KR102007148B1 - Formulations, use thereof as or for production of dishwashing detergents and production thereof - Google Patents
Formulations, use thereof as or for production of dishwashing detergents and production thereof Download PDFInfo
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- KR102007148B1 KR102007148B1 KR1020147032948A KR20147032948A KR102007148B1 KR 102007148 B1 KR102007148 B1 KR 102007148B1 KR 1020147032948 A KR1020147032948 A KR 1020147032948A KR 20147032948 A KR20147032948 A KR 20147032948A KR 102007148 B1 KR102007148 B1 KR 102007148B1
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- South Korea
- Prior art keywords
- formulation
- range
- weight
- acid
- cleaning
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 113
- 238000009472 formulation Methods 0.000 title claims abstract description 93
- 239000003599 detergent Substances 0.000 title description 13
- 238000004851 dishwashing Methods 0.000 title description 13
- 238000004519 manufacturing process Methods 0.000 title description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 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 abstract description 18
- 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 abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 12
- 239000004615 ingredient Substances 0.000 claims abstract description 9
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 8
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000013922 glutamic acid Nutrition 0.000 claims abstract description 8
- 239000004220 glutamic acid Substances 0.000 claims abstract description 8
- 239000011521 glass Substances 0.000 claims description 47
- 229920002873 Polyethylenimine Polymers 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000004140 cleaning Methods 0.000 claims description 21
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 18
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 11
- 229910001385 heavy metal Inorganic materials 0.000 claims description 9
- 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 6
- 239000010452 phosphate Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 229920000388 Polyphosphate Polymers 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000001205 polyphosphate Substances 0.000 claims description 4
- 235000011176 polyphosphates Nutrition 0.000 claims description 4
- 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
- 238000005260 corrosion Methods 0.000 description 26
- 230000007797 corrosion Effects 0.000 description 26
- -1 alkali metal salts Chemical class 0.000 description 24
- 239000007844 bleaching agent Substances 0.000 description 21
- 229910052783 alkali metal Inorganic materials 0.000 description 20
- 239000003623 enhancer Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 229920000962 poly(amidoamine) Polymers 0.000 description 11
- 150000001340 alkali metals Chemical class 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
- 239000002585 base Substances 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
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 238000011156 evaluation Methods 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
- 230000000007 visual effect Effects 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 150000001991 dicarboxylic acids Chemical class 0.000 description 5
- 239000003112 inhibitor Substances 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
- 235000021317 phosphate Nutrition 0.000 description 5
- 229920005646 polycarboxylate Polymers 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 4
- 102000004190 Enzymes Human genes 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
- 229940088598 enzyme Drugs 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 239000000243 solution Substances 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
- 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
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- 150000008064 anhydrides Chemical class 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 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
- 235000013532 brandy Nutrition 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
- 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005303 weighing Methods 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
- OMXANELYEWRDAW-UHFFFAOYSA-N 1-Hexacosene Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCC=C OMXANELYEWRDAW-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- SPURMHFLEKVAAS-UHFFFAOYSA-N 1-docosene Chemical compound CCCCCCCCCCCCCCCCCCCCC=C SPURMHFLEKVAAS-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-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
- RUZAHKTXOIYZNE-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid;iron(2+) Chemical compound [Fe+2].OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O RUZAHKTXOIYZNE-UHFFFAOYSA-N 0.000 description 2
- 240000002234 Allium sativum Species 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-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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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
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- 108091005804 Peptidases Proteins 0.000 description 2
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- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 2
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- 238000007792 addition Methods 0.000 description 2
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- 150000001412 amines Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical group 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
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- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
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- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 2
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 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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- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical compound [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001629 suppression Effects 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
- 229950003937 tolonium Drugs 0.000 description 1
- HNONEKILPDHFOL-UHFFFAOYSA-M tolonium chloride Chemical compound [Cl-].C1=C(C)C(N)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 HNONEKILPDHFOL-UHFFFAOYSA-M 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000005209 triethanolammonium group Chemical group 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
- 239000001993 wax 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Washing And Drying Of Tableware (AREA)
Abstract
Formulations comprising the following ingredients:
(A) one or more aminocarboxylates selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetate (GLDA), and salts and derivatives thereof, and
(B) an average molecular weight in the range from 800 to 25 000 g / mol, with a total charge alkoxylated alkyleneimine polymer, having a positive charge density of at least 5 meq / g and an alkylene oxide side chain in the range from 2 to up to 80% by weight; At least one alkoxylated alkyleneimine polymer of M w .
Description
The present invention relates to a formulation comprising the following ingredients:
(A) one or more aminocarboxylates selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetate (GLDA), and salts thereof, and
(B) an average molecular weight in the range from 800 to 25 000 g / mol, with a total charge alkoxylated alkyleneimine polymer, having a positive charge density of at least 5 meq / g and an alkylene oxide side chain in the range from 2 to up to 80% by weight; At least one alkoxylated alkyleneimine polymer of Mw.
The invention furthermore relates to a process for the preparation of the formulations according to the invention and to their use as or for preparing dishwashing detergents, in particular dishwashing detergents for machine dishwashing.
Dishwasher detergents must meet many requirements. For example, they must clean the bowl as a whole, they should not have any harmful or potentially harmful ingredients to the wastewater, they must allow the dripping and drying of the water from the bowl, and they should not cause problems during the operation of the dishwasher. do. Finally, they must not cause aesthetically undesirable results on the article to be cleaned. In this regard, glass corrosion is mentioned in particular.
