EP3102660B1 - Multi-phase pre-portioned detergent - Google Patents
Multi-phase pre-portioned detergent Download PDFInfo
- Publication number
- EP3102660B1 EP3102660B1 EP15702291.4A EP15702291A EP3102660B1 EP 3102660 B1 EP3102660 B1 EP 3102660B1 EP 15702291 A EP15702291 A EP 15702291A EP 3102660 B1 EP3102660 B1 EP 3102660B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cleaning agent
- weight
- bis
- liquid phase
- acid
- 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.)
- Active
Links
- 239000003599 detergent Substances 0.000 title description 71
- 239000007791 liquid phase Substances 0.000 claims description 93
- 239000012459 cleaning agent Substances 0.000 claims description 62
- -1 preferably powdered Substances 0.000 claims description 54
- 238000004851 dishwashing Methods 0.000 claims description 44
- 239000007790 solid phase Substances 0.000 claims description 36
- 229920001577 copolymer Polymers 0.000 claims description 27
- 239000012071 phase Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000007844 bleaching agent Substances 0.000 claims description 23
- 239000002736 nonionic surfactant Substances 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 21
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 17
- 229920005646 polycarboxylate Polymers 0.000 claims description 17
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 229910019142 PO4 Inorganic materials 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 238000009463 water soluble packaging Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 52
- 239000000178 monomer Substances 0.000 description 31
- 125000004432 carbon atom Chemical group C* 0.000 description 26
- 102000004190 Enzymes Human genes 0.000 description 22
- 108090000790 Enzymes Proteins 0.000 description 22
- 229940088598 enzyme Drugs 0.000 description 20
- 229920006395 saturated elastomer Polymers 0.000 description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 18
- 239000002253 acid Substances 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 13
- 150000002191 fatty alcohols Chemical class 0.000 description 12
- 235000021317 phosphate Nutrition 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- 108091005804 Peptidases Proteins 0.000 description 10
- 239000004365 Protease Substances 0.000 description 10
- 150000007513 acids Chemical class 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- CIEZZGWIJBXOTE-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)C(C)N(CC(O)=O)CC(O)=O CIEZZGWIJBXOTE-UHFFFAOYSA-N 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 238000009472 formulation Methods 0.000 description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 9
- 239000011572 manganese Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 108010065511 Amylases Proteins 0.000 description 8
- 102000013142 Amylases Human genes 0.000 description 8
- 239000012190 activator Substances 0.000 description 8
- 235000019418 amylase Nutrition 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000008187 granular material Substances 0.000 description 8
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229920000058 polyacrylate Polymers 0.000 description 7
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 6
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- OSCJHTSDLYVCQC-UHFFFAOYSA-N 2-ethylhexyl 4-[[4-[4-(tert-butylcarbamoyl)anilino]-6-[4-(2-ethylhexoxycarbonyl)anilino]-1,3,5-triazin-2-yl]amino]benzoate Chemical compound C1=CC(C(=O)OCC(CC)CCCC)=CC=C1NC1=NC(NC=2C=CC(=CC=2)C(=O)NC(C)(C)C)=NC(NC=2C=CC(=CC=2)C(=O)OCC(CC)CCCC)=N1 OSCJHTSDLYVCQC-UHFFFAOYSA-N 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 102000035195 Peptidases Human genes 0.000 description 5
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 5
- 125000002843 carboxylic acid group Chemical group 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000010410 layer 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
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 235000019419 proteases Nutrition 0.000 description 5
- 235000018102 proteins Nutrition 0.000 description 5
- 102000004169 proteins and genes Human genes 0.000 description 5
- 108090000623 proteins and genes Proteins 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 239000004382 Amylase Substances 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 108090001060 Lipase Proteins 0.000 description 4
- 102000004882 Lipase Human genes 0.000 description 4
- 239000004367 Lipase Substances 0.000 description 4
- 108090000854 Oxidoreductases Proteins 0.000 description 4
- 102000004316 Oxidoreductases Human genes 0.000 description 4
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 108010056079 Subtilisins Proteins 0.000 description 4
- 102000005158 Subtilisins Human genes 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 229940025131 amylases Drugs 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 235000019421 lipase Nutrition 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000002304 perfume Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000013543 active substance Substances 0.000 description 3
- 108090000637 alpha-Amylases Proteins 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 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 3
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 3
- 229940045872 sodium percarbonate Drugs 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- UYXFOIMFLBVYDL-UHFFFAOYSA-N 1,2,4,7-tetramethyl-1,4,7-triazonane Chemical compound CC1CN(C)CCN(C)CCN1C UYXFOIMFLBVYDL-UHFFFAOYSA-N 0.000 description 2
- WLDGDTPNAKWAIR-UHFFFAOYSA-N 1,4,7-trimethyl-1,4,7-triazonane Chemical compound CN1CCN(C)CCN(C)CC1 WLDGDTPNAKWAIR-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
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-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
- ZGZHWIAQICBGKN-UHFFFAOYSA-N 1-nonanoylpyrrolidine-2,5-dione Chemical compound CCCCCCCCC(=O)N1C(=O)CCC1=O ZGZHWIAQICBGKN-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 description 2
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 108010025880 Cyclomaltodextrin glucanotransferase Proteins 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- 102220644676 Galectin-related protein_D96L_mutation Human genes 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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
