EP2961822A1 - Formulations, use thereof as dishwashing detergents or for producing dishwashing detergents, and the production of said formulations - Google Patents
Formulations, use thereof as dishwashing detergents or for producing dishwashing detergents, and the production of said formulationsInfo
- Publication number
- EP2961822A1 EP2961822A1 EP14702846.8A EP14702846A EP2961822A1 EP 2961822 A1 EP2961822 A1 EP 2961822A1 EP 14702846 A EP14702846 A EP 14702846A EP 2961822 A1 EP2961822 A1 EP 2961822A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polypropyleneimine
- water
- present
- formulations
- range
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 128
- 238000009472 formulation Methods 0.000 title claims abstract description 102
- 238000004851 dishwashing Methods 0.000 title description 15
- 239000003599 detergent Substances 0.000 title description 8
- 238000004519 manufacturing process Methods 0.000 title description 8
- 229920000333 poly(propyleneimine) Polymers 0.000 claims abstract description 118
- 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 15
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 9
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004220 glutamic acid Substances 0.000 claims abstract description 8
- 235000013922 glutamic acid Nutrition 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 239000011521 glass Substances 0.000 claims description 42
- 125000002947 alkylene group Chemical group 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 21
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 150000003751 zinc Chemical class 0.000 claims description 16
- 239000011701 zinc Substances 0.000 claims description 14
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 229910001385 heavy metal Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 235000021317 phosphate Nutrition 0.000 claims description 5
- 229920000388 Polyphosphate Polymers 0.000 claims description 4
- 239000001205 polyphosphate Substances 0.000 claims description 4
- 235000011176 polyphosphates Nutrition 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 230000035622 drinking Effects 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 238000010411 cooking Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 93
- -1 alkali metal salts Chemical class 0.000 description 46
- 239000003054 catalyst Substances 0.000 description 32
- 150000001875 compounds Chemical class 0.000 description 25
- 238000005260 corrosion Methods 0.000 description 25
- 230000007797 corrosion Effects 0.000 description 25
- 239000007844 bleaching agent Substances 0.000 description 22
- 239000000460 chlorine Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229910052783 alkali metal Inorganic materials 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 16
- 238000006068 polycondensation reaction Methods 0.000 description 15
- 238000004140 cleaning Methods 0.000 description 14
- 238000009833 condensation Methods 0.000 description 13
- 150000004985 diamines Chemical class 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 238000005891 transamination reaction Methods 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 150000001340 alkali metals Chemical class 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical class NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 8
- 239000001509 sodium citrate Substances 0.000 description 8
- 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 8
- 238000003756 stirring Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002736 nonionic surfactant Substances 0.000 description 7
- 239000011734 sodium Substances 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 150000003141 primary amines Chemical class 0.000 description 6
- 150000003335 secondary amines Chemical class 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- 230000000007 visual effect Effects 0.000 description 6
- 238000004834 15N NMR spectroscopy Methods 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 5
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 150000001414 amino alcohols Chemical class 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 229940088598 enzyme Drugs 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 5
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 150000003512 tertiary amines Chemical class 0.000 description 5
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 4
- MXZROAOUCUVNHX-UHFFFAOYSA-N 2-Aminopropanol Chemical class CCC(N)O MXZROAOUCUVNHX-UHFFFAOYSA-N 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 125000001302 tertiary amino group Chemical group 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
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-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
- 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 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 229920002873 Polyethylenimine Polymers 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 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
- 125000002091 cationic group Chemical group 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
- 239000000539 dimer Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- OQGSHLFKXYVLRR-UHFFFAOYSA-N dodecane-1,2-diamine Chemical compound CCCCCCCCCCC(N)CN OQGSHLFKXYVLRR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920005646 polycarboxylate Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- 235000014692 zinc oxide Nutrition 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
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 2
- DWANEFRJKWXRSG-UHFFFAOYSA-N 1,2-tetradecanediol Chemical compound CCCCCCCCCCCCC(O)CO DWANEFRJKWXRSG-UHFFFAOYSA-N 0.000 description 2
- QGSOEHAYJKWCAJ-UHFFFAOYSA-N 1-aminodecan-1-ol Chemical compound CCCCCCCCCC(N)O QGSOEHAYJKWCAJ-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DDHUNHGZUHZNKB-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diamine Chemical compound NCC(C)(C)CN DDHUNHGZUHZNKB-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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 2
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-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
- YOOSAIJKYCBPFW-UHFFFAOYSA-N 3-[4-(3-aminopropoxy)butoxy]propan-1-amine Chemical compound NCCCOCCCCOCCCN YOOSAIJKYCBPFW-UHFFFAOYSA-N 0.000 description 2
- 240000002234 Allium sativum Species 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical class CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- 230000009471 action Effects 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
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- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- IFIDXBCRSWOUSB-UHFFFAOYSA-N potassium;1,3-dichloro-1,3,5-triazinane-2,4,6-trione Chemical compound [K+].ClN1C(=O)NC(=O)N(Cl)C1=O IFIDXBCRSWOUSB-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- FZHCFNGSGGGXEH-UHFFFAOYSA-N ruthenocene Chemical compound [Ru+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 FZHCFNGSGGGXEH-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical compound [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 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
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [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
- 239000003381 stabilizer Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 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
- 238000010998 test method Methods 0.000 description 1
- CQTBQILMJBCTRS-UHFFFAOYSA-N tetradecane-1,1-diol Chemical class CCCCCCCCCCCCCC(O)O CQTBQILMJBCTRS-UHFFFAOYSA-N 0.000 description 1
- GPBDHSIJWBKDLE-UHFFFAOYSA-N tetradecane-1,4-diol Chemical compound CCCCCCCCCCC(O)CCCO GPBDHSIJWBKDLE-UHFFFAOYSA-N 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent 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
- 150000003852 triazoles Chemical class 0.000 description 1
- IOYXJNDDBALLFR-UHFFFAOYSA-N tridecane-1,2-diol Chemical compound CCCCCCCCCCCC(O)CO IOYXJNDDBALLFR-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 description 1
- GRXOWOKLKIZFNP-UHFFFAOYSA-N undecane-1,1-diol Chemical class CCCCCCCCCCC(O)O GRXOWOKLKIZFNP-UHFFFAOYSA-N 0.000 description 1
- XSMIOONHPKRREI-UHFFFAOYSA-N undecane-1,11-diol Chemical compound OCCCCCCCCCCCO XSMIOONHPKRREI-UHFFFAOYSA-N 0.000 description 1
- BUMVVNKGNPPUME-UHFFFAOYSA-N undecane-1,2-diol Chemical compound CCCCCCCCCC(O)CO BUMVVNKGNPPUME-UHFFFAOYSA-N 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
- 230000004580 weight loss Effects 0.000 description 1
- 239000011746 zinc citrate Substances 0.000 description 1
- 235000006076 zinc citrate Nutrition 0.000 description 1
- 229940068475 zinc citrate Drugs 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 description 1
- 239000011670 zinc gluconate Substances 0.000 description 1
- 235000011478 zinc gluconate Nutrition 0.000 description 1
- 229960000306 zinc gluconate Drugs 0.000 description 1
- 239000011576 zinc lactate Substances 0.000 description 1
- 235000000193 zinc lactate Nutrition 0.000 description 1
- 229940050168 zinc lactate Drugs 0.000 description 1
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical group [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/18—Glass; Plastics
Definitions
- the present invention relates to formulations containing
- A at least one aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and their salts, and (B) at least one polypropyleneimine which may be alkoxylated.