Glass corrosion is primarily promoted by chemical effects, as well as occurring as a result of mechanical influences, for example as a result of rubbing the glass together or as a mechanical contact between the glass and the parts of the dishwasher. For example, certain ions can dissolve out of the glass as a result of repeated mechanical cleaning, which deforms the optics badly and alters the aesthetic properties.
Several effects are observed with regard to glass corrosion. First, the formation of microscopic microcracks is observed, which can be noticed by the formation of lines. Second, in many cases, general blurring can be observed (for example, making the glass under discussion look tacky). The effects of this type are further subdivided into overall patches, as well as brilliance fading and scoring, as well as patches and circular clouds.
WO 2006/108857 describes alkoxylated polyethyleneimines as additives for detergents. By way of example, detergents comprising zeolites or polyaminocarboxylates such as EDTA or triethylenediamine pentaacetate as complexing agents are described.
WO 01/96516 proposes formulations comprising alkoxylated polyethyleneimines for hard surface cleaning. Purified water is used for rinsing.
WO 2010/020765 proposes dishwashing detergents comprising polyethyleneimine. Dishwasher detergents of this type may comprise phosphate or may be free of phosphate. They contribute to good suppression of glass corrosion. Zinc-containing and bismuth-containing dishwashing detergents are disappointing. Glass corrosion, especially line corrosion and clouding, however, are in many cases still not adequately delayed or prevented.
It was therefore an object to provide formulations which are suitable as or for the preparation of dishwashing detergents and overcome the disadvantages known from the prior art and which inhibit glass corrosion or at least reduce it particularly well. It was also an object to provide a process for the preparation of a formulation suitable as or for the preparation of dishwashing detergents and overcoming the disadvantages known from the prior art. It was also an object to provide a use of the formulation.
Thus, the formulations defined at the outset have been found and are called shortly the formulations according to the invention.
The formulations according to the invention are free of heavy metals. In the context of the present invention, this is understood to mean that the formulations according to the invention are free of these heavy metal compounds, in particular iron and bismuth, which do not act as bleach catalysts. With regard to heavy metal compounds, in the context of the present invention, "without" means that the content of heavy metal compounds that do not act as bleach catalyst is determined by the Leach method and is based on a total of 0 to 100 ppm. It is understood to mean being in a range. Preferably, the formulations according to the invention have a heavy metal content of less than 0.05 ppm relative to the solids content of the formulation under discussion.
In the context of the present invention, "heavy metal" is any metal having a specific density of at least 6 g / cm 3. In particular, heavy metals are precious metals and also zinc, bismuth, iron, copper, lead, tin, nickel, cadmium and chromium.
Preferably, the formulations according to the invention do not comprise measurable fractions of zinc and bismuth compounds (ie less than 1 ppm, for example).
Formulations according to the invention comprise the following ingredients:
(A) one or more aminocarboxylates selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetate (GLDA), and salts thereof, also short aminocarboxylates in the context of the present invention (A) or else called compound (A), and preferably salts thereof.
Preferably, compound (A) is selected as the free acid, particularly preferably in partially or fully neutralized form, ie as a salt. Suitable counterions are for example inorganic cations such as ammonium, alkali metals or alkaline earth metals, preferably Mg 2+ , Ca 2+ , Na + , K + , or organic cations, preferably one or more organic radicals. Ammonium substituted with triethanolammonium, in particular N, N-diethanolammonium, N-mono-C 1 -C 4 -alkyldieethanolammonium, for example N-methyldiethanolammonium or Nn-butyldiethanolammonium, and N, N-di-C 1 -C 4 -alkylethanolammonium.
Very particularly preferred compounds (A) are alkali metal salts, in particular sodium salts of methylglycine diacetate (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetate (GLDA).
Very particularly preferably, methylglycine diacetate (MGDA), iminodisuccinic acid (IDA) or glutamic acid diacetate (GLDA) are completely neutralized.
In addition, the formulations according to the invention comprise the following components:
(B) 800 to 800, with respect to the total alkoxylated alkyleneimine polymer, having a positive charge density of at least 5 meq / g and having an alkylene oxide side chain in the range of 2 to up to 80% by weight, preferably 5 to 60% by weight. At least one alkoxylated alkyleneimine polymer having an average molecular weight M w in the range of 25 000 g / mol.
In the context of the present invention, modified alkyleneimine polymers of this type are also called shortly modified polyalkyleneimines (B).
In the context of the present invention, an alkyleneimine polymer is understood to mean a polymeric material obtained by homopolymerization or copolymerization of one or more cyclic imines or by grafting (co) polymers to one or more cyclic imines. . Examples are polyalkylenepolyamines and polyamidoamines grafted with ethyleneimine.
In the context of the present invention, the polyalkylenepolyamines preferably comprise at least 6 nitrogen atoms and at least 5 C 2 -C 10 -alkylene units, preferably C 2 -C 3 -alkylene units, per molecule. Is understood to mean polymers such as pentaethylenehexamine, and in particular polyethyleneimine.
Alkyleneimine polymers, in particular polyethyleneimine, may have, for example, an average molecular weight (M w ) of at least 300 g / mol; Preferably, the average molecular weight of polyethyleneimine is in the range of 800 to 20 000 g / mol, as identified by light scattering.
Polyalkylenepolyamines can be covalently modified in partially quaternized (alkylated) form as alkyleneimine polymers. Suitable quaternizing agents (alkylating agents) are, for example, alkyl halides, in particular C 1 -C 10 -alkyl chlorides such as methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, n-butyl chloride, tert- Butyl chloride, n-hexyl chloride, also epichlorohydrin, dimethyl sulfate, diethyl sulfate and benzyl chloride. When the quaternized (alkylated) polyalkylenepolyamine as an alkyleneimine polymer is covalently modified, the degree of quaternization (alkylation) is preferably 1 to 4 quaternizable (alkylated) N atoms in the alkyleneimine polymer. 25, particularly preferably 20 mol% or less.