- 238000003109 Karl Fischer titration Methods 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 108010077895 Sarcosine Proteins 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 241000223258 Thermomyces lanuginosus Species 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 102000004139 alpha-Amylases Human genes 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 239000004599 antimicrobial Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229960004106 citric acid Drugs 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 2
- 229940079919 digestives enzyme preparation Drugs 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000009969 flowable effect Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 108010002430 hemicellulase Proteins 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- MSLRPWGRFCKNIZ-UHFFFAOYSA-J tetrasodium;hydrogen peroxide;dicarbonate Chemical compound [Na+].[Na+].[Na+].[Na+].OO.OO.OO.[O-]C([O-])=O.[O-]C([O-])=O MSLRPWGRFCKNIZ-UHFFFAOYSA-J 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- BPSYZMLXRKCSJY-UHFFFAOYSA-N 1,3,2-dioxaphosphepan-2-ium 2-oxide Chemical compound O=[P+]1OCCCCO1 BPSYZMLXRKCSJY-UHFFFAOYSA-N 0.000 description 1
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 description 1
- HHBCEKAWSILOOP-UHFFFAOYSA-N 1,3-dibromo-1,3,5-triazinane-2,4,6-trione Chemical compound BrN1C(=O)NC(=O)N(Br)C1=O HHBCEKAWSILOOP-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
- LYPVKWMHGFMDPD-UHFFFAOYSA-N 1,5-diacetyl-1,3,5-triazinane-2,4-dione Chemical compound CC(=O)N1CN(C(C)=O)C(=O)NC1=O LYPVKWMHGFMDPD-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
- VDNSZPNSUQRUMS-UHFFFAOYSA-N 1-cyclohexyl-4-ethenylbenzene Chemical compound C1=CC(C=C)=CC=C1C1CCCCC1 VDNSZPNSUQRUMS-UHFFFAOYSA-N 0.000 description 1
- WJNKJKGZKFOLOJ-UHFFFAOYSA-N 1-dodecyl-4-ethenylbenzene Chemical compound CCCCCCCCCCCCC1=CC=C(C=C)C=C1 WJNKJKGZKFOLOJ-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- ATQUFXWBVZUTKO-UHFFFAOYSA-N 1-methylcyclopentene Chemical compound CC1=CCCC1 ATQUFXWBVZUTKO-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical compound CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- PKVDGQHNRICJLA-UHFFFAOYSA-N 2,4-dimethylhex-1-ene Chemical compound CCC(C)CC(C)=C PKVDGQHNRICJLA-UHFFFAOYSA-N 0.000 description 1
- AIIITCMZOKMJIM-UHFFFAOYSA-N 2-(prop-2-enoylamino)propane-2-sulfonic acid Chemical compound OS(=O)(=O)C(C)(C)NC(=O)C=C AIIITCMZOKMJIM-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- SZTBMYHIYNGYIA-UHFFFAOYSA-N 2-chloroacrylic acid Chemical compound OC(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-N 0.000 description 1
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- GDNYDTQPGWENAQ-UHFFFAOYSA-N 2-hydroxy-1-(2-methylprop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(O)C(S(O)(=O)=O)NC(=O)C(C)=C GDNYDTQPGWENAQ-UHFFFAOYSA-N 0.000 description 1
- KOQQKLZTINXBAS-UHFFFAOYSA-N 2-hydroxy-3-prop-2-enoxypropane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(O)COCC=C KOQQKLZTINXBAS-UHFFFAOYSA-N 0.000 description 1
- VSSGDAWBDKMCMI-UHFFFAOYSA-N 2-methyl-2-(2-methylprop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)NC(C)(C)CS(O)(=O)=O VSSGDAWBDKMCMI-UHFFFAOYSA-N 0.000 description 1
- 125000004398 2-methyl-2-butyl group Chemical group CC(C)(CC)* 0.000 description 1
- PSZAEHPBBUYICS-UHFFFAOYSA-N 2-methylidenepropanedioic acid Chemical compound OC(=O)C(=C)C(O)=O PSZAEHPBBUYICS-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- ONPJWQSDZCGSQM-UHFFFAOYSA-N 2-phenylprop-2-enoic acid Chemical compound OC(=O)C(=C)C1=CC=CC=C1 ONPJWQSDZCGSQM-UHFFFAOYSA-N 0.000 description 1
- KFNGWPXYNSJXOP-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)OCCCS(O)(=O)=O KFNGWPXYNSJXOP-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical class C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- ZRKSKKQONQUFMR-UHFFFAOYSA-N 3-amino-2-methyl-3-oxoprop-1-ene-1-sulfonic acid Chemical compound NC(=O)C(C)=CS(O)(=O)=O ZRKSKKQONQUFMR-UHFFFAOYSA-N 0.000 description 1
- BTTCOCQDAWAAJR-UHFFFAOYSA-N 3-ethylcyclohexyne Chemical compound CCC1CCCC#C1 BTTCOCQDAWAAJR-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- NYUTUWAFOUJLKI-UHFFFAOYSA-N 3-prop-2-enoyloxypropane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCOC(=O)C=C NYUTUWAFOUJLKI-UHFFFAOYSA-N 0.000 description 1
- DXFURPHVJQITAC-UHFFFAOYSA-N 4-benzyl-1-ethenyl-2-ethylbenzene Chemical compound C1=C(C=C)C(CC)=CC(CC=2C=CC=CC=2)=C1 DXFURPHVJQITAC-UHFFFAOYSA-N 0.000 description 1
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- 241000228245 Aspergillus niger Species 0.000 description 1
- 240000006439 Aspergillus oryzae Species 0.000 description 1
- 241000193744 Bacillus amyloliquefaciens Species 0.000 description 1
- 241000193422 Bacillus lentus Species 0.000 description 1
- 241000194108 Bacillus licheniformis Species 0.000 description 1
- 241000194110 Bacillus sp. (in: Bacteria) Species 0.000 description 1
- 108091005658 Basic proteases Proteins 0.000 description 1
- 108700038091 Beta-glucanases Proteins 0.000 description 1
- 102100032487 Beta-mannosidase Human genes 0.000 description 1
- 108010073997 Bromide peroxidase Proteins 0.000 description 1
- 108010053835 Catalase Proteins 0.000 description 1
- 102000016938 Catalase Human genes 0.000 description 1
- 108010031396 Catechol oxidase Proteins 0.000 description 1
- 102000030523 Catechol oxidase Human genes 0.000 description 1
- 108010084185 Cellulases Proteins 0.000 description 1
- 102000005575 Cellulases Human genes 0.000 description 1
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical class ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 1
- 108010035722 Chloride peroxidase Proteins 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 1
- 102000016680 Dioxygenases Human genes 0.000 description 1
- 108010028143 Dioxygenases Proteins 0.000 description 1
- 101710121765 Endo-1,4-beta-xylanase Proteins 0.000 description 1
- 108010067770 Endopeptidase K Proteins 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000193385 Geobacillus stearothermophilus Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- 108010029541 Laccase Proteins 0.000 description 1