- MGDA methylglycine diacetate
- IDS iminodisuccinic acid
- GLDA glutamic acid diacetate
- the present invention relates to a process for the preparation of formulations according to the invention and their use as or for the production of dishwashing agents, in particular dishwasher detergents for automatic dishwashing.
- Dishwashing detergents have many requirements to fulfill. So they have to thoroughly clean the dishes, they should have no harmful or potentially harmful substances in the wastewater, they should allow the draining and drying of the water from the dishes, and they should not cause problems when operating the dishwasher. Finally, they should not lead to aesthetically undesirable consequences on the good to be cleaned.
- Glass corrosion is caused not only by mechanical effects, for example, by juxtaposition of glasses or mechanical contact of the glasses with parts of the dishwasher, but is mainly promoted by chemical influences. For example, certain ions can be released from the glass by repeated mechanical cleaning, adversely altering the optical and thus the aesthetic properties.
- Glass corrosion has several effects. On the one hand, one can observe the formation of microscopically fine cracks, which are noticeable in the form of lines. On the other hand, one can often observe a general cloudiness, for example a roughening, which makes the glass in question look unaesthetic. Overall, such effects are also subdivided into iridescent discoloration, scoring and surface and annular opacities.
- WO 2006/108857 discloses alkoxylated polyethyleneimines as additives to detergents.
- Detergents containing zeolites or polyaminocarboxylates such as EDTA or triethylenediamine pentaacetate as complexing agents are disclosed by way of example.
- WO 01/96516 proposes formulations containing alkoxylated polyethylenimine for cleaning hard surfaces.
- purified water is used for rinsing.
- dishwashing agents which contain polyethyleneimine.
- dishwashing agents may contain phosphate or be phosphate-free. It is attributed to them a good inhibition of glass corrosion.
- zinc and bismuth-containing dishes Dishwashing is not recommended. The glass corrosion, in particular the line corrosion and the turbidity, but is not sufficiently delayed or prevented in many cases.
- formulations defined above were found, also called formulations according to the invention.
- formulations according to the invention Contain formulations according to the invention
- A at least one aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and salts thereof, in the context of the present invention also referred to as aminocarboxylate (A) or compound (A), and preferably their salts.
- MGDA methylglycine diacetate
- IDS iminodisuccinic acid
- GLDA glutamic acid diacetate
- inorganic cations such as ammonium, alkali or alkaline earth metal are suitable, preferably Mg 2+, Ca 2+, Na +, K +, or organic cations, preferably with one or more organic radicals, substituted ammonium, more particularly triethanolammonium, ⁇ , ⁇ -diethanolammonium, N-mono-C 1 -C 4 -alkyldiethanolammonium, for example N-methyldiethanolammonium or Nn-butyldiethanolammonium, and N, N-di-C 1 -C 4 -alkylethanolammonium.
- inorganic cations such as ammonium, alkali or alkaline earth metal are suitable, preferably Mg 2+, Ca 2+, Na +, K +, or organic cations, preferably with one or more organic radicals, substituted ammonium, more particularly triethanolammonium, ⁇ , ⁇ -diethanolammonium, N-mono-C 1 -C 4
- Very particularly preferred compounds (A) are the alkali metal salts, in particular the sodium salts of methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA).
- MGDA methylglycine diacetate
- IDS iminodisuccinic acid
- GLDA glutamic acid diacetate
- MGDA methylglycine diacetate
- IDS iminodisuccinic acid
- GLDA glutamic acid diacetate
- Formulations according to the invention also contain
- (B) at least one polypropyleneimine which may be alkoxylated.
- Alkoxylated polypropyleneimines are also referred to in the context of the present invention as "modified polypropyleneimine (B)” or “alkoxylated polypropyleneimine (B)".
- Non-alkoxylated polypropyleneimine is also referred to in the context of the present invention as “polypropyleneimine (B)” for short.
- polypropyleneimine (B) has a molecular weight M n in the range of 300 to 4,000 g / mol, preferably 400 to 2,000 g / mol.
- modified polypropyleneimine (B) has an average molecular weight M w in the range of 800 to 25,000 g / mol.
- polypropyleneimine in the context of the present invention does not only refer to homopolymers of propylenediamine, but also to those polyalkyleneimines which, in addition to NH-CH 2 -CH 2 -CH 2 -NH units and / or NH-CH 2 -CH (CH 3 ) -NH units have other alkylenediamine units, for example NH-CH 2 -CH 2 -NH units, NH- (CH 2 ) 4 -NH units, NH- (CH 2 ) 6 -NH units or NH- (CH 2 ) 8 -NH units, but where molar are NH-CH 2 -CH 2 -CH 2 -NH units and / or NH-CH 2 -CH (CH 3) -NH units in the majority , Preferred polypyrimines have, for example, at least 60 mol% of propylene imine units per molecule, more preferably at least 70 mol%.
- polypropyleneimine refers to those polyalkyleneimines which have only one or no structural element other than NH-CH 2 -CH 2 -CH 2 -NH.
- Polypropyleneimine can be linear, predominantly linear or branched, predominantly linear is preferred, and linear is particularly preferred.
- the structure of polypropyleneimine can be controlled by the nature of the synthesis.
- Polypropyleneimine in the context of the present invention may also be referred to as polypropylene polyamines.
- Polypropyleneimines in the context of the present invention have at least 6 N atoms per molecule, for example as NH 2 groups, as secondary amino groups or as tertiary amino groups.
- Branches of polypropyleneimines may be, for example, CH 2 -CH 2 -NH 2 groups, or (CH 2 ) 3 -NH 2 units.
- larger branches can be used
- Highly branched polypropyleneimines can be, for example, polypropylene end-dendrimers or related molecules, for example with a degree of branching (DB) in the range from 0.25 to 0.95, preferably from 0.3 to 0.80 and particularly preferably from at least 0.5.
- the degree of branching of polypropyleneimines can also be determined by 13 C-NMR or 15 N-NMR spectroscopy, preferably in D 2 O, and is defined as follows:
- DB D + T / D + T + L with D (dendritic) corresponding to the proportion of tertiary amino groups, L (linear) corresponding to the proportion of secondary amino groups and T (terminal) corresponding to the proportion of primary amino groups.
- Methyl groups are not considered as branches in the context of the present invention.
- polypropyleneimines having little or no branching that is to say predominantly linear and in particular linear polypropyleneimines.
- polypropyleneimine can be prepared by catalytic polycondensation of propanolamine and optionally at least one further aminoalcohol or by catalytic polycondensation of propanediol with propandiamine and optionally at least one further diol and / or at least one further diamine.
- Polypropyleneimine is preferably prepared by catalytic polycondensation of propanediamine with optionally at least one further diamine. The latter type of polycondensation is also referred to as transamination.
