KR20150013593A - 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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- KR20150013593A KR20150013593A KR1020147032948A KR20147032948A KR20150013593A KR 20150013593 A KR20150013593 A KR 20150013593A KR 1020147032948 A KR1020147032948 A KR 1020147032948A KR 20147032948 A KR20147032948 A KR 20147032948A KR 20150013593 A KR20150013593 A KR 20150013593A
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- KR
- South Korea
- Prior art keywords
- formulation
- weight
- acid
- range
- imine polymer
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 110
- 238000009472 formulation Methods 0.000 title claims abstract description 92
- 239000003599 detergent Substances 0.000 title description 13
- 238000004851 dishwashing Methods 0.000 title description 13
- 238000004519 manufacturing process Methods 0.000 title description 8
- -1 alkylene imine Chemical class 0.000 claims abstract description 55
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 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 14
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 12
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004615 ingredient Substances 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 7
- 235000013922 glutamic acid Nutrition 0.000 claims abstract description 7
- 239000004220 glutamic acid Substances 0.000 claims abstract description 7
- 239000011521 glass Substances 0.000 claims description 45
- 229920002873 Polyethylenimine Polymers 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000004140 cleaning Methods 0.000 claims description 19
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 17
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 10
- 229910001385 heavy metal Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 229920000388 Polyphosphate Polymers 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 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 24
- 230000007797 corrosion Effects 0.000 description 24
- 229910052783 alkali metal Inorganic materials 0.000 description 20
- 239000003623 enhancer Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 239000007844 bleaching agent Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 238000004061 bleaching Methods 0.000 description 10
- 229920001281 polyalkylene Polymers 0.000 description 9
- 229920000768 polyamine Polymers 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 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
- 159000000000 sodium salts Chemical class 0.000 description 8
- 238000012360 testing method Methods 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
- 150000001340 alkali metals Chemical class 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 239000003054 catalyst 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
- 238000005406 washing Methods 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
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-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
- 239000002253 acid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 108090000790 Enzymes Proteins 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 5
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 5
- 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
- 229920001400 block copolymer Polymers 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 150000001991 dicarboxylic acids Chemical class 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
- 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
- 235000021317 phosphate Nutrition 0.000 description 5
- 229920005646 polycarboxylate Polymers 0.000 description 5
- 230000000007 visual effect Effects 0.000 description 5
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 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
- 238000011156 evaluation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000962 poly(amidoamine) Polymers 0.000 description 4
- 239000000243 solution Substances 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
- 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
- 239000003513 alkali Substances 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
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 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
- 150000004683 dihydrates Chemical class 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
- 150000002500 ions Chemical class 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
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000003381 stabilizer Substances 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
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-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
- 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
- 240000002234 Allium sativum Species 0.000 description 2
- 239000004382 Amylase Substances 0.000 description 2
- 108010065511 Amylases Proteins 0.000 description 2
- 102000013142 Amylases Human genes 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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 108091005804 Peptidases Proteins 0.000 description 2
- 239000004365 Protease Substances 0.000 description 2
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 2
- 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
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GHDBLWVVUWTQCG-UHFFFAOYSA-N acetonitrile;n,n-dimethylmethanamine Chemical class CC#N.CN(C)C GHDBLWVVUWTQCG-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000019418 amylase Nutrition 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 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
- 230000003628 erosive effect Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 235000004611 garlic Nutrition 0.000 description 2
- 229930182470 glycoside Natural products 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000005355 lead glass Substances 0.000 description 2
- 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
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
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- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 229940045872 sodium percarbonate Drugs 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- ZDLBWMYNYNATIW-UHFFFAOYSA-N tetracos-1-ene Chemical compound CCCCCCCCCCCCCCCCCCCCCCC=C ZDLBWMYNYNATIW-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
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- 238000011179 visual inspection Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- DNISEZBAYYIQFB-PHDIDXHHSA-N (2r,3r)-2,3-diacetyloxybutanedioic acid Chemical compound CC(=O)O[C@@H](C(O)=O)[C@H](C(O)=O)OC(C)=O DNISEZBAYYIQFB-PHDIDXHHSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- IAUGBVWVWDTCJV-UHFFFAOYSA-N 1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CCC(S(O)(=O)=O)NC(=O)C=C IAUGBVWVWDTCJV-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- NYVVVBWEVRSKIU-UHFFFAOYSA-N 2,3-dihydroxybutanedioic acid;n,n-dimethyl-2-[6-methyl-2-(4-methylphenyl)imidazo[1,2-a]pyridin-3-yl]acetamide Chemical compound OC(=O)C(O)C(O)C(O)=O.N1=C2C=CC(C)=CN2C(CC(=O)N(C)C)=C1C1=CC=C(C)C=C1 NYVVVBWEVRSKIU-UHFFFAOYSA-N 0.000 description 1
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 1
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- 150000003852 triazoles Chemical class 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
- 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 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
- 238000005303 weighing Methods 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
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- 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
- 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
- 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
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) at least one aminocarboxylate 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 of 800 to 25 000 g / mole, with an alkylene oxide side chain in the range of 2 to 80% by weight, with a positive charge density of 5 meq / g or more for the total alkoxylated alkylene imine polymer M w of at least one alkoxylated alkylene imine polymer.