In addition, 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, for example, succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid or terephthalic acid. It is also possible to use mixtures of the aforementioned dicarboxylic acids, for example mixtures of adipic acid and glutaric acid or mixtures of maleic acid and adipic acid. Preference is given to using adipic acid to prepare polyamidoamines. Suitable polyalkylenepolyamines condensed with the aforementioned dicarboxylic acids are, for example, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine And bis-aminopropylethylenediamine. The aforementioned polyalkylenepolyamines can also be used in the form of mixtures in the preparation of polyamidoamines. The preparation of the polyamidoamine can preferably take place without dilution, but can optionally also be carried out in an inert solvent. Condensation of dicarboxylic acids with polyalkylenepolyamines occurs at elevated temperatures, for example in the range from 120 to 220 ° C. Water formed during the reaction is distilled off from the reaction mixture. Condensation may optionally be carried out in the presence of lactones or lactams of carboxylic acids having 4 to 8 carbon atoms. Generally, 0.8 to 1.4 moles of polyalkylenepolyamine are used per mole of dicarboxylic acid. Polyamidoamines usable in this manner have primary and secondary NH groups and are water soluble.
Polyamidoamines grafted with ethyleneimine are those in which ethyleneimine is described above in the presence of Bronstedt acid or Lewis acid, for example sulfuric acid, phosphoric acid or boron trifluoride etherate. It can be prepared by acting on. As a result, ethyleneimine is grafted onto the polyamidoamine under discussion. For example, 1 to 10 ethyleneimine units can be grafted per basic nitrogen atom in the polyamidoamine, ie, about 10 to 500 parts by weight of ethyleneimine are used per 100 parts by weight of polyamidoamine.
Preferred alkyleneimine polymers are polyethyleneimines.
In one embodiment of the invention, the polyethyleneimine is selected from highly branched polyethyleneimines. Highly branched polyethyleneimines are characterized by their high degree of branching (DB). The degree of branching can be measured, for example, by 13 C-NMR spectroscopy, preferably at D 2 O, and is defined as follows:
DB = D + T / D + T + L
Wherein D (resin) corresponds to the portion of the tertiary amino group, L (linear) corresponds to the portion of the secondary amino group, and T (terminal) corresponds to the portion of the primary amino group.
In the context of the present invention, highly branched polyethyleneimines are polyethyleneimines having a DB in the range from 0.1 to 0.95, preferably in the range from 0.25 to 0.90, particularly preferably in the range from 0.30 to 0.80, very particularly preferably at least 0.5. .
In one embodiment of the invention, the polyethylenimine is a highly branched polyethyleneimine (homopolymer) having an average molecular weight M w in the range of 600 to 20 000 g / mol, preferably in the range of 800 to 15 000 g / mol. to be.
In the context of the present invention, the alkyleneimine polymer is used in covalently modified form, specifically it is from 2 to 80% by weight, preferably from 5 to 60% by weight relative to the total alkoxylated alkyleneimine polymer (B). As having an alkylene oxide side chain in the range. For alkoxylation, epoxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide or epichlorohydrin can be used. Preferred alkoxylation reagents are ethylene oxide and propylene oxide, and also mixtures of ethylene oxide and propylene oxide.
In one embodiment, in the alkoxylated alkyleneimine polymer (B), the range of 5 to 60 mole% of the nitrogen atoms of the primary and secondary amino groups of the alkyleneimine polymer is alkoxylated.
In one embodiment of the invention, the modified alkyleneimine (B) is selected from polyethyleneimine reacted with ethylene oxide or propylene oxide.
The modified polyalkyleneimines (B) may have high or low molecular weight anions (organic or preferably inorganic) as counterions. In the context of the present invention, high molecular weight anions have an average molecular weight of at least 200 g / mol, for example 2500 g / mol, and low molecular weight anions have a molecular weight of less than 200 g / mol, for example 17-150 g / mol. Have Examples of low molecular weight organic counterions are acetate, propionate and benzoate. Examples of low molecular weight inorganic counterions are sulfates, chlorides, bromides, hydroxides, carbonates, methanesulfonates and hydrogencarbonates.
In one embodiment of the invention, the modified polyalkyleneimine (B) has a cationic charge density of at least 5 meq / g up to 25 meq / g (milligram equivalents / g), preferably up to 22 meq / g In g, data refers to modified polyalkyleneimines (B) that do not take counterions into account. Cationic charge density can be confirmed, for example, by titration, for example using polyvinyl sulfate solution.
In one embodiment of the invention, the modified polyalkyleneimine (B) has a molecular weight distribution M w / M n in the range from 1.1 to 10, preferably from 1.5 to 5.
In one embodiment of the invention, the formulations according to the invention, in each case with respect to the solids content of the formulation under discussion,
Aminocarboxylate (A) in the range of from 1 to 50% by weight, preferably from 10 to 25% by weight,
Modified polyalkyleneimines (B) in the range of 0.001 to 5% by weight, preferably 0.02 to 0.5% by weight in total.
In one variant of the invention, the formulation according to the invention comprises compound (A) and modified polyalkyleneimine (B) in a weight ratio in the range of 1000: 1 to 25: 1.
