Ladungsdichte wie folgt:
- LA: Ladungsdichte des betreffenden modifizierten Polyethylenimins (B), meq/g (Milliäquivalent/g)
- KV: Verbrauch der N/400-KPVS-Lösung [ml]
- 1 g of the respective modified polyethyleneimine (B) was dissolved in 100 ml of demineralized water. With a buffer solution and aqueous HCl was set to a pH of 4.0, determined potentiometrically. Three ml of an aqueous solution of toluidine blue (50 mg / l water) was added and titrated N / 400-KPVS (potassium polyvinyl sulfate) solution (Wako) with a concentration of 0.0004 meq / ml to a color change of blue pink. The charge density was calculated as follows:
- LA: charge density of the respective modified polyethyleneimine (B), meq / g (milliequivalent / g)
- KV: consumption of N / 400 KPVS solution [ml]
Zunächst wurden Basismischungen aus den Einsatzstoffen gemäß Tabelle 1 hergestellt. Die Einsatzstoffe wurden trocken vermischt.
Abkürzungen:
- MGDA: Methylglycindiessigsäure als Trinatriumsalz
- TAED: N,N,N',N'-Tetraacetylethylendiamin
- MGDA: methylglycine diacetic acid as trisodium salt
- TAED: N, N, N ', N'-tetraacetylethylenediamine
Es wurden modifizierte Polyethylenimine (B) gemäß Tabelle 2 verwendet, die nach der folgenden allgemeinen Vorschrift hergestellt worden waren:
- In einem 2-Liter-Autoklav wurden Polyethylenimin gemäß Tabelle 2, Spalte 2 und 3 sowie 0,7 Gew.-% KOH-Plätzchen, Wassergehalt 50 Gew.-%, Rest KOH), bezogen auf Polyethylenimin, vorgelegt. Man heizte unter reduziertem Druck (10 mbar) auf 120°C und rührte 2 Stunden bei 120°C, wobei man das Wasser entfernte. Danach wurde der Autoklav dreimal mit Stickstoff gespült und dann mit einem Anfangsdruck von 1 bar auf 140°C aufgeheizt. Man gab danach über einen Zeitraum von 2 Stunden entweder Ethylenoxid oder Propylenoxid gemäß Tabelle 2, Spalte 5 zu. Nach beendeter Zugabe rührte man weitere 3 Stunden bei 140°C. Danach entfernte man Wasser oder gegebenenfalls andere flüchtige Verbindungen unter vermindertem Druck (10 mbar) bei 90°C. Man erhielt modifizierte Polyethylenimine (B) gemäß Tabelle 2 als blassgelbe wachsartige Feststoffe.
- In a 2-liter autoclave polyethyleneimine according to Table 2, column 2 and 3 and 0.7 wt .-% KOH cookie, water content 50 wt .-%, balance KOH), based on polyethyleneimine were submitted. The mixture was heated under reduced pressure (10 mbar) to 120 ° C and stirred for 2 hours at 120 ° C, with the removal of the water. Thereafter, the autoclave was purged with nitrogen three times and then heated to 140 ° C at an initial pressure of 1 bar. Then, over a period of 2 hours, either ethylene oxide or propylene oxide according to Table 2, column 5 was added. After complete addition, the mixture was stirred for a further 3 hours at 140 ° C. Thereafter, water or optionally other volatile compounds were removed under reduced pressure (10 mbar) at 90.degree. Modified polyethyleneimines (B) according to Table 2 were obtained as pale yellow waxy solids.
Abkürzungen in Tabelle 2:
- AO: Alkylenoxid
- Spalte 2: Mw PEI bezieht sich auf das Molekulargewicht des zur Alkoxylierung eingesetzten Polyethylenimins, also auf nicht modifiziertes Polyethylenimin.
- Spalte 3: PEI bezieht sich auf nicht modifiziertes Polyethylenimin.
- Spalte 7: die molaren Anteile beziehen sich auf die Eingangsstoffe.
- Spalte 8: Gewichtsanteil Alkylenoxid im betreffenden gesamten alkoxylierten Alkylenimin-Polymer (B).
- AO: alkylene oxide
- Column 2: M w PEI refers to the molecular weight of the polyethyleneimine used for the alkoxylation, ie unmodified polyethyleneimine.