- amino alcohols, diols and diamines are selected from aliphatic aminoalcohols, aliphatic diols and aliphatic diamines.
- aminopropanols are 3-amino-1-propanol, 1-amino-2-propanol and 2-amino-1-propanol and mixtures of the abovementioned aminopropanols, with 3-amino-1-propanol being preferred.
- polypropyleneimines obtainable by polycondensation of aminoalcohols
- up to 40 mole% of aminopropanol, preferably up to 30 mole% of aminopropanol may be replaced by one or more amino alcohols bearing one hydroxy group and one primary or secondary amino group per mole.
- amino alcohols are linear or branched amino alcohols, for example monoethanolamine, diethanolamine, aminobutanol, for example 4-aminobutan-1-ol, 2-aminobutan-1-ol or 3-aminobutan-1-ol, aminopentanol, for example 5-aminopentane -1 -ol or 1-aminopentan-2-ol, aminodimethylpentanol, for example 5-amino-2,2-dimethylpentanol, aminohexanol, for example 2-aminohexan-1-ol or 6-aminohexan-1-ol, aminoheptanol, for Example 2-aminoheptan-1-ol or 7-aminoheptan-1-ol, amino octanol, for example 2-aminooctan-1-ol or 8-aminooctan-1-ol, aminononanol, for example 2-aminononan-1-ol or 9
- polypropyleneimine is obtained by catalytic polycondensation of 3-aminopropan-1-ol without the addition of aminoalcohol other than 3-aminopropan-1-ol.
- propanediamines and propanediols which can be processed by poly-co-condensation to polypropyleneimine are described below.
- propanediamines are propane-1,2-diamine and propane-1,3-diamine and mixtures of the above, with propane-1,3-diamine being preferred.
- propanediols examples are propane-1,3-diol and propane-1,2-diol and mixtures of the above, with propane-1,3-diol being preferred.
- propane-1,3-diol examples of the corresponding propanediols
- propane-1,3-diol examples of the corresponding propanediols
- propane-1,3-diol examples of the corresponding propanediols
- propane-1,3-diol examples include propane-1,3-diol and propane-1,2-diol and mixtures of the above, with propane-1,3-diol being preferred.
- propane-1,3-diol examples of the corresponding propanediols are propane-1,3-diol and propane-1,2-diol and mixtures of the above, with propane-1,3-diol being preferred.
- propane-1,3-diol examples of the corresponding propanediols are propane-1,3-di
- Examples of other aliphatic diols are linear or branched diols. Specific examples are ethylene glycol, 2-methyl-1,3-propanediol, butanediols, for example 1,4-butylene glycol or butane-2,3-diol or 1,2-butylene glycol, pentanediols, for example neopentyl glycol or 1,5-pentanediol or 1, 2-pentanediol, hexanediols, for example 1, 6-hexanediol or 1, 2-hexanediol, heptanediols, for example 1, 7-heptanediol or 1, 2-heptanediol, octanediols, for example 1, 8-octanediol or 1 , 2-octanediol, nonanediols, for example 1, 9-
- Octadecanediol wherein the respective ⁇ , ⁇ -diols are preferred over their 1, 2-isomers, 3,4-dimethyl-2,5-hexanediol, ⁇ , ⁇ -diethanolamines, for example Nn-butyldiethanolamine or N-methyldiethanolamine, and others dialcoholamines.
- Preference is given to ethylene glycol.
- Examples of other aliphatic diamines are linear or branched diamines.
- ethylenediamine, butylenediamines for example 1,4-butylenediamine or 1,2-butylenediamine
- diaminopentanes for example 1,5-diaminopentane or 1,2-diaminopentane, diaminohexane, for example 1,6-diaminohexane, 1,5 Diamino-2-methylpentane or 1,2-diaminohexane
- diaminoheptane for example 1,7-diaminoheptane or 1,2-diaminoheptane
- diaminooctane for example 1,8-diaminooctane or 1,2-diaminooctane, diaminononane, for example Example 1, 9-diaminononane or 1, 2-diaminononane, diaminodecane, for example 1, 10-diaminodecane or 1, 2-diamino
- compounds having two NH 2 groups and one tertiary amino group for example N, N-bis (3-aminopropyl) methylamine, are also to be considered as diamines.
- polypropyleneimine is prepared by catalytic poly-co-condensation of 1,3-propylene glycol with 1,3-propanediamine, without the use of diols and diamines derived from 1,3-propylene glycol and 1, respectively. 3- Propandiamine are different.
- the above-described polycondensations or poly-co-condensations can be carried out in the absence or in the presence of hydrogen, for example under a hydrogen pressure in the range from 1 to 10 MPa.
- the polycondensations or poly-co-condensations described above can be carried out at a temperature in the range from 20 to 250.degree. C., preferably at least 100 and at most 200.degree.
- the water formed during the reaction can be removed, for example by distillation.
- Suitable catalysts for the above-described polycondensations or poly-co-condensations can preferably be selected from homogeneous catalysts. Suitable homogeneous catalysts can be used in activated form or activated in situ during the polycondensation or poly-co-condensation.
- catalysts for homogeneous catalysis are Ru (p-cumene) Cl 2] 2, [Ru (benzene) Cl 2] y , [Ru (CO) 2 Cl 2 ] y, where y is in the range from 1 to 1000, [Ru (CO) 3 Cl 2 ] 2, [Ru (COD) (allyl)], RuCl 3 -H 2 O, [Ru (acetylacetonate) 3 ], [Ru (DMSO) 4 Cl 2 ], [Ru (Cp) ( CO) 2 Cl], [Ru (Cp) (CO) 2 H],
- Cp means cyclopentadienyl and Cp * means pentamethylcyclopentadienyl.
- COD is cycloocta-1, 5-dienyl, Et: ethyl, Me: methyl, Ph: phenyl, n-Pr: n-propyl, n-Bu: n-butyl, bipy: 2,2'-bipyridyl.
- polypropyleneimines prepared by the polycondensation or poly-co-condensation described above have an OH number in the range of 1 to 1000 mg KOH / g, preferably 2 to 500 mg KOH / g, more preferably from 10 to 300 mg KOH / g.
- the OH number can be determined according to DIN 53240.
- polypropyleneimines prepared by the above-described polycondensation or poly-co-condensation have a primary amine value in the range of 1 to 1,000 mg KOH / g, preferably 10 to 500 mg KOH / g preferably 50 to 300 mg KOH / g.
- polypropyleneimines prepared by the polycondensation or poly-co-condensation described above have a secondary amine value in the range of 1 to 1000 mg KOH / g, preferably 10 to 500 mg KOH / g, more preferably 50 up to 300 mg KOH / g.
- the secondary amine number can be determined according to ASTM D2074-07.
- polypropyleneimines prepared by the polycondensation or poly-co-condensation described above have a tertiary amine value in the range of 1 to 300 mg KOH / g, preferably 5 to 200 mg KOH / g, more preferably 10 to 100 mg KOH / g.
- the tertiary amine number can be determined according to ASTM D2074-07.
- the molar proportion of tertiary amine nitrogens is determined by 15 N NMR spectroscopy. In cases where the tertiary amine number and the values for the tertiary amine nitrogen atoms were inconsistent by 15 N-NMR spectroscopy, the values determined by means of 15 N-NMR spectroscopy apply.