In a preferred embodiment of the invention, the formulations according to the invention are free of phosphates and polyphosphates (also include hydrogen phosphates), for example trisodium phosphate, pentasodium tripolyphosphate and hexasodium metaphosphate. With regard to phosphate and polyphosphate, in the context of the present invention, "without" is understood to mean that the content of phosphate and polyphosphate ranges from 10 ppm to 0.2% by weight in total, as determined by gravimetric measurement. .
Formulations according to the invention may comprise further ingredients advantageous for use in washing dishes and / or kitchen appliances, for example.
In another embodiment of the invention, the formulations according to the invention do not comprise additional ingredients advantageous for use in washing dishes and / or kitchen appliances, for example, but can be easily formulated with the additional ingredients It is therefore suitable as starting material.
In one embodiment of the invention, the formulation according to the invention comprises sodium citrate (C). In this regard, the term sodium citrate includes monosodium salts and preferably disodium salts. Sodium citrate can be used as anhydrous salt or as a hydrate, for example as a dihydrate.
In one embodiment of the invention, the formulation according to the invention
(D) at least one compound selected from alkali metal percarbonates, alkali metal perborates and alkali metal persulfates (also called "bleach (D)" in the context of the present invention).
Preferred bleach (D) is selected from sodium perborate, anhydride or for example as monohydrate or as a tetrahydrate or as so-called dihydrate, as sodium percarbonate, anhydride or for example monohydrate, and sodium persulfate The term "persulfate" includes in each case salts of peracid H 2 SO 5 and also peroxodisulfate.
In this regard, the alkali metal salts may in each case also be alkali metal hydrogen-carbonates, alkali metal hydrogen percarbonates and alkali metal hydrogen persulfates. However, in each case, dialkali metal salts are preferred.
In one embodiment of the invention, the formulation according to the invention is in each case 0-50% by weight sodium citrate (C), preferably measured as anhydrous sodium citrate, with respect to the solids content of the formulation under discussion 1-15% by weight of bleach (D), in particular selected from at least 5% by weight or more of sodium citrate (C), alkali metal percarbonates, alkali metal perborates and alkali metal persulfates , Preferably at least 0.5% by weight of bleach (D).
In one embodiment of the invention, the formulation according to the invention is a solid, for example a powder or a tablet, at room temperature. In another embodiment of the invention, the formulations according to the invention are liquid at room temperature. In one embodiment of the invention, the formulations according to the invention are granules, liquid preparations or gels.
In one embodiment of the invention, the formulations according to the invention comprise 0.1 to 10% by weight of water, relative to the sum of all solids of the formulations under discussion.
In one embodiment of the invention, the formulations according to the invention comprise further components (E), for example one or more surfactants, one or more enzymes, one or more enhancers, in particular phosphorus-free enhancers, one or more co-enhancers. At least one alkali carrier, at least one bleach, at least one bleach catalyst, at least one bleach activator, at least one bleach stabilizer, at least one antifoam, at least one corrosion inhibitor, at least one enhancer component, a buffer, a dye, at least one perfume, one It may have at least one organic solvent, at least one purification aid, at least one disintegrant, at least one thickener, or at least one solubility promoter.
Examples of surfactants are in particular nonionic surfactants and also mixtures of anionic or zwitterionic surfactants with nonionic surfactants. Preferred nonionic surfactants are di- and multiblock copolymers of alkoxylated alcohols and alkoxylated fatty alcohols, ethylene oxide and propylene oxide and sorbitan and ethylene oxide or propylene oxide, alkyl glycosides and so-called amine oxides. Reaction product.
Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (I):
Where the variable is defined as follows:
R 1 is the same or different and is linear C 1 -C 10 -alkyl, preferably the same in each case and is selected from ethyl and particularly preferably methyl,
R 2 is 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 is C 1 -C 10 -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl , 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or isodecyl,
m and n range from 0 to 300 and the sum of n and m is at least 1. Preferably, m ranges from 1 to 100 and n ranges from 0 to 30).
Here, the compound of general formula (I) may be a block copolymer or a random copolymer, and a block copolymer is preferable.
Other preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (II)
Where the variable is defined as follows:
R 1 is the same or different and is linear C 1 -C 10 -alkyl, preferably the same in each case and is selected from ethyl and particularly preferably methyl,
R 4 is selected from C 6 -C 20 -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 ,
a is a number ranging from 1 to 6,
b is a number ranging from 4 to 20,
d is a number ranging from 4 to 25).
Here, the compound of general formula (II) may be a block copolymer or a random copolymer, and a block copolymer is preferable.
Further suitable nonionic surfactants are selected from di- and multiblock copolymers, consisting of ethylene oxide and propylene oxide. Further suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Amine oxides or alkyl glycosides are likewise suitable. An overview of suitable additional nonionic surfactants can be found in EP A 0 851 023 and DE-A 198 19 187.
Mixtures of two or more different nonionic surfactants may also be present.
Examples of anionic surfactants include C 8 -C 20 -alkyl sulfates, C 8 -C 20 -alkylsulfonates and C 8 -C 20 -alkyl ether sulfates having 1 to 6 ethylene oxide units per molecule. to be.
In one embodiment of the invention, the formulations according to the invention may comprise a surfactant in the range of 3 to 20% by weight.
Formulations according to the invention may comprise one or more enzymes. Examples of enzymes are lipase, hydrolase, amylae, protease, cellulase, esterase, pectinase, lactase and peroxidase.
Formulations according to the invention may in each case comprise, for example, up to 5% by weight, preferably 0.1 to 3% by weight, based on the total solids content of the formulations according to the invention.