Description
The present invention relates to formulations comprising the following ingredients:
(A) at least one aminocarboxylate 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 / mole, with an alkylene oxide side chain in the range of 2 to 80% by weight, with a positive charge density of 5 meq / g or more for the total alkoxylated alkylene imine polymer Mw of at least one alkoxylated alkylene imine polymer.
In addition, the invention relates to a process for the preparation of the formulations according to the invention and to dishwashing detergents, in particular as dishwashing detergents for mechanical dishwashing or their use for making them.
Dishwashing detergents must meet a number of requirements. For example, they must clean the vessel as a whole, and they must not have harmful or potentially harmful components in the wastewater, and they must allow the water to flow down and dry out of the vessel, and they must not cause problems during operation of the dishwasher do. Finally, they should not cause aesthetically undesirable consequences on the article to be cleaned. In this regard, glass corrosion is particularly mentioned.
Glass corrosion is mainly promoted by chemical influences as a result of mechanical influences, for example by rubbing the glass together or as a result of mechanical contact between the glass and parts of the dishwasher. For example, certain ions can dissolve out of the glass as a result of repeated machine cleaning, which can badly deform the optics and modify the aesthetic properties.
Several effects are observed in relation to glass corrosion. First, the formation of microscopic microcracks is observed, which can be noticed by the formation of lines. Secondly, in many cases, normal cloudiness can be observed (for example, making the glass under discussion seem unseemly). The effect of this type is again divided again into patches and circular cloud patterns as well as scintillation, scoring.
WO 2006/108857 describes alkoxylated polyethyleneimines as additives to detergents. By way of example, detergents containing zeolites or polyaminocarboxylates such as EDTA or triethylenediamine pentaacetate as complexing agents are described.
WO 01/96516 discloses formulations comprising alkoxylated polyethyleneimine for hard surface cleaning. Purified water is used for rinsing.
WO 2010/020765 proposes a dishwashing detergent comprising polyethylene imine. This type of dishwashing detergent may be phosphate containing or phosphate free. They contribute to good inhibition of glass corrosion. Zinc-containing and bismuth-containing dishwashing detergents are disappointing. Glass corrosion, especially lead corrosion and cloud pattern, however, is still not adequately retarded or prevented in many cases.
It was therefore an object to provide formulations which are suitable as dishwashing detergents or for their manufacture and which overcome the drawbacks known from the prior art and which inhibit the glass corrosion or reduce this particularly well at least. It was also an object to provide a process for the preparation of a formulation which is suitable as a dishwashing detergent or for its preparation and overcomes the disadvantages known from the prior art. It was also aimed to provide the use of the formulation.
Thus, the initially defined formulation was found and is also briefly referred to as the formulation according to the invention.
There is no heavy metal in the formulation according to the present invention. In the context of the present invention, this is understood to mean that the formulations according to the invention do not contain these heavy metal compounds, in particular iron and bismuth, which do not act as bleaching catalysts. With respect to heavy metal compounds, in the context of the present invention, "is absent" means that the content of heavy metal compounds which do not act as bleaching catalyst is measured by the Leach method and is in the range of 0 to 100 ppm Range < / RTI > Preferably, the formulations according to the present invention have a heavy metal content of less than 0.05 ppm, based on the solids content of the formulation being discussed.
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 formulation according to the present invention does not comprise a measurable fraction of zinc and bismuth compounds (i.e. less than 1 ppm, for example).
The formulation according to the invention comprises the following components:
(A) at least one aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetate (GLDA), and salts thereof, also in the context of the present invention short aminocarboxylate (A) or other compound (A), and preferably a salt thereof.
Preferably, the compound (A) is selected as a free acid, particularly preferably a partially or fully neutralized form, i.e., a salt. Suitable counter ions include, for example, inorganic cations such as ammonium, alkali metal or alkaline earth metals, preferably Mg 2+ , Ca 2+ , Na + , K + , or organic cations, preferably one or more organic radicals N, N-diethanolammonium, N-mono-C 1 -C 4 -alkyldiethanolammonium, such as N-methyldiethanolammonium or N, N-butyldiethanolammonium, and N, N-di-C 1 -C 4 -alkylethanolammonium.