- polypropyleneimines can be obtained by catalytic transamination of propanediamine and optionally at least one further diamine.
- propanediamines are 1, 2-propanediamine and 1, 3-propanediamine. Particularly preferred are transaminations of 1, 3-propanediamine.
- up to 40 mol% of propanediamine can be replaced by one or more propanediamine-different aliphatic diamines, in particular up to 30 mol%.
- propanediamine-different aliphatic diamines are linear or branched diamines.
- ethylenediamine, butylenediamines for example 1,4-butylenediamine or 1,2-butylenediamine
- diaminopentanes for example 1,5-diaminopentane or 1,2-diaminopentane, diaminohexane, for example 1,6-diaminohexane, 1,5 Diamino-2-methylpentane or 1,2-diaminohexane
- diaminoheptane for example 1,7-diaminoheptane or 1,2-diaminoheptane
- diaminooctane for example 1,8-diaminooctane or 1,2-diaminooctane, diaminononane, for example Example 1, 9-diaminononane or 1, 2-diaminononane, diaminodecane, for example 1, 10-diaminodecane or 1, 2-diamino
- N, N-bis (3-aminopropyl) methylamine are also to be regarded as diamines.
- polyp ropylenimin by catalytic transamination of 1, 3-propanediamine, without the addition of a different of 1, 3-propanediamine diamine.
- Catalysts suitable for the transamination of propanediamine and optionally at least one further diamine are preferably heterogeneous catalysts containing at least one transition metal selected from Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt, preferably of Co, Ni, Ru, Cu and Pd, and more preferably of Co, Ni and Cu.
- transition metal selected from Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt, preferably of Co, Ni, Ru, Cu and Pd, and more preferably of Co, Ni and Cu.
- the abovementioned metals may also be referred to as "catalytically active metals" in the context of the present invention.
- a catalytically active metal may be doped with one or more promoters other than the catalytically active metal, for example with Cr, Co, Mn, Mo, Ti, Sn, alkali metal, alkaline earth metal or phosphorus.
- Raney type catalyst which can be obtained by activating an alloy of a catalytically active metal with another metal, preferably aluminum.
- Preferred are Raney nickel and Raney cobalt.
- a supported Pd catalyst or a supported Pt catalyst may be employed.
- suitable support materials are carbon, for example as activated carbon, further AI2O3, ⁇ 2, ZrÜ2 and S1O2.
- catalysts which can be obtained by reducing a catalyst precursor are particularly preference.
- Catalyst precursors contain an active mass of precursors of one or more catalytically active components, optionally one or more promoters and optionally a carrier material.
- the catalytically active components are oxygen-containing compounds of the abovementioned catalytically active metals, for example their metal oxides or hydroxides, such as CoO, NiO, CuO and / or their mixed oxides.
- the transamination of propanediamine and optionally further diamine can be carried out in the absence or in the presence of hydrogen, for example under a hydrogen pressure in the range from 1 to 400 bar, preferably up to 200 bar and particularly preferably up to 100 bar.
- the transamination of propanediamine and optionally further diamine can be carried out at a temperature in the range of 50 to 200 ° C, preferably 90 to 180 ° C and particularly preferably 120 to 160 ° C.
- the transamination of propanediamine and optionally further diamine can be carried out at a pressure in the range from 1 to 400 bar, preferably up to 200 bar and particularly preferably up to 100 bar.
- a polypropyleneimine which has no hydroxyl groups is obtained.
- the OH number according to DIN 53240 is accordingly zero. This statement naturally refers to the polypropyleneimine prior to the alkoxylation.
- polypropyleneimines prepared by the transamination described above have a primary amine value in the range of 10 to 1000 mg KOH / g, preferably 80 to 800 mg KOH / g, more preferably 100 to 500 mg KOH / g ,
- polypropyleneimines prepared by the transamination described above have a secondary amine number in the range from 100 to 2,000 mg KOH / g, preferably from 200 to 1,500 mg KOH / g, more preferably from 300 to 1, 000 mg KOH / g.
- the secondary amine number can be determined according to ASTM D2074-07.
- polypropyleneimines prepared by the transamination described above have zero to 2 mole percent tertiary amine.
- Nitrogen atoms based on all N atoms in the molecule in question.
- the molar fraction of the tertiary amine nitrogen atoms is preferably determined by 15 N-NMR spectroscopy.
- the average molecular weight M n of polypropyleneimine (B) is in the range from 300 to 4,000 g / mol, particularly preferably in the range from 400 to 2,000 g / mol.
- the average molecular weight M n can be obtained, for example, by gel permeation chromatography (GPC) or by end group analysis, for example by NMR spectroscopy.
- the width of the molecular weight distribution Mw Mn of polypropyleneimine (B) is in the range of 1.2 to 20, preferably in the range of 1.5 to 7.5.
- the cationic charge density of alkoxylated polypropyleneimine is in the range of 4 to 22 meq / g dry matter, preferably in the
- Polypropyleneimine (B) is used in one embodiment of the present invention in a covalently modified form in such a way that preferably 90 to 100 mol% of the nitrogen atoms of the primary and secondary amino groups of the polypropyleneimine (B) are alkoxylated.
- alkoxylation one can use epoxides, for example ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide or epichlorohydrin.
- Preferred alkoxylation reagents are butylene oxide, ethylene oxide and propylene oxide as well as combinations of ethylene oxide and propylene oxide. If one uses combinations of ethylene oxide and propylene oxide, it is possible to incorporate the various alkylene oxides blockwise or statistically.
- modified polypropyleneimine (B) is selected from polypropyleneimines that are alkoxylated with ethylene oxide or propylene oxide.
- alkoxylated modified polypropyleneimine (B) is used with ethylene oxide as the sole alkylene oxide.
- the molar ratio of nitrogen atoms to alkylene oxide groups in modified polypropyleneimine (B) is in the range of 1: 1 to 1: 00, preferably in the range of 1: 2 to 1:15.
- the alkoxylation of polypropyleneimine (B) can be carried out, for example, as follows, and the alkoxylation is preferably carried out as a catalytic alkoxylation.
- suitable catalysts are Lewis acids, for example AlC or BF 3 etherate, BF 3, BF 3 ⁇ 3 ⁇ 4, SbCl 2 -2H 2 O and hydrotalcite.
- Preferred catalysts are strong bases, for example potassium hydroxide, sodium hydroxide, potassium or sodium alcoholates such as, for example, potassium methylate (KOCH3), sodium methoxide (NaOCHs), potassium ethanolate, sodium ethanolate and potassium tert-butoxide.
- Other suitable strong bases are sodium hydride, calcium hydride and alkali metal carbonates such as sodium carbonate and potassium carbonate.
- Particularly preferred catalysts are alkali metal hydroxides and alkali metal alcoholates, most preferably sodium hydroxide and potassium hydroxide. In general, it is possible to use 0.05 to 10% by weight of catalyst, preferably 0.5 to 2% by weight, based on the sum of polypropyleneimine and alkylene oxide.