In addition to sodium citrate (C), the formulations according to the invention may comprise one or more enhancers, in particular phosphate-free enhancers. Examples of suitable enhancers include silicates, in particular sodium disilicate and sodium metasilicate, zeolites, sheet silicates, in particular the formulas α-Na 2 Si 2 O 5 , β-Na 2 Si 2 O 5 , and δ-Na 2 Si 2 O 5 Of those, also fatty acid sulfonates, α-hydroxypropionic acid, alkali metal malonates, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartaric acid diacetate, tartaric acid monoacetate, oxidized starch, and polymeric enhancers, for example Polycarboxylates and polyaspartic acids.
In one embodiment of the invention, the enhancer is selected from polycarboxylates such as alkali metal salts of (meth) acrylic acid homopolymers 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. Suitable polymers are in particular polyacrylic acids, which preferably have an average molecular weight M w in the range of 2000 to 40 000 g / mol, preferably 2000 to 10 000 g / mol, in particular 3000 to 8000 g / mol. Also suitable are copolymeric polycarboxylates, in particular copolymerizable polycarboxylates of acrylic acid and methacrylic acid, and copolymerizable polycarboxylates of acrylic acid or methacrylic acid with maleic and / or fumaric acid.
Also monoethylenically unsaturated C 3 -C 10 -mono- or C 4 -C 10 -dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citracon It is possible to use copolymers of one or more monomers from the group consisting of acids with one or more hydrophilic or hydrophobically modified monomers 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 such as, for example, 1-decene, 1-dodecene, 1 Tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracosene and 1-hexacosene, C 22 -α-olefin, C 20 -C 24 -α-olefin And mixtures of polyisobutenes having an average of 12 to 100 carbon atoms per molecule.
Suitable hydrophilic monomers are monomers with sulfonate or phosphonate groups, and also nonionic monomers with hydroxyl functional or alkylene oxide groups. For example, allyl alcohol, isoprenol, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene jade Seed-co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and ethoxypoly Mention may be made of (propylene oxide-co-ethylene oxide) (meth) acrylate. The polyalkylene glycols may here comprise 3 to 50, in particular 5 to 40, in particular 10 to 30 alkylene oxide units per molecule.
Particularly preferred sulfone-acid-group-containing monomers here include 1-acrylamido-1 propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropane-sulfonic acid, 2-metha Krillamido-2-methylpropanesulfonic acid, 3-methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, metalylsulfonic acid, allyloxybenzenesulfonic acid, metalyloxybenzenesulfonic 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 Latex, sulfomethacrylamide, sulfomethylmethacrylamide, and salts of these acids, such as sodium, potassium or ammonium salts thereof.
Particularly preferred phosphonate-group-containing monomers are vinylphosphonic acid and salts thereof.
In addition, amphoteric polymers can also be used as enhancers.
Formulations according to the invention may comprise, for example, a range of 10 to 50% by weight in total, preferably up to 20% by weight of an enhancer.
In one embodiment of the invention, the formulations according to the invention may comprise one or more co-enhancers.
Examples of co-enhancers are phosphonates such as hydroxyalkanesphosphonates and aminoalkanesphosphonates. Of the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as co-enhancer. It is preferably used as sodium salt, disodium salt to provide neutral reaction and tetrasodium salt of alkaline reaction (pH 9). Suitable aminoalkanephosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and higher homologues thereof. They are preferably used in the form of neutrally reacting sodium salts, for example as the hexasodium salt of EDTMP or as the 7- and 8sodium salts of DTPMP.
Formulations according to the invention may comprise one or more alkali carriers. The alkali carrier ensures a pH of 9 or more, for example, when an alkaline pH is desired. Suitable are, for example, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal hydroxides and alkali metal metasilicates. Preferred alkali metals are potassium in each case, particularly preferably sodium.
In addition to bleach (D), the formulations according to the invention may comprise one or more chlorine-containing bleaches.
Suitable chlorine-containing bleaches 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 comprise, for example, in the range of 3 to 10% by weight of chlorine-containing bleach.
Formulations according to the invention may comprise one or more bleach catalysts. The bleach catalyst can be selected from bleach-supplemented transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and also cobalt-, iron-, copper- and ruthenium-amine complexes can also be used as bleaching catalysts.
Formulations according to the invention may comprise one or more bleach activators, for example N-methylmorpholinium-acetonitrile salt (“MMA salt”), trimethylammonium acetonitrile salt, N-acrylimides such as, for example , N-nonanoylsuccinimide, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine ("DADHT") or nitrile quarts (trimethylammonium acetonitrile salt) Can be.
Further examples of suitable bleach activators are tetraacetylethylenediamine (TAED) and tetraacetylhexylenediamine.
Formulations according to the invention may comprise one or more corrosion inhibitors. In this case, it is intended to include such compounds which inhibit the corrosion of metals. Examples of suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, and also phenol derivatives such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, Phloroglucinol or pyrogallol.
In one embodiment of the invention, the formulation according to the invention comprises a corrosion inhibitor in the range of from 0.1 to 1.5% by weight in total.
Formulations according to the invention may comprise one or more enhancer components, for example sodium sulfate.
Formulations according to the invention may comprise one or more antifoams, for example selected from silicone oils and paraffin oils.
In one embodiment of the invention, the formulation according to the invention comprises a defoaming agent in the range of 0.05 to 0.5% by weight in total.
Formulations according to the invention may comprise phosphonic acid or one or more phosphonic acid derivatives, for example hydroxyethane-1,1-diphosphonic acid.
The invention further provides for the use of the formulations according to the invention for the mechanical cleaning of dishes and kitchen appliances. Within the scope of the present invention, kitchen appliances which may be mentioned are, for example, pots, pans, steaming pans, and also products made of metals such as, for example, large spoons with holes, fish slices and garlic presses.