- 108010054320 Lignin peroxidase Proteins 0.000 description 1
- 108010059896 Manganese peroxidase Proteins 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- UDPYEFRYPGXIAL-UHFFFAOYSA-N NC(=O)C(C)=CCS(O)(=O)=O Chemical compound NC(=O)C(C)=CCS(O)(=O)=O UDPYEFRYPGXIAL-UHFFFAOYSA-N 0.000 description 1
- 108090000417 Oxygenases Proteins 0.000 description 1
- 102000004020 Oxygenases Human genes 0.000 description 1
- 108010029182 Pectin lyase Proteins 0.000 description 1
- 108700020962 Peroxidase Proteins 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 108010059820 Polygalacturonase Proteins 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- DUFKCOQISQKSAV-UHFFFAOYSA-N Polypropylene glycol (m w 1,200-3,000) Chemical class CC(O)COC(C)CO DUFKCOQISQKSAV-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241001292348 Salipaludibacillus agaradhaerens Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 108090000787 Subtilisin Proteins 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 102000003425 Tyrosinase Human genes 0.000 description 1
- 108060008724 Tyrosinase Proteins 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005263 alkylenediamine group Polymers 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229940024171 alpha-amylase Drugs 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229940027983 antiseptic and disinfectant quaternary ammonium compound Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- VUEDNLCYHKSELL-UHFFFAOYSA-N arsonium Chemical group [AsH4+] VUEDNLCYHKSELL-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 108010055059 beta-Mannosidase Proteins 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical class [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 108010005400 cutinase Proteins 0.000 description 1
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 229960004670 didecyldimethylammonium chloride Drugs 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- KHAYCTOSKLIHEP-UHFFFAOYSA-N docosyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCOC(=O)C=C KHAYCTOSKLIHEP-UHFFFAOYSA-N 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 description 1
- 108010093305 exopolygalacturonase Proteins 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 108010046301 glucose peroxidase Proteins 0.000 description 1
- 125000001046 glycoluril group Chemical group [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- 239000001257 hydrogen Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000008297 liquid dosage form Substances 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 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 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- WEWMLPXWLVIVNW-UHFFFAOYSA-N n-(2-ethylhexyl)prop-2-enamide Chemical compound CCCCC(CC)CNC(=O)C=C WEWMLPXWLVIVNW-UHFFFAOYSA-N 0.000 description 1
- JLCNIMCQBVMUIN-UHFFFAOYSA-N n-docosylprop-2-enamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCNC(=O)C=C JLCNIMCQBVMUIN-UHFFFAOYSA-N 0.000 description 1
- XQPVIMDDIXCFFS-UHFFFAOYSA-N n-dodecylprop-2-enamide Chemical compound CCCCCCCCCCCCNC(=O)C=C XQPVIMDDIXCFFS-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- CNWVYEGPPMQTKA-UHFFFAOYSA-N n-octadecylprop-2-enamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)C=C CNWVYEGPPMQTKA-UHFFFAOYSA-N 0.000 description 1
- AWGZKFQMWZYCHF-UHFFFAOYSA-N n-octylprop-2-enamide Chemical compound CCCCCCCCNC(=O)C=C AWGZKFQMWZYCHF-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000023837 negative regulation of proteolysis Effects 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- SXLLDUPXUVRMEE-UHFFFAOYSA-N nonanediperoxoic acid Chemical compound OOC(=O)CCCCCCCC(=O)OO SXLLDUPXUVRMEE-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 108020004410 pectinesterase Proteins 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- PATMLLNMTPIUSY-UHFFFAOYSA-N phenoxysulfonyl 7-methyloctanoate Chemical compound CC(C)CCCCCC(=O)OS(=O)(=O)OC1=CC=CC=C1 PATMLLNMTPIUSY-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 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
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000006337 proteolytic cleavage Effects 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 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
- 239000013049 sediment Substances 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 229910000031 sodium sesquicarbonate Inorganic materials 0.000 description 1
- 235000018341 sodium sesquicarbonate Nutrition 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007909 solid dosage form Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 229950009390 symclosene Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 108010031354 thermitase Proteins 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- ZKWDCFPLNQTHSH-UHFFFAOYSA-N tribromoisocyanuric acid Chemical compound BrN1C(=O)N(Br)C(=O)N(Br)C1=O ZKWDCFPLNQTHSH-UHFFFAOYSA-N 0.000 description 1
- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 108010068608 xanthan lyase Proteins 0.000 description 1
- 108010083879 xyloglucan endo(1-4)-beta-D-glucanase Proteins 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000004246 zinc acetate 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
- C11D17/045—Multi-compartment
-
- 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
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid 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
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
Definitions
- the present invention relates to pre-portioned multi-phase detergents, in particular automatic dishwashing detergents and their use.
- Hard surface cleaners such as dishwashing detergents
- dishwashing detergents are available to the consumer in a variety of forms.
- traditional solid agents are gaining increasingly increasingly flowable and especially liquid to gel detergent in importance.
- the consumer particularly appreciates the rapid solubility and the associated rapid availability of the ingredients in the cleaning liquor, especially in short-dishwashing programs and at low temperatures.