Very particularly preferred compounds (A) are alkali metal salts, especially sodium salts, of methylglycine diacetate (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetate (GLDA).
Very particularly preferably, methylglycine diacetate (MGDA), iminodisuccinic acid (IDA) or glutamate diacetate (GLDA) is completely neutralized.
In addition, the formulations according to the invention comprise the following ingredients:
(B) an alkylene oxide side chain having a positive charge density of 5 meq / g or more and 2 to 80 wt%, preferably 5 to 60 wt%, based on the total alkoxylated alkylene imine polymer. 25 000 g / mol average molecular weight of at least one alkoxylated alkylene imine polymers of M w in the range.
In the context of the present invention, modified alkylene imine polymers of this type are also referred to as short modified polyalkyleneimines (B).
In the context of the present invention, an alkylene imine polymer is understood to mean a polymeric material obtained by homopolymerization or copolymerization of one or more cyclic imines, or by grafting (co) polymers into one or more cyclic imines . Examples are polyalkylene polyamines grafted with ethyleneimine and polyamidoamines.
In the context of the present invention, the polyalkylene polyamines preferably contain at least 6 nitrogen atoms and at least 5 C 2 -C 10 -alkylene units, preferably C 2 -C 3 -alkylene units per molecule ≪ / RTI > such as pentaethylene hexamine, and especially polyethyleneimine.
Alkylene imine polymers, in particular polyethylene imine may be, for example, more than 300 g / mol having a number average molecular weight (M w); Preferably, the average molecular weight of the polyethyleneimine is in the range of 800 to 20 000 g / mole, as confirmed by light scattering.
The polyalkylene polyamine is an alkylene imine polymer and can be partially modified in a quaternized (alkylated) form. Suitable quaternizing agents (alkylating agents) include, for example, alkyl halides, especially C 1 -C 10 -alkyl chlorides such as methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, n- Butyl chloride, n-hexyl chloride, also epichlorohydrin, dimethyl sulphate, diethyl sulphate and benzyl chloride. When the quaternized (alkylated) polyalkylene polyamine is covalently modified as the alkylene imine polymer, the degree of quaternization (alkylation) is preferably from 1 to 10, preferably from 1 to 4, 25, and particularly preferably not more than 20 mol%.
In addition, polyimidoamines grafted with ethyleneimine are suitable as alkyleneimine polymers. Suitable polyamidoamines are obtainable, for example, by reacting a C 4 -C 10 -dicarboxylic acid with a polyalkylene polyamine preferably containing from 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 a mixture of the above-mentioned dicarboxylic acids, for example, a mixture of adipic acid and glutaric acid or a mixture of maleic acid and adipic acid. It is preferable to use adipic acid to prepare polyamidomaine. Suitable polyalkylene polyamines to be condensed with the above-mentioned dicarboxylic acids are, for example, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine And bis-aminopropylethylenediamine. The above-mentioned polyalkylene polyamines can also be used in the form of mixtures in the preparation of polyamidomines. The preparation of the polyamidomas can preferably take place without dilution, but may also optionally be carried out in an inert solvent. Condensation of dicarboxylic acids with polyalkylene polyamines takes place at elevated temperatures, for example in the range of 120 to 220 占 폚. The water formed during the reaction is distilled off from the reaction mixture. Condensation may optionally be carried out in the presence of a lactone or lactam of a carboxylic acid having from 4 to 8 carbon atoms. Generally, 0.8 to 1.4 moles of polyalkylene polyamine is used per mole of dicarboxylic acid. Polyamideamines that can be used in this manner are water soluble with primary and secondary NH groups.
Polyimidoamines grafted with ethyleneimine are prepared by reacting ethyleneimine with the polyimidoamine phase described above in the presence of Bronstedt acid or Lewis acid, such as sulfuric acid, phosphoric acid or boron trifluoride etherate As shown in FIG. As a result, ethyleneimine is grafted onto the polyamidoamine phase under discussion. For example, from 1 to 10 ethyleneimine units per basic nitrogen atom in polyamidoamine can be grafted, i.e. about 10 to 500 parts by weight of ethyleneimine per 100 parts by weight of polyamidomine.
A preferred alkylene imine polymer is polyethyleneimine.
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 determined, for example, by 13 C-NMR spectroscopy, preferably in D 2 O, and is defined as follows:
DB = D + T / D + T + L
Wherein L (linear) corresponds to the portion of the secondary amino group, and T (terminal) corresponds to the portion of the primary amino group), wherein D (resinous) corresponds to the portion of the tertiary amino group.
In the context of the present invention, the highly branched polyethyleneimine is a polyethyleneimine having a DB in the range of from 0.1 to 0.95, preferably in the range of from 0.25 to 0.90, particularly preferably in the range of from 0.30 to 0.80, very particularly preferably of at least 0.5 .