- Column 3: PEI refers to unmodified polyethyleneimine.
- Column 7: the molar proportions refer to the input substances.
- Column 8: Weight fraction of alkylene oxide in the respective entire alkoxylated alkyleneimine polymer (B).
Vorgehen:
- In einem 100-ml-Becherglas legte man 20 ml destilliertes Wasser vor und gab modifiziertes Polyethylenimin (B) gemäß Tabellen 2 und 3 unter Rühren zu.
- In a 100 ml beaker, 20 ml of distilled water was added and modified polyethyleneimine (B) according to Tables 2 and 3 added with stirring.
Dann rührte man 10 Minuten. Anschließend gab man MGDA-Trinatriumsalz (A.1), gelöst in 30 ml Wasser, gemäß Tabelle 3 zu. Man erhielt eine klar durchsichtige Lösung. Danach gab man Basismischung gemäß Tabelle 3 zu, rührte erneut um und verdampfte das Wasser.Then it was stirred for 10 minutes. Then, MGDA trisodium salt (A.1) dissolved in 30 ml of water was added as shown in Table 3. A clear solution was obtained. Thereafter, base mixture according to Table 3 was added, stirred again and evaporated the water.
Wenn man beim Test die entsprechenden Anteile Basismischung getrennt von wässriger Lösung von (A.1), (B), (C.1) oder (D.1) dosierte, erhielt man die gleichen Ergebnisse, wie wenn man die getrocknete Formulierung mit gleichen Mengen an Wirkstoffen testete. Es kommt also nicht auf die Reihenfolge der Dosierung an.If one dosed in the test, the appropriate proportions base mixture separately from aqueous solution of (A.1), (B), (C.1) or (D.1), gave the same results as when the dried formulation with the same Tested quantities of active ingredients. So it does not depend on the order of the dosage.
Allgemeines: Es wurde darauf geachtet, dass man nach dem ersten Reinigen der Prüfkörper in der Haushaltsgeschirrspülmaschine bis nach dem Wiegen und visuellen Abmustern der Gläser die Prüfkörper nur mit sauberen Baumwollhandschuhen angefasst wurden, damit das Gewicht bzw. der visuelle Eindruck der Prüfkörper nicht verfälscht wurde.General: Care was taken that after the first cleaning of the specimens in the household dishwasher until after weighing and visual patterning of the glasses, the specimens were only touched with clean cotton gloves, so that the weight or the visual impression of the specimens was not falsified.
Die Prüfung von erfindungsgemäßen Formulierungen und Vergleichsformulierungen erfolgte wie folgt.The testing of formulations according to the invention and comparative formulations was carried out as follows.
Zum Reinigen wurden die Gläser im oberen Geschirrkorb der Spülmaschine eingeordnet. Als Geschirrspülmittel setzte man jeweils 25 g erfindungsgemäße Formulierung oder 25 g Vergleichsformulierung gemäß Tabelle 3 ein, wobei Tabelle 3 die aktiven Komponenten (A.1), Basismischung , Silikat (C.1 oder C.2) und Verbindung (D) bzw. (E) und (B) von erfindungsgemäßer Formulierung jeweils einzeln spezifiziert. Man spülte bei einer Klarspültemperatur von 55°C. Die Wasserhärte lag jeweils im Bereich von null bis 2 °dH. Man spülte jeweils 100 Spülzyklen, d.h., man ließ das Programm 100 x ablaufen. Die Auswertung erfolgte gravimetrisch und visuell nach 100 Spülzyklen.For cleaning, the glasses were placed in the upper dish rack of the dishwasher. The dishwashing agent used was in each case 25 g of formulation according to the invention or 25 g of comparison formulation according to Table 3, where Table 3 shows the active components (A.1), base mixture, silicate (C.1 or C.2) and compound (D) or ( E) and (B) of inventive formulation individually specified. Rinsing was carried out at a rinse temperature of 55 ° C. The water hardness was in each case in the range of zero to 2 ° dH. One rinsed 100 rinse cycles each, i.e., the program was run 100 times. The evaluation was carried out gravimetrically and visually after 100 rinsing cycles.
Das Gewicht der Gläser wurde vor Beginn des ersten Spülzyklus und nach dem Trocknen nach dem letzten Spülzyklus bestimmt. Der Gewichtsverlust ist die Differenz der beiden Werte.The weight of the glasses was determined before the beginning of the first rinse cycle and after drying after the last rinse cycle. The weight loss is the difference between the two values.