- the alkoxylation is carried out at a temperature in the range of 90 to 240 ° C, preferably in the range of 120 to 180 ° C, in a closed vessel, for example in an autoclave.
- the alkoxylation is carried out at a pressure in the range from 1 to 10 bar, preferably up to 8 bar.
- alkylene oxide (e) and polypropyleneimine and, if appropriate, catalyst are reacted with one another under the vapor pressure of the relevant alkylene oxide or of the mixture of the respective alkylene oxides at the selected temperature.
- Alkylene oxide (s) can be introduced in pure form or, as an alternative, in a form diluted with inert gas, for example in 30 to 60% by volume mixture.
- suitable inert gases are noble gases and in particular nitrogen.
- a dilution can be chosen, for example, as a safety measure against an explosive polyaddition of alkylene oxides.
- the various alkylene oxide units may be randomly distributed or blocky. If several alkylene oxides are introduced simultaneously into the reaction, deviations from the strict random principle during incorporation of the alkylene oxide units can result from different alkylene oxides having a different reactivity. It is possible to achieve a predetermined incorporation of the alkylene oxide units by means of a programmed feed of the alkylene oxides. If the alkylene oxides are fed in successively, a block-like distribution of the alkylene oxide units is generally obtained.
- the alkoxylation may preferably be carried out in two or more substeps, the first step being to first to analkoxylate polypropyleneimine.
- first step being to first to analkoxylate polypropyleneimine.
- polypropyleneimine with a molar number of alkylene oxide to the reaction, which corresponds to the number of primary and secondary amino groups in the respective polypropyleneimine.
- the alkoxylation is preferably carried out in aqueous solution and without catalyst.
- the alkoxylation at a reaction temperature in the range from 70 to 200 ° C., preferably in the range from 80 to 160 ° C. In one embodiment of the present invention, it is possible to carry out the alkoxylation at a pressure of up to 10 bar, preferably up to 8 bar. The lower limit is normal pressure.
- the second substep-and optionally the further substeps- can be carried out in each case in bulk, embodiment (i), or in an organic solvent, embodiment (ii).
- the water can be removed from the partial step, preferably before the addition of a water-sensitive catalyst.
- the water can be distilled off, for example, by heating to a temperature in the range of 80 to 150 ° C at a reduced pressure in the range of 0.01 to 0.5 bar. If the catalyst is insensitive to water, for example alkali metal hydroxide, it is also possible first to add the catalyst and then to remove the water.
- the further alkoxylation can be carried out at a reaction temperature in the range from 70 to 200 ° C., preferably in the range from 100 to 180 ° C.
- further alkoxylation can be carried out at a pressure of up to 10 bar, preferably up to 8 bar.
- the lower limit is normal pressure.
- the further alkoxylation is carried out over a period of 30 minutes to 12 hours.
- suitable solvents for carrying out embodiment (ii) are nonpolar and polar aprotic organic solvents.
- suitable nonpolar aprotic organic solvents are aliphatic and aromatic hydrocarbons such as n-hexane, n-heptane, cyclohexane, toluene and the various isomers of xylene.
- polar aprotic solvents examples include ethers, in particular Other cyclic ethers such as tetrahydrofuran and 1, 4-dioxane, further ⁇ , ⁇ -dialkylamides such as dimethylformamide and dimethylacetamide and N-alkyl lactams such as N-methylpyrrolidone and N-ethylpyrrolidone. It is also possible to use mixtures of two or more of the aforementioned solvents. Particularly preferred solvents are xylene, especially as a mixture of isomers, and toluene.
- embodiment (ii) it is also advantageous for embodiment (ii) to remove any water originating from the sub-step of the alkoxylation, preferably even before the addition of the catalyst, for example at a temperature in the range from 120 to 180 ° C. and at reduced temperature Pressure, for example, 0.01 to 0.5 bar, or by stripping with nitrogen.
- the further alkoxylation then takes place as in the second and, if appropriate, further substeps of embodiment (ii).
- Polypropyleneimine (B) which may be alkoxylated, may have as counter ions high molecular weight or low molecular weight anions, organic or preferably inorganic.
- High molecular weight anions in the context of the present invention have an average molecular weight of 200 g / mol or more, for example up to 2500 g / mol, low molecular weight anions have a molecular weight of less than 200 g / mol, for example from 17 to 150 g / mol.
- low molecular weight organic counterions are acetate, propionate and benzoate.
- low molecular weight inorganic counterions are sulfate, chloride, bromide, hydroxide, carbonate, methanesulfonate and bicarbonate.
- modified polypropylenimine (B) has a cationic charge density of at least 5 meq / g to preferably at most 25 meq / g (milliequivalents / g), preferably to 22 meq / g, with the indication in g being modified Polypropyleneimine (B) without consideration of the counterions relates.
- the cationic charge density can be determined, for example, by titration, for example with polyvinyl sulfate solution.
- modified polypropylene in (B) has a molecular weight distribution M w / M n in the range of 1.1 to 10, preferably 1.5 to 5.
- formulation according to the invention contains compound (A) and polypropyleneimine (B), which may be alkoxylated, in a weight ratio in the range from 1000 to 1 to 25 to 1.
- formulation according to the invention is free from Phosphates and polyphosphates, wherein hydrogen phosphates are subsumed with, for example, free of trisodium phosphate, pentasodium tripolyphosphate and Hexanatri- ummetaphosphat.
- free from in connection with phosphates and polyphosphates in the context of the present invention should be understood to mean that the total content of phosphate and polyphosphate ranges from 10 ppm to 0.2% by weight, determined by gravimetry.
- formulations according to the invention comprise at least one zinc salt.
- Zinc salts can be selected from water-soluble and non-water-soluble zinc salts.
- zinc salt is selected from zinc benzoate, zinc gluconate, zinc lactate, zinc formate, ZnC, ZnS0 4 , zinc acetate, zinc nitrate, Zn (NOs) 2,
- Zn (CH 3 SO 3 ) 2 and zinc gallate ZnC, ZnSO 4 , zinc acetate, zinc citrate, Zn (NO 2) 2, Zn (CH 3 SO 3 ) 2 and zinc gallate are preferred.
- zinc salt is selected from ZnO, ZnOaq, Zn (OH) 2 and ZnCO-3. ZnOaq is preferred.
- zinc salt is selected from zinc oxides having an average particle diameter (weight average) in the range of 10 nm to 100 ⁇ m.
- the cation in zinc salt can be complexed, for example, complexed with ammonia ligands or water ligands, and in particular be present hydrated.
- ligands are generally omitted in the context of the present invention, if they are water ligands.
- zinc salt can be converted. It is thus possible, for example, to use zinc acetate or ZnC for the preparation of the formulation according to the invention, but this converts to ZnO, Zn (OH) 2 or ZnOaq at a pH of 8 or 9 in an aqueous environment, which in non-complexed or may be in complexed form.
- Zinc salt is present in such inventive formulations, which are solid at room temperature, preferably in the form of particles, for example, have a mean diameter (number average) in the range of 10 nm to 100 ⁇ , preferably 100 nm to 5 ⁇ , determined for example by X-ray scattering.
- Zinc salt is present in such inventive formulations, which are liquid at room temperature, in dissolved or solid or in colloidal form.