In an embodiment of the present invention, polyethyleneimine is from 600 to 20 000 g / mol range, preferably from 800 to 15, a highly branched polyethylene imine having an average molecular weight M w in the range from 000 g / mol (homopolymer) to be.
In the context of the present invention, the alkylene imine polymer is used in a covalently modified form, and specifically it is used in an amount of from 2 to 80% by weight, preferably from 5 to 60% by weight, based on the total alkoxylated alkylene imine polymer (B) Lt; RTI ID = 0.0 > alkylene < / RTI > In the case of alkoxylation, epoxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide or epichlorohydrin may 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 alkylene imine polymer (B), a range of 5 to 60 mole percent of the nitrogen atoms of the primary and secondary amino groups of the alkylene imine polymer is alkoxylated.
In one embodiment of the invention, the modified alkyleneimine (B) is selected from polyethyleneimines which have been reacted with ethylene oxide or propylene oxide.
The modified polyalkyleneimine (B) may have a high molecular weight or a low molecular weight anion (organic or preferably inorganic) as a counterion. In the context of the present invention, the high molecular weight anions have an average molecular weight of at least 200 g / mole, for example less than 2500 g / mole, and low molecular weight anions have a molecular weight of less than 200 g / mole, for example from 17 to 150 g / . 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 hydrogen carbonate.
In one embodiment of the present invention, the modified polyalkyleneimine (B) has a cationic charge density of at least 5 meq / g (milligram equivalent / g) and preferably at most 22 meq / g , And data in g units refer to a modified polyalkyleneimine (B) that does not take counter ions into consideration. The cationic charge density can be ascertained, for example, by titration using a polyvinyl sulphate solution, for example.
In one embodiment of the invention, the modified polyalkyleneimine (B) has a molecular weight distribution M w / M n in the range of from 1.1 to 10, preferably from 1.5 to 5.
In one embodiment of the invention, the formulations according to the invention are characterized in that for each case the solids content of the formulation being discussed,
Amino carboxylates (A) in a total amount of 1 to 50% by weight, preferably 10 to 25% by weight,
(B) in the range of 0.001 to 5 wt%, preferably 0.02 to 0.5 wt%, based on the total amount of the modified polyalkyleneimine (B).
In one variation of the present invention, the formulation according to the invention comprises the compound (A) and the modified polyalkyleneimine (B) in a weight ratio ranging from 1000: 1 to 25: 1.
In a preferred embodiment of the invention, the formulations according to the invention are free of phosphates and polyphosphates and (including also hydrogen phosphates), for example 3-sodium phosphate, 5-sodium tripolyphosphate and 6-sodium metaphosphate. With respect to phosphates and polyphosphates, in the context of the present invention, "is absent" is understood to mean that the content of phosphate and polyphosphate is in the range of 10 ppm to 0.2% by weight, .
The formulations according to the invention may, for example, comprise additional ingredients which are advantageous for use in the cleaning of dishes and / or kitchen appliances.
In another embodiment of the present invention, the formulations according to the invention do not contain additional ingredients which are advantageous for use, for example, in the cleaning of dishes and / or kitchen appliances, but can be easily formulated with additional ingredients Therefore, it is suitable as a 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 comprises
(D) at least one compound selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate (also referred to in the context of the present invention as "bleaching agent (D)").
Preferred bleaching agents (D) are selected from sodium perborate, anhydride or, for example, monohydrate or as a dihydrate or so-called dihydrate, as sodium percarbonate, anhydrous or as monohydrate, and sodium persulfate , The term "persulfate" includes in each case peracid H 2 SO 5 and also salts of peroxodisulfate.
In this connection, the alkali metal salts may in each case also be alkali metal hydrogen-carbonates, alkali metal hydrogen perborates and alkali metal hydrogen persulfates. However, in each case, a dialkali metal salt is preferred.
In one embodiment of the invention, the formulations according to the invention comprise, in each case, from 0 to 50% by weight of sodium citrate (C), preferably from 0 to 50% by weight, (D) a total of 0 to 15% by weight, selected from sodium citrate (C), alkali metal percarbonate, alkali metal perborate and alkali metal persulfate, in an amount of 1 to 30% by weight, particularly preferably 5% , Preferably at least 0.5 wt% bleaching agent (D).
In one embodiment of the invention, the formulation according to the invention is a solid at room temperature, for example a powder or tablet. In another embodiment of the invention, the formulation according to the invention is a liquid at room temperature. In one embodiment of the invention, the formulation according to the invention is a granule, a liquid preparation or a gel.
In one embodiment of the invention, the formulations according to the invention comprise from 0.1 to 10% by weight of water, based on the sum of all solids of the formulation being discussed.