Neben der gravimetrischen Auswertung wurde eine visuelle Bewertung des Spülguts nach 100 Zyklen in einer abgedunkelten Kammer unter Licht hinter einer Lochblende unter Verwendung einer Notenskala von 1 (sehr schlecht) bis 5 (sehr gut) vorgenommen. Dabei wurden jeweils Noten für flächige Korrosion / Trübung bzw. Linienkorrosion vergeben.In addition to the gravimetric evaluation, a visual assessment of the washware was made after 100 cycles in a darkened chamber under light behind a pinhole using a grading scale from 1 (very poor) to 5 (very good). In each case grades for area corrosion / turbidity or line corrosion were awarded.
Zunächst spülte man zum Zwecke der Vorbehandlung die Prüfkörper in einer Haushaltsgeschirrspülmaschine (Bosch SGS5602) mit 1 g Tensid (n-C18H37(OCH2CH2)10OH) und 20 g Zitronensäure, um eventuelle Verunreinigungen zu entfernen. Man trocknete die Prüfkörper, bestimmte ihr Gewicht und fixierte sie auf dem Gitterbodeneinsatz.First, for the purpose of pretreatment, the specimens were rinsed in a domestic dishwasher (Bosch SGS5602) with 1 g of surfactant (nC 18 H 37 (OCH 2 CH 2 ) 10 OH) and 20 g of citric acid to remove any impurities. The test pieces were dried, their weight determined and fixed on the grid floor insert.
Zur Beurteilung des gravimetrischen Abtrags wurden die trockenen Prüfkörper gewogen. Anschließend erfolgte die visuelle Beurteilung der Prüfkörper. Hierbei beurteilte man die Oberfläche der Prüfkörper hinsichtlich Linienkorrosion (Glasriefen) und Trübungskorrosion (flächenartige Trübung).To assess the gravimetric removal, the dry specimens were weighed. This was followed by the visual assessment of the test specimens. The surface of the test specimens was evaluated for line corrosion (glass scoring) and haze corrosion (areal haze).
Die Bewertungen erfolgten nach folgendem Schema.The assessments were made according to the following scheme.
Linienkorrosion:
- L5:
- keine Linien zu erkennen
- L4:
- in sehr wenigen Bereichen geringe Linienbildung, feine Linienkorrosion
- L3:
- in einigen Bereichen Linienkorrosion
- L2:
- in mehreren Bereichen Linienkorrosion
- L1:
- Stark ausgeprägte Linienkorrosion
- L5:
- no lines to recognize
- L4:
- in few areas low lines, fine line corrosion
- L3:
- in some areas line corrosion
- L2:
- in several areas line corrosion
- L1:
- Strong line corrosion
Glastrübung
- T5:
- keine Trübung zu erkennen
- T4:
- in sehr wenigen Bereichen geringe Trübung
- T3:
- in einigen Bereichen Trübungen
- T2:
- in mehreren Bereichen Trübungen
- T1:
- Stark ausgeprägte Trübung über fast die ganze Glasoberfläche
- T5:
- no haze visible
- T4:
- low turbidity in very few areas
- T3:
- in some areas cloudiness
- T2:
- in several areas cloudiness
- T1:
- Strong haze over almost the entire glass surface
Bei der Abmusterung wurden auch Zwischennoten (z.B. L3-4) zugelassen.Interim scores (e.g., L3-4) were also allowed on the match.
Wenn man statt Wasser Härtewasser mit 2° dH für die Tests einsetzte, so waren erfindungsgemäße Formulierungen den entsprechenden Vergleichsformulierungen ebenfalls stets überlegen, was die Inhibierung der Glaskorrosion betrifft.If hardness water at 2 ° dH was used instead of water for the tests, formulations according to the invention were also always superior to the corresponding comparative formulations in terms of the inhibition of glass corrosion.
Die Ergebnisse sind in den Tabelle 3 zusammengefasst.
In den erfindungsgemäßen Beispielen konnte stets nur geringe oder gar keine Glaskorrosion festgestellt werden.In the examples according to the invention, only little or no glass corrosion could always be determined.