- formulations according to the invention contain in total from 0.05 to 0.4% by weight of zinc salt, based in each case on the solids content of the relevant formulation.
- the proportion of zinc salt is given as zinc or zinc ions. Thus one can calculate out the portion of the Jacobions.
- formulations according to the invention are heavy-metal-free, with the exception of zinc compounds.
- this is understood to mean that formulations according to the invention are free of those heavy metal compounds which do not act as bleach catalysts, in particular compounds of iron and bismuth.
- "free from” is to be understood in connection with heavy metal compounds as meaning that the content of heavy metal compounds which do not act as bleach catalysts is in the range from 0 to 100 ppm, determined by the Leach method and based on
- the formulation according to the invention preferably has a heavy metal content of less than 0.05 ppm, based on the solids content of the relevant formulation, ie the proportion of zinc is not included.
- heavy metals all metals are in the context of the present invention having a specific density of at least 6 g / cm 3 with the exception of zinc.
- precious metals and bismuth iron, copper, lead, tin, nickel, cadmium and chromium ,
- formulation according to the invention contains no measurable proportions of bismuth compounds, that is to say, for example, less than 1 ppm.
- Formulations of the invention may contain other components which are advantageous, for example, for use in washing dishes and / or kitchen utensils.
- formulations according to the invention contain no further components which are suitable, for example, for use in the
- Rinsing dishes and / or kitchen utensils are advantageous, but can be easily formulated with other components and are therefore suitable as a starting material.
- formulations according to the invention contain sodium citrate (C).
- the term sodium citrate comprises the mono- and preferably the disodium salt with.
- Sodium citrate can be used as anhydrous salt or as a hydrate, for example as a dihydrate.
- (D) at least one compound selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate, in the context of the present invention also called “bleaching agent (D)".
- Preferred bleaching agents (D) are selected from sodium perborate, anhydrous or, for example, as monohydrate or as tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as monohydrate, and sodium persulphate, where the term "persulphate" in each case the salt of peracid H2SO5 and the Peroxodisulfate includes.
- the alkali metal salts may each also be alkali metal hydrogencarbonate, alkali metal hydrogen perborate and alkali metal hydrogen persulphate. However, preference is given in each case to the dialkali metal salts.
- formulation according to the invention comprises zero to 50% by weight of sodium citrate (C), preferably 1 to 30% by weight, particularly preferably at least 5% by weight of sodium citrate (C), determined as anhydrous sodium citrate,
- bleaching agent (D) preferably at least 0.5% by weight of bleaching agent (D), selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate.
- formulation according to the invention is solid at room temperature, for example a powder or a tablet.
- formulation of the invention is liquid at room temperature.
- the formulation according to the invention is a granulate, a liquid preparation or a gel.
- the formulation according to the invention contains from 0.1 to 10% by weight of water, based on the sum of all solids of the relevant formulation.
- formulation according to the invention may comprise further ingredients (E), for example one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus-free builders, one or more cobuilders, one or more alkali carriers, one or more several bleaches, one or more bleach catalysts, one or more bleach activators, one or more bleach stains, bilisators, one or more defoamers, one or more corrosion inhibitors, one or more builders, buffers, dyes, one or more fragrances, one or more organic solvents, one or more tabletting aids, one or more disintegrating agents, one or more thickeners, or one or more solubilizers.
- surfactants for example one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus-free builders, one or more cobuilders, one or more alkali carriers, one or more several bleaches, one or more bleach catalysts, one or more bleach activators, one or more bleach stains, bilisators, one or more defoamers,
- surfactants are, in particular, nonionic surfactants and mixtures of anionic or zwitterionic surfactants with nonionic surfactants.
- Preferred nonionic surfactants are alkoxylated alcohols and alkoxylated fatty alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl glycosides and so-called amine oxides.
- alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (I)
- variables are defined as follows: identical or different and selected from linear C 1 -C 10 -alkyl, preferably in each case identical and ethyl and particularly preferably methyl, selected from C 5 -C 22 -alkyl, for example nC & Hn, n-doF i, n- Ci2H25, nC-uF s), n-Ci6H33 selected from C 1 -C 10 -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl , neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl
- Compounds of the general formula (I) may be block copolymers or random copolymers, preference being given to block copolymers.
- alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (II) in which the variables are defined as follows:
- R 1 is identical or different and selected from linear C 1 -C 10 -alkyl, preferably in each case identical and ethyl and particularly preferably methyl,
- R 4 is selected from C 6 -C 20 -alkyl, in particular n-CsH-i, n-doH-i, n-C 12 H 25, nC-uF s), n-C 16 H 33, n
- a is a number in the range of 1 to 6,
- b is a number in the range of 4 to 20
- d is a number in the range of 4 to 25.
- these may be block copolymers or random copolymers, preference being given to block copolymers.
- suitable nonionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide.
- suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters.
- amine oxides or alkyl glycosides are also suitable.
- An overview of suitable further nonionic surfactants can be found in EP-A 0 851 023 and in DE-A 198 19 187. Mixtures of several different nonionic surfactants may also be present.
- anionic surfactants are C 8 -C 20 -alkyl sulfates, C 8 -C 20 -alkyl sulfonates and C 8 -C 20 -alkyl ether sulfates having one to six ethylene oxide units per molecule.
- formulation according to the invention may contain from 3 to 20% by weight of surfactant.
- Formulations of the invention may contain one or more enzymes.
- enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.
- Formulations according to the invention may contain, for example, up to 5% by weight of enzyme, preferably from 0.1 to 3% by weight, in each case based on the total solids content of the formulation according to the invention.
- Formulations according to the invention may comprise, in addition to sodium citrate (C), one or more builders, in particular phosphate-free builders.
- Suitable builders are silicates, in particular sodium disilicate and sodium metasilicate, zeolites, phyllosilicates, especially those of the formula a-Na 2 Si 2 O, ⁇ -Na 2 Si 2 O, and 5-Na 2 Si 2 O, furthermore fatty acid sulfonates, ⁇ -hydroxypropionic acid, alkali malonates, fatty acid sulfonates, alkyl- and alkenyl disuccina tartaric acid diacetate, tartaric acid monoacetate, oxidized starch, and polymeric builders such as polycarboxylates and polyaspartic acid.
- builders of polycarboxylates for example, alkali metal salts of (meth) acrylic acid homo- or
- Suitable comonomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid.
- a suitable polymer is in particular polyacrylic acid, which preferably has an average molecular weight M w in the range from 2000 to 40,000 g / mol, preferably 2,000 to 10,000 g / mol, in particular 3,000 to 8,000 g / mol.
- copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid.
- copolymers of at least one monomer from the group consisting of monoethylenically unsaturated C3-Cio-mono- or C4-Cio-dicarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid with at least one hydrophilic or hydrophobically modified monomers as enumerated below.
- Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins having 10 or more carbon atoms or mixtures thereof, for example 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1 - Eicosene, 1-docoses, 1-tetracoses and 1-hexacoses, C22- ⁇ -olefin, a mixture of C2o-C24- ⁇ -olefins and polyisobutene having an average of 12 to 100 carbon atoms per molecule.