In one embodiment of the invention, the formulation according to the invention comprises a further component (E), for example one or more surfactants, one or more enzymes, one or more enhancers, in particular phosphorus-free enhancers, At least one bleaching agent, at least one bleaching stabilizer, at least one defoaming agent, at least one corrosion inhibitor, at least one enhancer component, at least one enhancer component, at least one bleaching agent, at least one bleaching catalyst, at least one bleaching catalyst, at least one bleach activator, One or more disintegrants, one or more thickeners, or one or more soluble accelerators.
Examples of surfactants are, in particular, nonionic surfactants and also mixtures of anionic or zwitterionic surfactants with nonionic surfactants. Preferred nonionic surfactants include alkoxylated alcohols and alkoxylated fatty alcohols, di- and multi-block copolymers of ethylene oxide and propylene oxide, sorbitan and ethylene oxide or propylene oxide, alkyl glycosides and so-called amine oxides Lt; / RTI >
Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (I)
(Wherein the variables are defined as follows:
R 1 is the same or different and is selected from linear C 1 -C 10 -alkyl, preferably in each case identical and ethyl and especially 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 selected from the group consisting of C 1 -C 10 -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- N-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or isodecyl,
m and n are in the range of 0 to 300, and the sum of n and m is 1 or more. 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)
(Wherein the variables are defined as follows:
R 1 is the same or different and is selected from linear C 1 -C 10 -alkyl, preferably in each case identical and ethyl and especially 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,
and 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 non-ionic surfactants are selected from di- and multi-block copolymers composed 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 non-ionic 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 surface active agents are C 8 -C 20 -alkyl sulfates, C 8 -C 20 -alkyl sulfonates and C 8 -C 20 -alkyl ether sulfates having from 1 to 6 ethylene oxide units per molecule to be.
In one embodiment of the invention, the formulation according to the invention may comprise from 3 to 20% by weight of a surfactant.
The formulations according to the invention may comprise one or more enzymes. Examples of enzymes are lipase, hydrolase, amylase, protease, cellulase, esterase, pectinase, lactase and peroxidase.
The formulations according to the invention can in each case comprise, for example, up to 5% by weight, preferably from 0.1 to 3% by weight, of the enzyme, based on the total solids content of the formulation according to the invention.
In addition to sodium citrate (C), the formulations according to the invention may comprise at least one enhancer, in particular a phosphate-free enhancer. Examples of suitable enhancing agent is a silicate, in particular sodium disilicate and sodium metasilicate, zeolites, sheet silicates, in particular the general formula α-Na 2 Si 2 O 5 , β-Na 2 Si 2 O 5, and δ-Na 2 Si 2 O 5 And fatty acid sulphonates, alpha -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, polycarboxylate and polyaspartic acid.
In one embodiment of the present invention, the enhancer is selected from polycarboxylates, for example, 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 from 2000 to 40 000 g / mol, preferably from 2000 to 10 000 g / mol, especially from 3000 to 8000 g / mol. Also suitable are copolymeric polycarboxylates, in particular copolymeric polycarboxylates of acrylic acid and methacrylic acid, and copolymeric polycarboxylates of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid.
Also included are 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 include, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins having 10 or more carbon atoms or mixtures thereof such as 1-decene, 1-hexadecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-dococene, 1-tetracosene and 1-hexacosene, C 22 -alcohole, C 20 -C 24- And polyisobutene 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 functionality or alkylene oxide groups. (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypoly (propylene oxide) acrylate, methoxypolyethylene glycol (meth) (Meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate and ethoxypoly (Propylene oxide-co-ethylene oxide) (meth) acrylate can be mentioned. Polyalkylene glycols may contain from 3 to 50, especially from 5 to 40, especially from 10 to 30, alkylene oxide units per molecule.
Particularly preferred sulfon-acid-group-containing monomers are selected from the group consisting of 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2- 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 methacrylate, Sulfomethacrylamide, sulfomethylmethacrylamide, and the salts of such acids, such as the sodium, potassium or ammonium salts thereof.
Particularly preferred phosphonate-group-containing monomers are vinyl phosphonic acid and its salts.
In addition, an ampholytic polymer may also be used as the enhancer.
The formulations according to the invention may comprise, for example, a total of 10 to 50% by weight, preferably up to 20% by weight of augmenting agent.
In one embodiment of the invention, the formulations according to the invention may comprise one or more auxiliary-enhancers.
Examples of auxiliary-enhancers are phosphonates, such as hydroxyalkane phosphonates and aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is particularly important as a co-enhancer. It is preferably used as a sodium salt, a disodium salt to provide a neutral reaction, and a tetrasodium salt of an alkaline reaction (pH 9). Suitable aminoalkanephosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepenta methylenephosphonate (DTPMP) and its higher order homologues. They are preferably used in the form of a neutrally reacting sodium salt, for example as a 6 sodium salt of EDTMP or as a 7- and 8 sodium salt of DTPMP.