Claims (14)
- A formulation which is free from heavy metals, comprising(A) in total in the range from 1 to 50% by weight of at least one aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetate (GLDA), and salts thereof,(B) in total in the range from 0.001 to 2% by weight of at least one alkoxylated alkyleneimine polymer with an average molecular weight Mw in the range from 800 to 25 000 g/mol which has a positive charge density of at least 5 meq/g and which has in the range from 2 to at most 80% by weight alkylene oxide side chains, based on total alkoxylated alkyleneimine polymer,based in each case on the solids content of the formulation in question.
- The formulation according to claim 1, which is free from phosphates and polyphosphates.
- The formulation according to claim 1 or 2, wherein (B) is selected from polyethyleneimines which have been reacted with ethylene oxide or propylene oxide.
- The formulation according to any one of claims 1 to 3, which has a heavy metal content below 0.05 ppm, based on the solids content of the formulation in question.
- The formulation according to any one of claims 1 to 4, wherein alkyleneimine polymer (B) is selected from those in which at most 30 mol% of the nitrogen atoms of the alkyleneimine polymer have been reacted with propylene oxide.
- The formulation according to any one of claims 1 to 5, which is solid at room temperature.
- The formulation according to any one of claims 1 to 6, which comprises in the range from 0.1 to 10% by weight of water.
- The formulation according to any one of claims 1 to 7, wherein the molar ratio of nitrogen atoms to alkylene oxide groups in the alkoxylated alkyleneimine polymer (B) is at most 5.
- The use of formulations according to any one of claims 1 to 8 for washing dishes and kitchen utensils, where washing is carried out with water of hardness from 2 to 25° German hardness.
- The use of formulations according to any one of claims 1 to 8 for washing objects which have at least one surface made of glass, which may be decorated or undecorated.
- The use according to claim 9 or 10, wherein the washing is washing using a dishwasher.
- The use according to any one of claims 9 to 11, wherein at least one formulation according to any one of claims 1 to 8 is used for washing drinking glasses, glass vases and glass vessels for cooking.
- A process for producing formulations according to any one of claims 1 to 8, wherein(A) aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetate (GLDA), and salts thereof, and(B) at least one alkoxylated alkyleneimine polymer with an average molecular weight Mw in the range from 800 to 25 000 g/mol which has a positive charge density of at least 5 meq/g and which has in the range from 2 to at most 80% by weight alkylene oxide side chains, based on total alkoxylated alkyleneimine polymer,and optionally further components are mixed in one or more steps with one another in the presence of water and then the water is completely or partially removed.
- The process according to claim 13, wherein the water is removed by spray-drying or spray-granulation.
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EP13720303.0A EP2841549B1 (en) | 2012-04-25 | 2013-04-23 | Formulations, use of same as or for manufacture of dish-washing agents and their manufacture |
PL13720303T PL2841549T3 (en) | 2012-04-25 | 2013-04-23 | Formulations, use of same as or for manufacture of dish-washing agents and their manufacture |
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US201261637901P | 2012-04-25 | 2012-04-25 | |
US201261637891P | 2012-04-25 | 2012-04-25 | |
EP12165545 | 2012-04-25 | ||
EP12165556 | 2012-04-25 | ||
EP12165550 | 2012-04-25 | ||
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EP12168044 | 2012-05-15 | ||
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US201261697817P | 2012-09-07 | 2012-09-07 | |
EP12183437 | 2012-09-07 | ||
PCT/EP2013/058391 WO2013160301A1 (en) | 2012-04-25 | 2013-04-23 | Formulations, use thereof as or for production of dishwashing detergents and production thereof |
EP13720303.0A EP2841549B1 (en) | 2012-04-25 | 2013-04-23 | Formulations, use of same as or for manufacture of dish-washing agents and their manufacture |