- compositions in which in particular the water content is reduced compared to conventional compositions, increases.
- compositions whose water content is as low as possible are particularly desirable.
- Disposable portions in particular water-soluble bags or multi-chamber tablets made of water-soluble material, enjoy the consumer not only because of increasing popularity, because the consumer with the chemical composition is no longer in contact, but not least because of the attractive appearance of the bag. For the consumer, it is therefore a nuisance if the bags lose their attractive appearance.
- Multifunctional automatic dishwashing detergents save the user the separate use of rinse aid and the refilling of salt in the dishwasher.
- certain builders are used in their formulations which achieve a good rinse aid result and counteract the formation of coatings even at higher water hardness.
- Modern dishwashers provide for dosing of cleaning products before a dosing, which automatically opens during the wash program and releases the product.
- the size of the metering chamber is however limited in its capacity. For a good cleaning performance, however, sufficient quantities of various functional blocks of the dishwashing detergent formulation, such as builder, alkalinity, enzymes, surfactants, etc., must be made available. This means that the available volume of the dosing chamber must be used optimally in order to produce a sufficient amount of the active substances and thus a good cleaning performance.
- the object of the present invention was to provide a multi-phase pre-portioned detergent, in particular dishwashing detergent, preferably automatic dishwashing detergent, with at least one liquid and at least one solid, preferably pulverulent phase, which fits into the dispensing compartment of the dishwasher and still exhibits good cleaning performance.
- a pre-portioned detergent preferably machine dishwashing detergent, in a package having at least two compartments, comprising at least one solid, preferably pulverulent phase and at least one liquid phase, characterized in that the detergent contains 2 to 20% by weight, in particular 2 to 10% by weight (based on the total weight of the composition) of polymeric or co-polymeric polycarboxylates and / or sulfonic acid group-containing polymers and the solid phase (or solid phases) less than 1 wt .-% (based on the weight of the solid phase), polymeric and / or co-polymeric polycarboxylates and / or sulfonic acid group-containing polymers, wherein the cleaning agent contains less than 1% by weight of phosphate, based on the total weight of the cleaning agent.
- co-builders In particular in cleaning agents, in particular in those which contain only small amounts of phosphate or which are substantially free of phosphates, co-builders must be used in addition to the phosphate-containing and / or phosphate-free builders in order to achieve a sufficiently high complexation of divalent cations from the used Rinse water, usually local tap water to ensure that otherwise leave on the dishes coverings.
- Polymeric, polycarboxylate-containing cobuilders are usually marketed as aqueous preparations. In aqueous machine dishwashing detergents, they are therefore usually formulated directly into the aqueous cleaning agents. If they are to be used in solid formulations, they must first be dried time-consuming and energy-intensive and then formulated as granules. Then they are particularly suitable for solid, especially granular products.
- aqueous preparations of co-builders are not suitable due to the high water input.
- a space-saving formulation In a multi-phase pre-portioned detergent, in particular machine dishwashing detergent, which contains at least one solid and one liquid phase, which is optimized in terms of the dimensions of the metering chamber in dishwashers, a space-saving formulation must be used in particular.
- polymeric polycarboxylate-containing components and / or polymers containing sulfonic acid groups in liquid cleaning agents, in particular liquid machine dishwashing detergents, which are preferably essentially free of water
- the solid components must be finely distributed (as a dispersion) in an organic matrix and also stable in storage in the dispersion remain and must not sediment.
- the dried (de-watered) polycarboxylate-containing component and / or the sulfonic acid group-containing polymers are used in finely ground form.
- the cleaning agent according to the invention in particular machine dishwashing detergent, contains a total of 2 to 20 wt .-%, in particular 2 to 10 wt .-% (each based on the total weight of the composition, ie the total weight of all phases) polymeric or co-polymeric polycarboxylates or sulfonic acid-containing polymers.
- the cleaning agents according to the invention may in particular contain a sulfonic acid group-containing polymer (hereinafter also referred to as sulfopolymer).
- sulfopolymer a sulfonic acid group-containing polymer
- the proportion by weight of the sulfopolymer in the total weight of the cleaning agent according to the invention is preferably from 0.1 to 20 wt .-%, in particular from 0.5 to 18 wt .-%, particularly preferably 1.0 to 15 wt .-%, most preferably 2.0 to 14 wt .-%, in particular from 4 to 14 wt .-%, especially from 4.5 to 12 wt .-%.
- the sulfopolymer is used here in particular in a dried, particularly preferably in a dried and granulated (solid) form, which may optionally additionally be ground.
- the sulfopolymer used is preferably a copolymeric polysulfonate, for example a hydrophobically modified copolymeric polysulfonate.
- the inventive cleaning agent contains a total of 2 to 20 wt .-%, in particular 2 to 10 wt .-% (each based on the total weight of the composition) (co) polymeric polycarboxylates and sulfonic acid-containing polymers.
- the solid phase (s) are substantially free of polymeric or co-polymeric polycarboxylates and / or sulfonic acid group-containing polymers.
- the cleaning agent itself preferably contains from 2 to 20% by weight (based on the total weight of the cleaning agent (total weight of all phases)) of polymeric or co-polymeric polycarboxylates and sulfonic acid-containing polymers.
- polymeric or copolymeric polycarboxylates are suitable according to the invention as builders, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 500 to 70,000 g / mol.
- the polyacrylate or the polyacrylates are used here in particular in a dried, particularly preferably in a dried and granulated (solid) form, which may optionally additionally be ground.
- Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of about 1000 to 20,000, in particular from 2000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of about 1000 to 10,000, of 2,000 to 10,000 g / mol, and particularly preferably of 3,000 to 5,000 g / mol, may again be preferred from this group.
- copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
- Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
- Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
- polycarboxylic acids (carboxylic acids having more than one carboxylate function) in monomeric form are not to be understood as polymeric polycarboxylates.