The formulations according to the invention may comprise one or more alkali carriers. The alkali carrier ensures a pH of, for example, 9 or more when the alkali pH is desired. Suitable are, for example, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal hydroxides and alkali metal meta silicates. The preferred alkali metal is in each case potassium, 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 include, 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.
The formulations according to the invention may, for example, comprise chlorine-containing bleaches in the range from 3 to 10% by weight.
Formulations according to the present invention may comprise one or more bleach catalysts. The bleaching catalyst may be selected from bleach-replenishing 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 present invention may also comprise one or more bleaching activators such as N-methylmorpholinium-acetonitrile salts ("MMA salts"), trimethylammonium acetonitrile salts, N-acrylimides such as, for example, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine ("DADHT") or nitrile quat (trimethylammonium acetonitrile salt) .
Additional examples of suitable bleach activators are tetraacetyl ethylenediamine (TAED) and tetraacetyl hexylenediamine.
The formulations according to the invention may comprise one or more corrosion inhibitors. In this case, this is intended to include the above compounds which inhibit corrosion of the metal. Examples of suitable corrosion inhibitors are triazoles, especially benzotriazole, bisbenzotriazole, aminotriazole, alkylaminotriazole, also phenolic derivatives such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, Is fluoroglucinol or pyrogallol.
In one embodiment of the invention, the formulation according to the invention comprises a corrosion inhibitor in a total amount of 0.1 to 1.5% by weight.
The formulations according to the invention may comprise one or more enhancer components, for example sodium sulfate.
The formulations according to the invention may comprise, for example, one or more defoamers, selected from silicone oils and paraffin oils.
In one embodiment of the invention, the formulation according to the invention comprises a defoamer in the total range of 0.05 to 0.5% by weight.
Formulations according to the present invention may comprise phosphonic acid or one or more phosphonic acid derivatives, such as hydroxyethan-1,1-diphosphonic acid.
The invention further provides the use of the formulations according to the invention for machine cleansing of bowls and kitchen appliances. Within the scope of the present invention, kitchen appliances which may be mentioned are, for example, pots, pans, steamed pots and also products made of metal, such as large spoons with holes, fish slices and garlic presses.
Preferably, there is provided the use of a formulation according to the invention for machine cleaning of an article having one or more surfaces made of glass which may or may not be decorated. In this context, in the context of the present invention, it is understood that a surface made of glass means that the article under discussion has at least one zone made of glass that comes into contact with ambient air and becomes dirty during use. Thus, the article under discussion may be made essentially of glass, such as a glass or glass bowl. However, they may also be, for example, lids having individual components made of different materials, for example a pot lid with a rim and handle made of metal.
Surfaces made of glass can be decorated, for example colored, stamped, or not decorated.
The term "glass " includes any desired type of glass, for example lead glass, especially soda-lime glass, crystal glass and borosilicate glass.
Preferably, the machine is cleaned by a dishwasher (automatic dishwashing).
In one embodiment of the invention, one or more formulations according to the invention are used for machine cleaning of glassware, glass vases and glass containers for cooking.
In one embodiment of the invention, for cleaning, water with a hardness in the range of 1 to 30 degrees German hardness, preferably in the range of 2 to 25 degrees German hardness is used (German hardness is in particular indicative of calcium hardness Understood).
Likewise, for rinsing, it is also possible to use water having a hardness in the range of 1 to 30 ° German hardness, preferably in the range of 2 to 25 ° German hardness.
When a formulation according to the invention is used for machine cleaning, even in the case of repeated machine cleaning of products with one or more surfaces made of glass, and in the case of products with one or more surfaces made of glass, When cleaned with a dish, only a very weak tendency toward glass corrosion is observed. In addition, it is significantly less harmful to use the formulations according to the invention for cleaning glass together with articles made of metal, for example with pots, pans or garlic presses.
In addition, it can be observed that the formulations according to the invention have 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 a formulation according to the present invention (also briefly referred to as the preparation method according to the present invention). In order to carry out the production process according to the invention, the procedure is carried out, 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 of 800 to 25 000 g / mole, with an alkylene oxide side chain in the range of 2 to 80% by weight, with a positive charge density of 5 meq / g or more for the total alkoxylated alkylene imine polymer M w of at least one alkoxylated alkylene imine polymer,
And optionally
(C) sodium citrate or
(D) at least one compound selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate,
And optionally further components (E) are mixed with one another in one or more stages in the presence of water, and then the water is completely or partially removed.
The compound (A), the modified polyalkyleneimine (B) and the bleaching agent (D) are defined above.