- Suitable hydrophilic monomers are monomers having sulfonate or phosphonate groups, as well as nonionic monomers having hydroxy functionality or alkylene oxide groups. Examples which may be mentioned are: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate.
- Polyalkylene glycols may contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units per molecule.
- Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2- hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacryl
- amphoteric polymers can also be used as builders.
- Formulations according to the invention may contain, for example, in the range from 10 to 50% by weight, preferably up to 20% by weight, of builder.
- formulations according to the invention may contain one or more co-builders.
- cobuilders are phosphonates, for example hydroxyalkanephosphonates and aminoalkanephosphonates.
- hydroxyalkane phosphonates the 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9).
- Preferred aminoalkanephosphonates are ethylenediaminetetra-methylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
- Formulations of the invention may contain one or more alkali carriers.
- Alkaline carriers for example, provide the pH of at least 9 when an alkaline pH is desired.
- Suitable examples are alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal hydroxides and alkali metal metasilicates.
- Preferred alkali metal is in each case potassium, particularly preferred is sodium.
- Formulations according to the invention may contain, in addition to bleaching agent (D), one or more chlorine-containing bleaching agents.
- Suitable chlorine-containing bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate.
- formulations according to the invention may contain in the range of from 3 to 10% by weight of chlorine-containing bleach.
- Formulations of the invention may contain one or more bleach catalysts.
- Bleach catalysts can be selected from bleach-enhancing transition metal salts or transition metal complexes such as manganese, iron, cobalt, ruthenium or molybdenum-salene complexes or carbonyl complexes.
- Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and cobalt, iron, copper and ruthenium-amine complexes can also be used as bleach catalysts.
- Formulations according to the invention may contain one or more bleach activators, for example N-methylmorpholinium acetonitrile salts ("MMA salts”), trimethylammonium acetonitrile salts, N-acylimides such as N-nonanoylsuccinimide "1, 5-diacetyl-2,2-dioxohexahydro -1, 3,5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).
- MMA salts N-methylmorpholinium acetonitrile salts
- DADHT 3,5-triazine
- nitrile quats trimethylammonium acetonitrile salts
- TAED tetraacetylethylenediamine
- TAED tetraacetylhexylenediamine
- Formulations of the invention may contain one or more corrosion inhibitors.
- corrosion inhibitors such compounds that inhibit the corrosion of metal.
- suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, furthermore phenol derivatives such as, for example, hydroquinone, catechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.
- formulations according to the invention contain a total of in the range of 0.1 to 1, 5 wt .-% corrosion inhibitor.
- Formulations of the invention may contain one or more builders, for example, sodium sulfate.
- Formulations according to the invention may contain one or more defoamers, selected for example from silicone oils and paraffin oils.
- formulations according to the invention contain in total in the range from 0.05 to 0.5% by weight defoamer.
- Formulations according to the invention may contain phosphonic acid or one or more phosphonic acid derivatives, for example hydroxyethane-1,1-diphosphonic acid.
- Another object of the present invention is the use of formulations according to the invention for the automatic cleaning of dishes and kitchen utensils. As kitchen utensils in the context of the present invention, for example, pots, pans, casseroles to call, and metal objects such as, for example, skimmers, roasters and garlic presses.
- a surface of glass is to be understood as meaning that the object in question has at least one piece of glass which comes into contact with the ambient air and can be contaminated when the object is used.
- the objects in question may be those which are essentially glassware such as drinking glasses or glass bowls. However, it may also be, for example, covers that have individual components made of a different material, for example pot lid with border and handle made of metal.
- Glass surface may be decorated, for example colored or printed, or not decorated.
- glass includes any glass, for example lead glass and in particular soda lime glass, crystal glass and borosilicate glasses.
- Machine cleaning is preferably dishwashing with a dishwasher (English: automatic dishwashing).
- At least one formulation according to the invention for automated cleaning of drinking glasses, glass vases and glass jars is used for cooking.
- water having a hardness in the range from 1 to 30 ° dH, preferably from 2 to 25 ° dH, is used for cleaning, German hardness being taken to mean in particular the calcium hardness.
- water with a hardness in the range of 1 to 30 ° dH, preferably 2 to 25 ° dH, may also be used.
- machine-cleaning formulations according to the invention are used, even with repeated mechanical cleaning of objects which have at least one surface made of glass, there is very little tendency for glass corrosion, even if objects comprising at least one surface made of glass are used have, along with heavily soiled cutlery or dishes cleans. In addition, it is much less harmful to use the formulation according to the invention in order to mix glass together with articles. To clean the metal, for example, together with pots, pans or garlic presses.
- formulations according to the invention have a very good bleaching action when used for rinsing dishes and kitchen utensils and glass surfaces.
- a further subject of the present invention is a process for the preparation of formulations according to the invention, in short also called production process according to the invention.
- preparation process according to the invention it is possible, for example, to proceed in such a way that
- a aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and their salts, and
- Compound (A), modified polypropyleneimine (B) and bleaching agent (D) are defined above.
- one or more surfactants for formulation according to the invention, for example with one or more surfactants, one or more enzymes, one or more builders, one or more builders several co-builders, in particular phosphorus-free builders, one or more alkali carriers, one or more bleaches, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers, one or more corrosion inhibitors, one or more builders , with buffer or dye.
- the water is completely or partially removed, for example, to a residual moisture in the range from 0.1 to 10% by weight of the formulation according to the invention by evaporation, in particular by spray drying, spray granulation or compaction.
- the water is removed, in whole or in part, at a pressure in the range of 0.3 to 2 bar. In one embodiment of the present invention, the water is removed, in whole or in part, at temperatures in the range of 60 to 220 ° C.
- the cleaning formulations according to the invention can be provided in liquid or solid form, single- or multiphase, as tablets or in the form of other dosage units, packaged or unpackaged.
- the water content of liquid formulations can vary from 35 to 90% water.
- modified polypropyleneimines (B) prepared by alkoxylation of polypropyleneimine, which is prepared by transamination of propanediamine and optionally up to 40 mol% of at least one other aliphatic diamines. Preparation and properties of modified polypropyleneimines (B) according to the invention are described above.
- the invention is illustrated by working examples.
- Data in% are wt .-%, unless expressly stated otherwise.
- Data in ° dH always relate to the permanent hardness.
- 1, 3-propanediamine 1, 3-PDA
- PDA 1, 3-propanediamine
- 50 Nl of hydrogen passed through a fixed bed Ni / Co catalyst supported on ZrO2 in the tube reactor at a reaction temperature of 160 ° C.
- gas and liquid phase were separated and the liquid portion was introduced into the steel vessel From there, it was pumped back over the catalyst and the reaction was carried out for 2 hours to give L-PPI.1 whose properties are listed in Table 1.
- a tubular reactor with an internal diameter of 27 mm was used to continuously conduct 1, 3-PDA, together with 10 standard liters / h of hydrogen, over a cobalt-fixed bed catalyst.
- the total pressure was 50 bar, the temperature 170 ° C.
- the intake of 1, 3-PDA was 0.8 kg / L ca fh.
- a crude product was obtained. Unreacted 1, 3-PDA and the corresponding dimer and trimer were distilled off from the crude product and gave L-PPI.4 as a colorless liquid.