Preferably, the use of a formulation according to the invention for the mechanical cleaning of an article having one or more surfaces made of glass which may or may not be decorated is provided. In this regard, in the context of the present invention, a surface made of glass is understood to mean that the article under discussion has one or more zones made of glass that come into contact with the ambient air and become dirty upon use. Thus, the article in question can be made essentially of glass, such as a glass or glass bowl. However, they can also be, for example, lids with individual components made of different materials, for example pot lids with rims and handles made of metal.
Surfaces made of glass may be decorated, for example colored, stamped or undecorated.
The term "glass" includes any desired type of glass, such as lead glass, in particular soda-lime glass, crystal glass and borosilicate glass.
Preferably, the machine wash is a wash by a dishwasher (automatic dishwashing).
In one embodiment of the invention, one or more formulations according to the invention are used for the mechanical cleaning of glasses, glass vases and cooking glass containers.
In one embodiment of the invention, for cleaning, water having a hardness in the range of 1 to 30 ° German hardness, preferably in the range of 2 to 25 ° German hardness is used (German hardness especially means calcium hardness Understand).
For rinsing likewise it is also possible to use water with a hardness in the range of 1 to 30 ° German hardness, preferably in the range of 2 to 25 ° German hardness.
When the formulations according to the invention are used for machine cleaning, even in the case of repeated machine cleaning of products having one or more surfaces made of glass, and on the surface of which the product having one or more surfaces made of glass is heavily soiled or In the case of washing with the dish, only a very tendency towards glass corrosion is observed. In addition, the use of the formulations according to the invention for cleaning the glass together with articles made of metal, for example with pots, pans or garlic presses, is significantly less harmful.
In addition, it can be observed that the formulation according to the invention has a very good bleaching effect when used for cleaning dishes and kitchen appliances and glass surfaces.
The present invention further provides a method for producing the formulation according to the invention (shortly also called the preparation method according to the invention). In order to carry out the manufacturing method according to the invention, the procedure is for example,
(A) aminocarboxylates selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetate (GLDA), and salts thereof, and
(B) an average molecular weight in the range from 800 to 25 000 g / mol, with a total charge alkoxylated alkyleneimine polymer, having a positive charge density of at least 5 meq / g and an alkylene oxide side chain in the range from 2 to up to 80% by weight; One or more alkoxylated alkyleneimine polymers of M w ,
And optionally
(C) sodium citrate or
(D) at least one compound selected from alkali metal percarbonates, alkali metal perborates and alkali metal persulfates,
And optionally further components (E) are mixed with one another in one or more stages in the presence of water, followed by complete or partial removal of water.
Compounds (A), modified polyalkyleneimines (B) and bleach (D) are defined above.
In one embodiment of the invention, before at least partially removing the water, at least one further component (E) for the formulation according to the invention is for example at least one surfactant, at least one enzyme, at least one enhancer At least one co-enhancer, in particular phosphorus-free enhancers, at least one alkali carrier, at least one bleach, at least one bleach catalyst, at least one bleach activator, at least one bleach stabilizer, at least one antifoam, at least one corrosion inhibitor, one It is possible to mix the above enhancer components with a buffer or a dye.
In one embodiment, the procedure comprises, in particular, spray-drying, spray granulation or consolidation by evaporating water from the formulation according to the invention in whole or in part, for example to a residual humidity in the range of 0.1 to 10% by weight. Removal by is included.
In one embodiment of the invention, the water is removed completely or partially at a pressure in the range of 0.3 to 2 bar.
In one embodiment of the invention, the water is removed completely or partially at a temperature in the range of 60 to 220 ° C.
By means of the preparation process according to the invention, the formulation according to the invention can be easily obtained.
The cleaning formulations according to the invention may be provided in packaged or unpacked form, in liquid or solid form, in single or multiphase, as tablets or in the form of other dosage units. The water content of the liquid formulation can vary from 35 to 90% water.
The invention is illustrated by the following examples.
General: In the household dishwasher, after the first cleaning of the test specimens and after the weighing and visual inspection of the glass, the test specimens were treated only with clean cotton gloves to ensure that the weight and / or visual impression of the test specimens was not distorted.
Data in% are by weight unless expressly stated otherwise.
I. Preparation of Formulations According to the Invention
The charge density of the modified polyethyleneimine (B) was always measured as follows (also: see Horn, Prog. Colloid & Polym. Sci. 1978 , 65 , 251):
1 g of the modified polyethyleneimine (B) in question was dissolved in 100 ml of deionized water. Buffer and aqueous HCl were used to establish a pH of 4.0 measured by potentiometric correction. 3 ml of aqueous solution of toluidine blue (50 mg / l of water) are added and the color will change from blue to pink with N / 400-KPVS (potassium polyvinyl sulfate) solution (Wako) with a concentration of 0.0004 meq / ml. Titration until The charge density was calculated as follows:
LA = 0.4KV
LA: charge density of the modified polyethyleneimine (B) under discussion, meq / g (milligram equivalents / g)
KV: consumption of N / 400-KPVS solution [ml]
I.1 Preparation of the Base Mixture
First, a base mixture was prepared from the feed materials according to Table 1. The feed material was dry mixed.
Table 1: Base mixtures for experimentation with formulations according to the invention and comparative formulations
All data is g.