In one embodiment of the invention, prior to at least partial removal of the water, one or more additional components (E) for the formulation according to the invention may be added, for example one or more surfactants, one or more enzymes, At least one bleaching agent, at least one bleaching stabilizer, at least one defoaming agent, at least one corrosion inhibitor, at least one bleach activator, at least one bleach stabilizer, at least one antifoaming agent, at least one antioxidant, at least one auxiliary enhancer, It is possible to mix the above enhancer component with a buffer or a dye.
In one embodiment, the procedure may include, for example, spray-drying, spray granulation or consolidation by evaporating water from the formulations according to the invention, wholly or partly, for example in the range of from 0.1 to 10% . ≪ / RTI >
In one embodiment of the present invention, the water is completely or partially removed at a pressure in the range of 0.3 to 2 bar.
In one embodiment of the present invention, water is completely or partially removed at a temperature in the range of 60 to 220 캜.
By the production process according to the present invention, the formulations according to the present invention can be easily obtained.
The cleaning formulations according to the present invention may be provided in a liquid or solid form, in single or multi-phase, in tablets or in the form of other dosage units, in packaged or unpackaged form. The water content of the liquid formulation may vary from 35 to 90% water.
The invention is illustrated by the following examples.
General: From the first washing of the specimen in the household dishwasher, the specimen is treated only as a clean cotton glove until the weight of the glass is weighed and after visual inspection, to ensure that the weight and / or visual impression of the specimen is not distorted.
The percentages of data are by weight unless otherwise expressly stated.
I. Preparation of Formulations According to the Invention
The charge density of the modified polyethyleneimine (B) was always measured as follows (see also 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 as measured by potentiometric titration. 3 ml of an aqueous solution of toluidine blue (50 mg / l of water) was added and the color changed from blue to pink with N / 400-KPVS (potassium polyvinyl sulphate) solution (Wako) with a concentration of 0.0004 meq / ml . The charge density was calculated as follows:
LA = 0.4 KV
LA: charge density, meq / g (milligram equivalent / g) of modified polyethyleneimine (B)
KV: consumption of N / 400-KPVS solution [ml]
I.1 Preparation of base mixture
First, a base mixture was prepared from the feed material according to Table 1. The feed materials were dry mixed.
Table 1: Formulations according to the invention and base mixtures for testing with comparative formulations
All data is g.
Abbreviation:
MGDA: methylglycinediacetic acid as a 3 sodium 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
The modified polyethyleneimine (B) according to Table 2 was used which was prepared according to the following general procedure:
Polyethyleneimine according to Table 2, columns 2 and 3, and 0.7 wt% KOH pellets (polyethylene glycol with 50 wt% water content, residual KOH) for polyethyleneimine were introduced into a 2 liter autoclave. The mixture was heated to 120 < 0 > C under reduced pressure (10 mbar) and stirred at 120 [deg.] C for 2 h, during which time water was removed. The autoclave was then flushed three times with nitrogen and then heated to 140 DEG C with a starting pressure of 1 bar. Thereafter, ethylene oxide or propylene oxide was added according to Table 2, column 5 over 2 hours. When the addition was complete, the mixture was stirred at 140 < 0 > C for a further 3 hours. Water or optionally other volatile compounds were then removed at 90 [deg.] C under reduced pressure (10 mbar). Thereby, the modified polyethyleneimine (B) according to the table was calculated as a solid such as pale yellow wax.
Table 2: Modified polyethyleneimine (B)
Abbreviations in Table 2:
AO: alkylene oxide
Column 2: M w PEI refers to the molecular weight of the polyethyleneimine used for alkoxylation, i.e., the non-modified polyethyleneimine.
Column 3: PEI refers to non-modified polyethyleneimine.
Column 7: Mole fraction refers to the starting component.
Column 8: Weight fraction of alkylene oxide in total alkoxylated alkylene imine polymer (B) being discussed.
step:
20 ml of distilled water was placed in a 100 ml beaker and the modified polyethyleneimine (B) according to Tables 2 and 3 was added with stirring.
Stirring was then carried out for 10 minutes. MGDA 3 sodium salt (A.1) dissolved in 30 ml of water was then added according to Table 3 below. This resulted in a clear and transparent solution. The base mixture according to Table 3 was then added, the mixture was stirred again, and the water was evaporated.
In the test, when the corresponding fraction of the base mixture is measured separately from the aqueous solution of (A.1), (B), (C.1) or (D.1), the dried formulation is mixed with the same amount of active ingredient The same results are obtained as in the case of testing. Therefore, the sequence of the additions measured is not important.
II. Use of formulations and comparative formulations according to the invention for machine washing of glass
General: From the first washing of the specimen in the household dishwasher, the specimen is treated only as a clean cotton glove until the weight of the glass is weighed and after visual inspection, to ensure that the weight and / or visual impression of the specimen is not distorted.