- it does not include those polycarboxylic acids as described in detail below as organic cobuilders and which may be present in the liquid phase (s) as well as the solid phase (s) according to the invention (ie they are is not included in the amounts indicated for polymeric polycarboxylates and are thus not taken into account for the quantitative restrictions).
- the cleaning agents according to the invention can, as described above, contain a sulfonic acid group-containing polymer (also referred to below as sulfopolymer).
- a sulfonic acid group-containing polymer also referred to below as sulfopolymer.
- the sulfopolymer used is preferably a copolymeric polysulfonate, for example a hydrophobically modified copolymeric polysulfonate.
- the copolymers may have two, three, four or more different monomer units.
- Preferred copolymeric polysulfonates contain not only sulfonic acid group-containing monomer (s) but also at least one monomer selected from the group consisting of unsaturated carboxylic acids.
- unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid, alpha-cyanoacrylic acid, crotonic acid, alpha-phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.
- Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic 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, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble
- the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
- metal ions preferably alkali metal ions and in particular for sodium ions.
- partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
- the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.
- the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
- Preferred cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
- the copolymers in addition to the carboxyl group-containing monomer and the monomer containing the sulfonic acid group, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer.
- the use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.
- Anionic copolymers comprising monomers containing carboxylic acid groups, monomers containing sulfonic acid groups and nonionic monomers, in particular hydrophobic monomers, are therefore preferred according to the invention.
- nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyne, 1-octene, alpha-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and
- the monomer distribution of the hydrophobically modified copolymers preferably used according to the invention is preferably in each case from 5 to 80% by weight, with respect to the sulfonic acid group-containing monomer, the hydrophobic monomer and the carboxylic acid group-containing monomer, the proportion of the sulfonic acid group-containing monomer and of the each hydrophobic monomer 5 to 30 wt .-% and the proportion of the carboxylic acid group-containing monomer 60 to 80 wt .-%, the monomers are in this case preferably selected from the aforementioned.
- organic co-builders are polycarboxylates / polycarboxylic acids, aspartic acid, polyacetals, dextrins, other organic cobuilders and phosphonates. These classes of substances are described below.
- Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function.
- polycarboxylic acids meaning those carboxylic acids which carry more than one acid function.
- NTA nitrilotriacetic acid
- the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of the automatic dishwashing detergents.
- citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
- aminocarboxylic acids and / or their salts are aminocarboxylic acids and / or their salts. Particularly preferred members of this class are methylglycinediacetic acid (MGDA) or its salts and glutamic diacetic acid (GLDA) or its salts or ethylenediamine diacetic acid or its salts (EDDS). Also suitable are iminodisuccinic acid (IDS) and iminodiacetic acid (IDA). Aminocarboxylic acids and their salts can be used together with the abovementioned builders, in particular also with the phosphate-free builders.
- MGDA methylglycinediacetic acid
- GLDA glutamic diacetic acid
- IDA iminodiacetic acid
- Aminocarboxylic acids and their salts can be used together with the abovementioned builders, in particular also with the phosphate-free builders.
- MGDA MGDA
- GLDA GLDA
- salts thereof MGDA
- MGDA MGDA
- MGDA can be used preferably as granules, and particularly preferably in the solid phase. Particular preference is given to those MGDA granules which contain as little water as possible and / or have low hygroscopicity.
- MGDA or salts thereof in a total amount of 3 to 50 wt .-% based on the total weight of the cleaning agent.
- the detergents may contain, in particular, phosphonates as builder.
- the phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate.
- hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance.
- aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
- Phosphonate-containing components are contained in the compositions preferably in amounts of 0.1 to 10 wt .-%, in particular in amounts of 0.5 to 8 wt .-%, each based on the total weight of the cleaning agent.
- the compositions according to the invention contain from 0.01 to 25% by weight, preferably from 5 to 20% by weight, from 8 to 15% by weight. % Phosphonate (in each case based on the total weight of the composition).
- the phosphonates are preferably contained in the solid phase (s).
- substantially free of water means that a composition contains less than 7% by weight, in particular less than 5% by weight, preferably less than 3% by weight, more preferably less than 1% by weight. Contains% water.
- the water content refers to the water content determined by Karl Fischer titration.
- the liquid phase is according to "substantially free of water", this means that the liquid phase less than 7 wt .-%, in particular less than 5 wt .-%, preferably less than 3 wt .-%, more preferably less than 1 wt .-% water.
- the water content as defined herein refers to the water content determined by Karl Fischer titration.
- all liquid phases and all solid phases of the detergent of the invention are "substantially free of water", i. each of the individual phases contains in each case less than 7% by weight, in particular less than 5% by weight, preferably less than 3% by weight, particularly preferably less than 1% by weight of water (in each case based on the total weight of the respective phase ).
- Liquid as used herein with respect to the cleaning agent of the present invention includes all flowable compositions and, in particular, also encompasses gels and pasty compositions. In particular, the term also includes non-Newtonian fluids having a yield point.
- At least one means 1 or more, for example, 1, 2, 3, 4, 5, or more.
- solid as used herein with respect to the cleaning composition of the invention includes all solid compositions, and includes in particular powdered, granulated, amorphous, compressed, in particular pressed, tabletted compositions. In addition to powdery constituents, powdery compositions may also partially contain granules.
- the cleaning agent according to the invention is present in a water-soluble packaging.
- the water-soluble packaging allows a portioning of the detergent.
- the amount of detergent in the sachet is preferably 5 to 50 g, more preferably 10 to 30 g, especially 15 to 25 g.
- the detergent is preferably in an amount sufficient to carry out the cleaning, in machine dishwashing detergents in particular a cycle or a complete program run of a dishwasher).