Abbreviation:
MGDA: methylglycine diacetic acid as trisodium salt
TAED: N, N, N ', N'-tetraacetylethylenediamine
I.2 Preparation of Formulations According to the Invention
I.2.1 Preparation of Formulations 2 to 8 and Comparative Formulation V1 According to the Invention
Modified polyethyleneimine (B) according to Table 2 was used according to the following general procedure:
Polyethyleneimines according to Table 2, columns 2 and 3, and 0.7% by weight of KOH pellets (50% by weight of water, remaining KOH) relative to polyethyleneimine were introduced into a 2 liter autoclave. The mixture was heated to 120 ° C. under reduced pressure (10 mbar) and stirred at 120 ° C. for 2 hours during which time the water was removed. The autoclave was then flushed three times with nitrogen and then heated to 140 ° C. using a starting pressure of 1 bar. Thereafter, over 2 hours, ethylene oxide or propylene oxide was added according to Table 2, column 5. When the addition was complete, the mixture was stirred at 140 ° C. for an additional 3 hours. Then water or optionally other volatile compounds were removed at 90 ° C. under reduced pressure (10 mbar). This gave the modified polyethyleneimine (B) according to the table as a solid, such as a pale yellow wax.
Table 2: Modified Polyethylenimine (B)
Abbreviations in Table 2:
AO: alkylene oxide
Column 2: M w PEI refers to the molecular weight of the polyethyleneimine used for the alkoxylation, ie the non-modified polyethyleneimine.
Column 3: PEI refers to non-modified polyethyleneimine.
Column 7: molar fraction refers to the starting component.
Column 8: Weight fraction of alkylene oxide in the total alkoxylated alkyleneimine polymer (B) under discussion.
step:
20 ml of distilled water were placed in a 100 ml beaker and the modified polyethyleneimine (B) according to Tables 2 and 3 was added with stirring.
Then stirring was carried out for 10 minutes. MGDA trisodium salt (A.1) dissolved in 30 ml of water was then added according to Table 3. This gave a clear and clear solution. The base mixture according to Table 3 was then added, the mixture was stirred again and water was evaporated.
In the test, when the corresponding fraction of the base mixture is measured separately from an aqueous solution of (A.1), (B), (C.1) or (D.1), the dried formulation is used with the same amount of active ingredient. The same results are obtained as in the case of the test. Therefore, the order of the measured additions is not important.
II. Use of the formulation according to the invention and the comparative formulation for the mechanical cleaning of glass
General: In the household dishwasher, after the first cleaning of the test specimens and after the weighing and visual inspection of the glass, the test specimens were treated only with clean cotton gloves to ensure that the weight and / or visual impression of the test specimens was not distorted.
Tests of the formulations according to the invention and comparative formulations were carried out as follows.
II.1 Test Methods for Dishwashers Using Continuous Operation
Dishwasher: Miele G 1222 SCL
Program: 65 ° C (with prewash)
Crockery: 3 "GILDE" Champagne glasses, 3 "INTERMEZZO" brandy glasses
For cleaning, the glasses were aligned with the top dish basket of the dishwasher. The dishwashing detergents used were in each case 25 g of the formulation according to the invention or 25 g of the comparative formulation according to Table 3, which in each case individually contained the active ingredient (A.1), base of the formulation according to the invention. Mixtures, silicates (C.1 or C.2) and compounds (D) and / or (E) and (B) are specified. Washing was carried out at a wash-rinse temperature of 55 ° C. Water hardness ranged from 0 to 2 ° German hardness in each case. The wash was performed in each case for 100 wash cycles, ie the program was left to run 100 ×. Weighing and visual evaluation after 100 wash cycles.
The weight of the glass was measured before the start of the first wash cycle and after drying after the last wash cycle. The weight loss is the difference between the two values.
In addition to the gravimetric evaluation, a visual evaluation of the vessel after 100 cycles in the dark room where light enters from behind the perforated plate was performed using a rating scale of 1 (very poor) to 5 (very good). In this connection, in each case a rating is given for patch type corrosion / clouding and / or line corrosion.
Experimental procedure:
First, for the purpose of pretreatment, the specimens were removed in a household dishwasher (Bosch SGS5602) with 1 g of surfactant (nC 18 H 37 (OCH 2 CH 2 ) 10 OH) and 20 g of citric acid in order to remove any dirt. Washing with water. The test bodies were dried and their weights were fixed and fixed to the grid base inserts.
To evaluate gravimetric wear, the dry test bodies were weighed. Thereafter, visual evaluation of the test body was performed. For this purpose, the surface of the test specimens was evaluated in relation to line corrosion (score line) and cloud pattern corrosion (patch type cloud pattern).
The evaluation was carried out according to the following plan.
Line corrosion:
L5: Line is not clear
L4: slight line formation in very small areas, fine line corrosion
L3: line corrosion in some areas
L2: Line corrosion in multiple areas
L1: noticeable line corrosion
Glass cloud
L5: Cloud pattern is not clear
L4: Slight cloudiness in very small areas
L3: Clouds in some areas
L2: Clouds over multiple areas
L1: Significant cloud pattern over virtually the entire glass surface
In the case of the test, intermediate grades (eg L3-4) were also accepted.
When hard water with 2 ° German hardness instead of water was used for the test, the formulations according to the invention were always superior to the corresponding comparative formulations as far as glass corrosion inhibition was concerned.
II.3 Results
The results are summarized in Table 3.
Table 3: Test results with dishwasher (continuous work)
In the example according to the invention only slight glass corrosion is established or even glass corrosion is not always established.