Tests of formulations and comparative formulations according to the invention were carried out as follows.
II.1 Test method for dishwasher using continuous operation
Dishwasher: Miele G 1222 SCL
Program: 65 ° C (with pre-wash)
Bowl: 3 "GILDE" Champagne glass, 3 "INTERMEZZO" Brandy glass
For cleaning, the glass was aligned with the upper bowl basket of the dishwasher. The dishwashing detergent used was in each case 25 g of the formulation according to the invention or 25 g of the comparative formulation according to Table 3 and Table 3 shows in each case the active ingredient (A.1) of the formulation according to the invention, (C.1 or C.2) and compound (D) and / or (E) and (B). Washing was carried out at a rinse-rinse temperature of 55 ° C. The water hardness was in the range of 0 to 2 ° German hardness in each case. Washing was performed in each case for 100 wash cycles, i.e., the program was run at 100 x. After 100 wash cycles, weighed and visually evaluated.
The weight of the glass was measured before the beginning of the first washing cycle and after drying after the last washing cycle. Weight loss is the difference between the two values.
In addition to the gravimetric evaluation, the visual evaluation of the vessel after 100 cycles in a darkened room in the back of the perforated plate was performed using grade scales from 1 (very poor) to 5 (very good). In this regard, grades were assigned for patch type corrosion / cloud pattern and / or line corrosion in each case.
Experimental procedure:
First, for the purpose of the pretreatment, the specimen was immersed in 1 g of surfactant (nC 18 H 37 (OCH 2 CH 2 ) 10 OH) and 20 g of citric acid in a household dishwasher (Bosch SGS5602) to remove any dirt . The specimens were dried, their weights were measured, and they were fixed to the lattice base insert.
Weighing To evaluate wear, the dry test piece was weighed. A visual evaluation of the test specimens was then carried out. For this purpose, the surface of the specimen was evaluated in relation to line erosion (score line) and cloud pattern erosion (patch type cloud pattern).
Evaluation was carried out according to the following plan.
Line corrosion:
L5: Line is not clear
L4: slight line formation in very small area, fine line corrosion
L3: Line corrosion in some areas
L2: Line corrosion on multiple areas
L1: Striking line corrosion
Glass cloud pattern
L5: cloud pattern is not clear
L4: Very small area with a slight cloud pattern
L3: Cloud pattern on some areas
L2: Cloud pattern in many areas
L1: A prominent cloud pattern over substantially the entire glass surface
In the case of inspection, an intermediate rating (e.g., L3-4) was also allowed.
When hard water with 2 ° German hardness was used for the test instead of water, the formulation according to the invention was always superior to the corresponding comparative formulation, as far as glass corrosion inhibition was concerned.
II.3 Results
The results are summarized in Table 3.
Table 3: Test results using dishwasher (continuous operation)
In the examples according to the invention, only a slight glass corrosion was established or even glass corrosion was not always established.
Claims (15)
(A) at least one aminocarboxylate 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 / mole, with an alkylene oxide side chain in the range of 2 to 80% by weight, with a positive charge density of 5 meq / g or more for the total alkoxylated alkylene imine polymer M w of at least one alkoxylated alkylene imine polymer.
(A) ranging from 1 to 50% by weight in total,
Alkoxylated alkylene imine polymer (B) in a total amount of 0.001 to 2% by weight.
(B) an average molecular weight in the range of 800 to 25 000 g / mole, with an alkylene oxide side chain in the range of 2 to 80% by weight, with a positive charge density of 5 meq / g or more for the total alkoxylated alkylene imine polymer M w of at least one alkoxylated alkylene imine polymer,
10. The process according to any one of claims 1 to 9, wherein the optional ingredients are mixed with each other in one or more steps in the presence of water and then the water is completely or partially removed.
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 | ||
| EP12168038.3 | 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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| KR20150013593A true KR20150013593A (en) | 2015-02-05 |
| KR102007148B1 KR102007148B1 (en) | 2019-08-05 |
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| EP (1) | EP2841549B1 (en) |
| JP (1) | JP6133971B2 (en) |
| KR (1) | KR102007148B1 (en) |
| 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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| 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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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
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- 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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| 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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| Publication number | Publication date |
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| JP6133971B2 (en) | 2017-05-24 |
| ES2693772T3 (en) | 2018-12-13 |
| EP2841549A1 (en) | 2015-03-04 |
| CN104379717A (en) | 2015-02-25 |
| ES2612342T3 (en) | 2017-05-16 |
| CN104379717B (en) | 2017-08-11 |
| KR102007148B1 (en) | 2019-08-05 |
| 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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