- a tubular reactor with an internal diameter of 27 mm was used to continuously conduct 1, 3-PDA, together with 10 standard liters / h of hydrogen, over a cobalt-fixed bed catalyst.
- the total pressure was 50 bar, the temperature 160 ° C.
- the intake of 1, 3-PDA was 0.6 kg / L ca fh.
- a crude product was obtained which, according to gas chromatography, had 7% by weight unreacted 1,3-PDA. Distilled 1, 3-PDA and the corresponding dimer and trimer and received L-PPI.6 as a colorless liquid.
- alkoxylated polypropyleneimine (B.3) according to the invention as a yellow waxy solid (630.6 g).
- Amine number 57.2 mg KOH / g.
- LA charge density of the relevant modified polypropyleneimine (B), meq / g (milliequivalent / g)
- base mixtures were prepared from the starting materials according to Table 2. The starting materials were mixed dry.
- MGDA methylglycine diacetic acid as trisodium salt
- TAED ⁇ , ⁇ , ⁇ ', ⁇ '-tetraacetylethylenediamine
- Polypropyleneimines (B) and modified polypropyleneimines (B) according to Table 3 were used.
- Washware 3 champagne glasses “GILDE”, 3 shot glasses, "INTERMEZZO"
- the dishwashing agent used was in each case 25 g of formulation according to the invention or 25 g of comparison formulation according to Table 4, wherein Table 4 individually specifies the active components (A.1), base mixture and (B) of formulation according to the invention.
- Rinsing was carried out at a rinse temperature of 55 ° C.
- the water hardness was in each case in the range of zero to 2 ° dH.
- the evaluation was carried out gravimetrically and visually after 100 rinsing cycles.
- the weight of the glasses was determined before the beginning of the first rinse cycle and after drying after the last rinse cycle.
- the weight loss is the difference between the two values.
- test pieces were rinsed for the purpose of pretreatment, the test pieces in a domestic dishwashing machine (Bosch SGS5602) with 1 g of surfactant (n-Ci8H37 (OCH 2 CH 2) ioOH) and 20 g of citric acid, to remove any impurities.
- surfactant n-Ci8H37 (OCH 2 CH 2) ioOH
- citric acid 20 g
- the dry specimens were weighed. This was followed by the visual assessment of the test specimens. The surface of the test specimens was evaluated for line corrosion (glass scoring) and haze corrosion (areal haze).
- Interim scores (e.g., L3-4) were also allowed on the match.
- formulations according to the invention were also always superior to the corresponding comparative formulations in terms of the inhibition of glass corrosion.
- Table 4 Results of tests with dishwasher (endurance runner)
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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EP14702846.8A EP2961822B1 (en) | 2013-02-28 | 2014-02-04 | Formulations, use of same as or for manufacture of dishwashing agents and their manufacture |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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EP13157192 | 2013-02-28 | ||
PCT/EP2014/052174 WO2014131585A1 (en) | 2013-02-28 | 2014-02-04 | Formulations, use thereof as dishwashing detergents or for producing dishwashing detergents, and the production of said formulations |
EP14702846.8A EP2961822B1 (en) | 2013-02-28 | 2014-02-04 | Formulations, use of same as or for manufacture of dishwashing agents and their manufacture |
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EP2961822A1 true EP2961822A1 (en) | 2016-01-06 |
EP2961822B1 EP2961822B1 (en) | 2017-04-12 |
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EP14702846.8A Active EP2961822B1 (en) | 2013-02-28 | 2014-02-04 | Formulations, use of same as or for manufacture of dishwashing agents and their manufacture |
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Country | Link |
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US (1) | US10301576B2 (en) |
EP (1) | EP2961822B1 (en) |
ES (1) | ES2632465T3 (en) |
PL (1) | PL2961822T3 (en) |
WO (1) | WO2014131585A1 (en) |
Families Citing this family (7)
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PL2961819T3 (en) | 2013-02-28 | 2018-02-28 | Basf Se | Aqueous formulations, their manufacture, and their use in hard surface cleaning |
EP2842936A1 (en) | 2013-08-26 | 2015-03-04 | Basf Se | Etheramines based on alkoxylated glycerine or trimethylolpropane. |
SG11201601128RA (en) | 2013-08-26 | 2016-03-30 | Basf Se | Alkoxylated polyethyleneimine with a low melting point |
EP3118296A1 (en) * | 2015-07-16 | 2017-01-18 | Clearwhite GmbH | Cleaning tablet for carafes |
BR112022024051A2 (en) * | 2020-05-29 | 2022-12-27 | Basf Se | AMPHOTERICALLY MODIFIED OLIGOPROPYLENIMINE ETHOXYLATES, COMPOUND MIXTURE, MIXING, PROCESS FOR MAKING AMPHOTERICALLY MODIFIED OLIGOPROPYLENIMINE ETHOXYLATES, USE OF AMPHORETHERICALLY MODIFIED OLIGOPROPYLENIMINE ETHOXYLATES, AND FORMULATION FOR LAUNDRY WASHING |
US20230125610A1 (en) | 2020-06-17 | 2023-04-27 | Basf Se | Amphiphilic alkoxylated polyethylene/-propylene imine copolymers for multi-benefit detergent formulations |
MX2024007601A (en) * | 2021-12-20 | 2024-07-09 | Basf Se | Polypropylene imine polymers (ppi), their preparation, uses, and compositions comprising such ppi. |
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DE19819187A1 (en) | 1998-04-30 | 1999-11-11 | Henkel Kgaa | Solid dishwasher detergent with phosphate and crystalline layered silicates |
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ES2626819T3 (en) | 2011-10-19 | 2017-07-26 | Basf Se | Formulations, their use as or for the manufacture of dishwashing detergents and their manufacture |
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JP6133971B2 (en) * | 2012-04-25 | 2017-05-24 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | Formulations, their use as dishwashing detergents or for producing dishwashing detergents, and their production |
ES2678543T3 (en) * | 2012-08-24 | 2018-08-13 | The Procter & Gamble Company | Dishwashing method |
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PL2961819T3 (en) | 2013-02-28 | 2018-02-28 | Basf Se | Aqueous formulations, their manufacture, and their use in hard surface cleaning |
US8987518B2 (en) | 2013-02-28 | 2015-03-24 | Basf Se | Polyamines and process for preparation thereof |
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2014
- 2014-02-04 US US14/765,149 patent/US10301576B2/en not_active Expired - Fee Related
- 2014-02-04 EP EP14702846.8A patent/EP2961822B1/en active Active
- 2014-02-04 PL PL14702846T patent/PL2961822T3/en unknown
- 2014-02-04 ES ES14702846.8T patent/ES2632465T3/en active Active
- 2014-02-04 WO PCT/EP2014/052174 patent/WO2014131585A1/en active Application Filing
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US20150361379A1 (en) | 2015-12-17 |
WO2014131585A1 (en) | 2014-09-04 |
ES2632465T3 (en) | 2017-09-13 |
EP2961822B1 (en) | 2017-04-12 |
US10301576B2 (en) | 2019-05-28 |
PL2961822T3 (en) | 2017-09-29 |
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