Claims (15)
(A) at least one aminocarboxylate in the range of from 1 to 50 weight percent in total, selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetate (GLDA), and salts thereof, and
(B) an average molecular weight in the range of 800 to 25 000 g / mol, having a positive charge density of at least 5 meq / g and having an alkylene oxide side chain in the range of from 2 to up to 80% by weight relative to the total alkoxylated alkyleneimine polymer At least one alkoxylated alkyleneimine polymer in the range of 0.001 to 2% by weight of M w .
(B) an average molecular weight in the range of 800 to 25 000 g / mol, having a positive charge density of at least 5 meq / g and having an alkylene oxide side chain in the range of from 2 to up to 80% by weight relative to the total alkoxylated alkyleneimine polymer One or more alkoxylated alkyleneimine polymers of M w ,
And optionally the additional ingredients are mixed with one another in at least one step in the presence of water and then the water is removed completely or partially.
Applications Claiming Priority (21)
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| US201261637901P | 2012-04-25 | 2012-04-25 | |
| US201261637891P | 2012-04-25 | 2012-04-25 | |
| EP12165550 | 2012-04-25 | ||
| EP12165545.0 | 2012-04-25 | ||
| US61/637,891 | 2012-04-25 | ||
| EP12165550.0 | 2012-04-25 | ||
| US61/637,901 | 2012-04-25 | ||
| EP12165556 | 2012-04-25 | ||
| EP12165556.7 | 2012-04-25 | ||
| EP12165545 | 2012-04-25 | ||
| EP12168044.1 | 2012-05-15 | ||
| EP12168054 | 2012-05-15 | ||
| EP12168044 | 2012-05-15 | ||
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| US201261697817P | 2012-09-07 | 2012-09-07 | |
| EP12183437 | 2012-09-07 | ||
| EP12183437.8 | 2012-09-07 | ||
| US61/697,817 | 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 |
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| KR102007148B1 true KR102007148B1 (en) | 2019-08-05 |
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| JP (1) | JP6133971B2 (en) |
| KR (1) | KR102007148B1 (en) |
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| BR (1) | BR112014026565A2 (en) |
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| WO2014173473A1 (en) * | 2013-04-23 | 2014-10-30 | Basf Se | Formulations, use thereof as or for production of dishwashing detergents and production thereof |
| ES2632465T3 (en) * | 2013-02-28 | 2017-09-13 | Basf Se | Formulations, their use as or for the preparation of dishwashing products and their preparation |
| US9994797B2 (en) * | 2013-04-02 | 2018-06-12 | Basf Se | Formulations, preparation thereof, and use thereof as, or for preparing, dishwashing compositions |
| KR102205587B1 (en) * | 2013-05-27 | 2021-01-20 | 바스프 에스이 | Aqueous solutions containing a complexing agent in high concentration |
| JP2015086295A (en) * | 2013-10-30 | 2015-05-07 | 花王株式会社 | Dishwashing detergent composition |
| EP3224338B1 (en) * | 2014-11-26 | 2019-04-17 | Basf Se | Aqueous solution containing combination 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 |
| RU2742268C2 (en) | 2016-06-20 | 2021-02-04 | Басф Се | Powders and granules and method of producing 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 |
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| ES2412684T3 (en) * | 2009-06-19 | 2013-07-12 | The Procter & Gamble Company | Liquid dishwashing detergent composition by hand |
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2013
- 2013-04-23 CN CN201380033256.6A patent/CN104379717B/en not_active Expired - Fee Related
- 2013-04-23 RU RU2014147082A patent/RU2623440C2/en active
- 2013-04-23 CA CA2871210A patent/CA2871210A1/en not_active Abandoned
- 2013-04-23 BR BR112014026565A patent/BR112014026565A2/en not_active Application Discontinuation
- 2013-04-23 WO PCT/EP2013/058391 patent/WO2013160301A1/en active Application Filing
- 2013-04-23 EP EP13720303.0A patent/EP2841549B1/en active Active
- 2013-04-23 KR KR1020147032948A patent/KR102007148B1/en active IP Right Grant
- 2013-04-23 ES ES13720303.0T patent/ES2612342T3/en active Active
- 2013-04-23 PL PL13720303T patent/PL2841549T3/en unknown
- 2013-04-23 JP JP2015507501A patent/JP6133971B2/en not_active Expired - Fee Related
- 2013-04-23 MX MX2014013009A patent/MX2014013009A/en unknown
- 2013-10-07 ES ES13774145.0T patent/ES2693772T3/en active Active
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| WO1999005248A1 (en) | 1997-07-23 | 1999-02-04 | Unilever Plc | Automatic dishwashing compositions containing water soluble cationic or amphoteric polymers |
| JP2008050410A (en) | 2006-08-22 | 2008-03-06 | Diversey Ip Internatl Bv | Granular cleanser composition for automatic tableware washer and method for producing the composition, and method for using the composition |
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| JP6133971B2 (en) | 2017-05-24 |
| ES2693772T3 (en) | 2018-12-13 |
| EP2841549A1 (en) | 2015-03-04 |
| CN104379717A (en) | 2015-02-25 |
| KR20150013593A (en) | 2015-02-05 |
| ES2612342T3 (en) | 2017-05-16 |
| CN104379717B (en) | 2017-08-11 |
| BR112014026565A2 (en) | 2017-06-27 |
| MX2014013009A (en) | 2015-08-06 |
| RU2623440C2 (en) | 2017-06-26 |
| PL2841549T3 (en) | 2017-04-28 |
| EP2841549B1 (en) | 2016-10-26 |
| WO2013160301A1 (en) | 2013-10-31 |
| RU2014147082A (en) | 2016-06-10 |
| CA2871210A1 (en) | 2013-10-31 |
| JP2015515531A (en) | 2015-05-28 |
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