- the water-soluble packaging in this case has at least two or more spatially separated compartments (chambers) in which spatially separated at least one solid, preferably pulverulent, and at least one liquid phase are filled.
- two-chamber bags or two-chamber tablets which contain a solid and a liquid phase in separate compartments.
- multi-chamber packages multi-chamber bags or multi-chamber shaped bodies
- a phase is understood here to mean a detergent (partial) composition which, in combination with the other phase or phases, results in a cleaning agent, in particular a machine dishwashing detergent.
- the cleaning agent according to the invention in particular machine dishwashing detergent, can also be present in a water-soluble packaging, which in particular contains more than two, so for example, three, four, five or six compartments.
- the package contains two, three or more chambers (compartments), wherein one, two or more of these chambers are filled with liquid phases, which are preferably different from each other, and in particular one or more mutually different ingredients.
- pre-portioned detergents in which the water-soluble package contains one, two or more solid phase chambers (compartments) in addition to one, two or more liquid phases.
- solid phase chambers components
- two or more solid phases it is preferred that they be of different composition and / or have a different solid form.
- pre-portioned cleaning compositions which have at least one solid, preferably at least one pulverulent phase and at least one liquid phase in separate compartments.
- pre-portioned detergents which have at least one solid, preferably at least one compressed phase and one liquid phase in separate compartments.
- the pre-portioned cleaning agent may also be preferable for the pre-portioned cleaning agent to have two or more solid phases, of which at least one powdery and at least one compressed and at least one, also two, three or more liquid phases are in each case separate compartments.
- the pre-portioned detergent in particular the multi-chamber bag, contains a solid, one of which is different powdery and two liquid phases in each separate compartments.
- the at least one liquid phase in the cleaning agent according to the invention is substantially free of organic components which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol;
- Substantially free of organic components which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol means that in the liquid phase (in the case of several liquid phases in each individual liquid phase) less than 5 Wt .-%, preferably less than 3 wt .-% of such organic compounds are contained, which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol.
- the presence of usually short-chain organic solvents having an average molecular weight of less than 175 g / mol, such as dipropylene glycol dimethyl ether, preferably less than 150 g / mol, such as decane, octane, dipropylene glycols, glycerol, propanediols, monoethanolamine, diethanolamine be avoided, which are particularly prone to migration between the compartments.
- said organic components preferably organic solvents, which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol, in each case only to a proportion of less be contained as 5 wt .-%, preferably of less than 3 wt .-% (each based on the composition of the individual liquid phase).
- the total amount of the organic components contained in the liquid phase or the liquid phases, preferably organic solvents, which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol, is not more than 20 wt .-% (relative on the total weight of each liquid phase).
- the pre-portioned cleaning agent in particular machine dishwashing detergent, comprises a plurality of liquid phases in separate compartments
- each of the liquid phases is essentially free of organic components having an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol (except the components mentioned under a), since otherwise there is a migration of the components between the individual liquid phases in the separate compartments.
- the liquid phase or the liquid phases of the cleaning agents according to the invention contain at least one component according to a).
- Formula (I) are also a large part of the nonionic surfactants to grasp.
- Low-foaming alkoxylated nonionic surfactants in particular ethoxylated, low-foaming nonionic surfactants, are preferably used with preference.
- the automatic dishwashing agents contain nonionic surfactants from the group of alkoxylated alcohols.
- surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
- Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
- nonionic surfactants used are low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
- surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
- nonionic surfactants having a C 9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units.
- the cleaning performance of the preparations according to the invention can be significantly improved both in comparison to surfactant-free system and in comparison to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols contain
- the group of these nonionic surfactants includes, for example, the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular also the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ethers and the C 4-22 fatty alcohol ethers. (EO) 40-80 -2-hydroxyalkyl ether.
- R 1 is -O- (CH 2 -CH (R 2 ) -O) w - (CH 2 -CH (R 3 ) -O) x- (CH 2 -CH (R 4 ) -O) y - (CH 2 -CH (R 5 ) -O) z -R 6
- R 6 a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and w for values of 1 and 2 (for mixtures of such products also numerical values between 1 and 2, eg 1.5) and x stands for a value of at least 15.
- the group of these nonionic surfactants includes, for example, the C 2-26 fatty alcohol (PO) 1 - (EO) 15-40 -2-hydroxyalkyl ethers, in particular also the C 8-10 fatty alcohol (PO) 1 - (EO) 22 -2 -hydroxydecylether.
- At least one, preferably at least two, in particular at least three of the components according to a) have a melting point (at 1 bar) of ⁇ 30 ° C., preferably ⁇ 25 ° C., in the liquid phase, in particular ⁇ 20 ° C on.
- the cleaning agent in particular machine dishwashing detergent in the liquid phase, has as one of the components according to a) at least one polyalkylene glycol, preferably at least one polyethylene glycol or at least one polypropylene glycol, in particular at least one polyethylene glycol, with an average molecular weight between about 180 and approx 6000, preferably about 200 to about 5000, in particular between about 300 and about 4000, for example about 400, is included. It is particularly preferred if a component according to a) at least one polyalkylene glycol, preferably at least one polyethylene glycol, which has an average molecular weight between 300 and 600 g / mol.
- the liquid phase (at least one of the liquid phases, preferably the liquid phases) is a component according to a) at least one further polyalkylene glycol, preferably at least one polyethylene glycol (PEG), which has an average molecular weight between 2000 and 6000 g / mol, preferably an average molecular weight between 3500 to 4500, in particular about 4000, (INCI: PEG 4000).
- PEG polyethylene glycol
- the liquid phase has a PEG having an average molecular weight of about 400 (INCI: PEG 400) and a PEG having an average molecular weight of about 4000 (INCI: PEG 4000).
- the liquid phase or the at least one liquid phase, or the liquid phases of the cleaning agent according to the invention preferably additionally contain at least one nonionic surfactant, preferably one which also represents a component according to a) according to formula I.