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JP (1) | JP6133971B2 (en) |
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CN (1) | CN104379717B (en) |
BR (1) | BR112014026565A2 (en) |
CA (1) | CA2871210A1 (en) |
ES (2) | ES2612342T3 (en) |
MX (1) | MX2014013009A (en) |
PL (1) | PL2841549T3 (en) |
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WO2014131585A1 (en) * | 2013-02-28 | 2014-09-04 | Basf Se | Formulations, use thereof as dishwashing detergents or for producing dishwashing detergents, and the production of said formulations |
US9994797B2 (en) * | 2013-04-02 | 2018-06-12 | Basf Se | Formulations, preparation thereof, and use thereof as, or for preparing, dishwashing compositions |
EP2989192B1 (en) * | 2013-04-23 | 2018-08-08 | Basf Se | Formulations, use of same as or for manufacture of dish-washing agents and their manufacture |
BR112015029557A2 (en) * | 2013-05-27 | 2020-03-10 | Basf Se | aqueous solution, process for manufacturing an aqueous solution, and use of an aqueous solution |
JP2015086295A (en) * | 2013-10-30 | 2015-05-07 | 花王株式会社 | Dishwashing detergent composition |
RU2696284C2 (en) * | 2014-11-26 | 2019-08-01 | Басф Се | Aqueous solution containing complex of complexing agents |
EP3034596B2 (en) | 2014-12-17 | 2021-11-10 | The Procter & Gamble Company | Detergent composition |
JP2018529788A (en) * | 2015-07-09 | 2018-10-11 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | How to wash dishes |
US11028350B2 (en) | 2016-06-20 | 2021-06-08 | Basf Se | Powders and granules and process for making such powders and granules |
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PE6995A1 (en) * | 1994-05-25 | 1995-03-20 | Procter & Gamble | COMPOSITION INCLUDING A PROPOXYLATED POLYKYLENE OAMINE POLYKYLENE OAMINE POLYMER AS DIRT SEPARATION AGENT |
US5837663A (en) | 1996-12-23 | 1998-11-17 | Lever Brothers Company, Division Of Conopco, Inc. | Machine dishwashing tablets containing a peracid |
AU8864298A (en) * | 1997-07-23 | 1999-02-16 | Unilever Plc | Automatic dishwashing compositions containing water soluble cationic or amphoteric polymers |
DE19819187A1 (en) | 1998-04-30 | 1999-11-11 | Henkel Kgaa | Solid dishwasher detergent with phosphate and crystalline layered silicates |
JP2004503370A (en) | 2000-06-14 | 2004-02-05 | ザ、プロクター、エンド、ギャンブル、カンパニー | Surface cleaning method |
US7138462B2 (en) * | 2003-08-22 | 2006-11-21 | Los Alamos National Security, Llc | Functionalized polymers for binding to solutes in aqueous solutions |
MX2007012612A (en) * | 2005-04-15 | 2008-01-11 | Basf Ag | Amphiphilic water-soluble alkoxylated polyalkylenimines with an internal polyethylene oxide block and an external polypropylene oxide block. |
JP5213091B2 (en) * | 2006-08-22 | 2013-06-19 | ディバーシー株式会社 | Granular detergent composition for automatic dishwasher, method for producing the same, and method for using the same |
TW200927915A (en) * | 2007-10-25 | 2009-07-01 | Croda Int Plc | Laundry formulations and method of cleaning |
UA103760C2 (en) * | 2008-01-24 | 2013-11-25 | Юнилевер Н.В. | Machine dishwash detergent composition |
GB0815022D0 (en) * | 2008-08-16 | 2008-09-24 | Reckitt Benckiser Nv | Composition |
EP2264136B1 (en) * | 2009-06-19 | 2013-03-13 | The Procter & Gamble Company | Liquid hand dishwashing detergent composition |
EP2392638B1 (en) * | 2010-06-04 | 2017-10-18 | Dalli-Werke GmbH & Co. KG | Low-hygroscopic particulate composition comprising one or more aminopolycarboxylate chelating compounds |
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JP6133971B2 (en) | 2017-05-24 |
MX2014013009A (en) | 2015-08-06 |
CA2871210A1 (en) | 2013-10-31 |
BR112014026565A2 (en) | 2017-06-27 |
JP2015515531A (en) | 2015-05-28 |
PL2841549T3 (en) | 2017-04-28 |
KR20150013593A (en) | 2015-02-05 |
CN104379717A (en) | 2015-02-25 |
CN104379717B (en) | 2017-08-11 |
RU2623440C2 (en) | 2017-06-26 |
ES2693772T3 (en) | 2018-12-13 |
EP2841549A1 (en) | 2015-03-04 |
RU2014147082A (en) | 2016-06-10 |
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ES2612342T3 (en) | 2017-05-16 |
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