- components according to a) are particularly advantageous because they may optionally provide a basis for the liquid phase in addition to the liquid polyalkylene glycols, without organic components, in particular organic solvents having an average molecular weight of less than 175 g / mol, preferably from less than 150 g / mol, must be used. It is particularly preferred in this case if in addition to one of the preferred components according to a) as a further preferred component according to a) at least one polyalkylene glycol, preferably at least one polyethylene glycol having an average molecular weight between about 300 and about 5000, in particular approx 4000 g / mol is used.
- the liquid phase is additionally a component according to a) at least one further polyalkylene glycol, preferably at least one polyethylene glycol (PEG), which has an average molecular weight between 2000 and 6000 g / mol, in particular PEG 4000 , having.
- PEG polyethylene glycol
- the liquid phase has a PEG having an average molecular weight of about 400 (INCI: PEG 400) and a PEG having an average molecular weight of about 4000 (INCI: PEG 4000).
- the amount of all components mentioned according to a) in the liquid phase is between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (in each case based on the total weight of the liquid phase).
- the amount of all of the components referred to as preferred according to a) in the liquid phase is between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (each based on the total weight of the liquid phase) ,
- the amount of all of the components referred to as preferred according to a) in the liquid phase is between 15 to 80 wt .-%, preferably between 20 to 70 wt .-% (each based on the total weight of the liquid phase) ,
- the amount of all of the components referred to as preferred according to a) in the liquid phase is between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (each based on the total weight of the liquid phase) ,
- the amount of all components mentioned as being preferred according to a) in the liquid phase is between 10 and 80% by weight, preferably between 20 and 70% by weight (in each case based on the total weight of the liquid phase) ,
- a end-capped nonionic surfactant according to formula II R 8 O [CH 2 CH (R 9 ) O] h [CH 2 ] k CH (OH) [CH 2 ] j OR 10 , be contained, in particular poly (oxyalkylated) nonionic surfactants of formula II in which R 8 and R 10 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 9 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, h are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
- each R 9 in the above formula R 8 O [CH 2 CH (R 9 ) O] h [CH 2 ] k CH (OH) [CH 2 ] j OR 10 may be different.
- R 8 and R 10 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
- R 9 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
- Particularly preferred values for h are in the range from 1 to 20, in particular from 6 to 15.
- each R 9 in the above formula may be different if h ⁇ 2.
- the alkylene oxide unit in the square bracket can be varied.
- the value 3 for h has been chosen here by way of example and may well be greater, with the variation range increasing with increasing h values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
- R 8 , R 10 and R 9 are as defined above and x represents numbers of 1 to 30, preferably 1 to 20 and in particular from 6 to 18.
- Particularly preferred are surfactants in which the radicals R 8 and R 10 have 9 to 14 C atoms, R 9 is H and h assumes values of 6 to 15.
- the amount of all components according to a) in the liquid phase is between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (in each case based on the total weight of the liquid phase).
- the ratio of the weight of one or more solid phases (of which preferably at least one solid phase is powdery, (in the case of several solid / powder phases the total weight of all solid and powder phases) to the weight of one or more liquid phases (in the case of several liquid phases preferably 1:10 to 10: 1, particularly preferably 1: 5 to 5: 1, very particularly preferably 4: 1 to 1: 2.
- the cleaning agent in particular machine dishwashing detergent, is substantially free of anionic surfactants
- substantially free of anionic surfactants means that a composition is less than 7% by weight, preferably less than 5% by weight, more preferably less than 3% by weight, most preferably less than 1% by weight. -%, particularly preferably less than 0.1 wt .-% anionic surfactant (based on the total weight of the composition). This preferably applies to all, in particular also the combinations according to the invention explicitly mentioned as preferred above.
- the water-soluble coating of the cleaning agent, the packaging is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends.
- the wrapper may be formed of one or two or more layers of the water-soluble film material.
- the water-soluble film material of the first layer and the further layers, if present, may be the same or different. Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent.
- the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
- Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.
- Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose Molecular weight in the range of 10,000 to 1,000,000 gmol -1 , preferably from 20,000 to 500,000 gmol -1 , more preferably from 30,000 to 100,000 gmol -1 and in particular from 40,000 to 80,000 gmol -1 .
- polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible.
- polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
- a polymer selected from the group consisting of (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid, or mixtures of the above may be additionally used in a polyvinyl alcohol-containing film material suitable for producing the water-soluble coating Be added polymers.
- a preferred additional polymer is polylactic acids.
- Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers.
- Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
- polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters.
- Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.
- the film material contains further additives.
- the film material may contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof.
- Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-sticking agents or mixtures thereof.
- Suitable water-soluble films for use in the water-soluble casings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900.
- Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
- the cleaning agents according to the invention can be used as dishwashing agents, in particular automatic dishwasher detergents.
- the corresponding use is also the subject of the invention.
- the invention likewise relates to a dishwashing process, in particular a machine dishwashing process, in which a cleaning agent according to the invention is used.
- the particular embodiments described above also apply to the use or the method.
- the cleaning agents according to the invention are preferably a dishwasher detergent, in particular a machine dishwashing detergent.
- the pre-portioned detergent according to the invention in particular machine dishwashing detergent, is essentially free of phosphates. This preferably applies to all, in particular also the combinations according to the invention explicitly mentioned as preferred above.
- Substantially free of phosphates means that the total cleaning agent resulting from the addition of all phases (or all ingredients of all compartments) is preferably substantially free of phosphate-containing components.
- Phosphates or else phosphate-containing components in the context of the present invention are in particular phosphates, polyphosphates and pyrophosphates. However, phosphonates or hexafluorophosphate are not covered by this term.
- the total detergent thus contains less than 1% by weight, preferably 0.5% by weight, of phosphate based on the total weight of the detergent (i.e., the total weight of all phases (i.e., all liquid and solid phases).
- the detergents according to the invention in particular machine dishwashing detergents, comprise builders, such as, for example, zeolites, silicates, carbonates, in particular the alkali metal carbonates, for example sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, and organic cobuilders.
- builders such as, for example, zeolites, silicates, carbonates, in particular the alkali metal carbonates, for example sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, and organic cobuilders.
- Particularly suitable silicates are crystalline layered silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred Values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20, into consideration. It is also possible to use amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.
- the content of silicates based on the total weight of the cleaning agent, to amounts below 10 wt .-%, preferably below 5 wt .-%.
- compositions according to the invention preferably comprise at least one further constituent, preferably selected from the group consisting of cationic and amphoteric surfactants, bleaching agents, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances, bitter substances , and antimicrobial agents.
- bleaching agents can also be used.
- sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
- Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. It is also possible to use all other inorganic or organic peroxy bleaches known to the person skilled in the art.
- chlorine or bromine releasing substances can be used.
- suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
- DICA dichloroisocyanuric acid
- Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
- detergents preferably dishwashing agents, in particular automatic dishwasher detergents, which contain 1 to 35% by weight, preferably 2.5 to 30% by weight, particularly preferably 3.5 to 25% by weight, very particularly preferably 4.0 to 20 wt .-% and in particular 5 to 18 wt .-% (based on the total weight of the cleaning agent) bleach, preferably sodium percarbonate.
- bleach preferably sodium percarbonate in the solid phase (or in one of the solid phases) is bleach, preferably sodium percarbonate, preferably in an amount of 5 to 40 wt .-%, preferably from 10 to 20 wt .-% (based on the total weight of the solid phases).
- the cleaning agents may contain bleach catalysts.
- Useful bleach catalysts include, but are not limited to, the group of bleach-enhancing transition metal salts and transition metal complexes, preferably Mn, Fe, Co, Ru or Mo complexes, more preferably from the group of manganese and / or cobalt salts and / or or complexes, in particular the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, the manganese sulfate and the complexes of manganese with 1,4,7- trimethyl-1,4,7-triazacyclononane (Mn 3 -TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Mn 4 -TACN).
- detergents preferably dishwashing agents, in particular automatic dishwasher detergents, which contain from 0.001 to 1% by weight, preferably from 0.01 to 0.1% by weight (based in each case on the total weight of the cleaning agent) of bleach catalyst, preferably a Mn complex.
- a Mn complex in particular a complex of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Mn 3 -TACN) or 1,2,4,7-tetramethyl-1,4,7-tri-azacyclononane (Mn 4 -TACN).
- the cleaning agents preferably dishwashing agents, in particular automatic dishwasher detergents, additionally comprise at least one bleach activator.
- bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
- polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), are acylated Glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferably used.
- TAED tetraacetylethylenediamine
- DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
- TAGU tetraacet
- Combinations of conventional bleach activators can also be used. These bleach activators are preferably used in amounts of up to 10% by weight, in particular from 0.1% by weight to 8% by weight, especially from 2 to 8% by weight and more preferably from 2 to 6% by weight, based in each case on the total weight of the detergents used.
- the bleaching agent and also bleach catalysts and / or bleach activators are preferably contained in the solid phase (s).
- Suitable amphoteric surfactants are, for example, betaines of the formula (R iii ) (R iv ) (R v ) N + CH 2 COO - , in which R iii is an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R iv and R v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C 10 -C 18 -Alkyldimethylcarboxymethylbetain and C 11 -C 17 -Alkylamidopropyl-dimethylcarboxymethylbetain.
- Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R vi ) (R vii ) (R viii ) (R ix ) N + X - , in which R vi to R ix are four identical or different, in particular two long and two short-chain, alkyl radicals and X - are an anion, in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof.
- quaternary surface-active compounds in particular having a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
- the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.
- the enzymes include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents, which are preferably used accordingly.
- Detergents according to the invention preferably contain enzymes in total amounts of from 1 ⁇ 10 -6 to 5% by weight, based on active protein.
- the protein concentration can be determined by known methods, for example the BCA method or the biuret method.
- subtilisin type those of the subtilisin type are preferable.
- these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
- amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the further developments of the aforementioned amylases which are improved for use in cleaning agents. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
- lipases or cutinases are also usable according to the invention.
- these include, for example, the lipases originally obtainable from, or further developed, Humicola lanuginosa ( Thermomyces lanuginosus ), in particular those having one or more of the following amino acid exchanges starting from said lipase in positions D96L, T213R and / or N233R, most preferably all of the exchanges D96L, T213R and N233R.
- Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
- a protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
- damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
- inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
- Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
- Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage and transportable preparations.
- These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or Gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or other auxiliaries.
- the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
- further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
- Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
- such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
- the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
- Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10 wt .-% of the enzyme protein.
- detergents which, based in each case on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight, of enzyme preparations.
- the enzymes in particular the amylase (s) and / or protease (s), are preferably present in (one) of the solid phase (s), preferably as granules or granules.
- Glass corrosion inhibitors used are metal salts, in particular zinc salts or bismuth salts, preferably zinc salts, in particular zinc acetate.
- Polyethyleneimines and polyvinylamines which are obtainable for example under the name Lupasol® or Lupamin® from BASF, in particular non-alkoxylated polyethyleneimines, are also preferably used as glass corrosion inhibitors.
- Glass corrosion inhibitors are preferably present in compositions according to the invention in an amount of from 0.05 to 5% by weight, in particular in an amount of from 0.1 to 2% by weight.
- the cleaning agents according to the invention are characterized in that they are stable on storage and even after a prolonged period, no phase separation occurs.
- a further subject of the present invention is also a machine dishwashing process in which a cleaning agent according to the invention is used.
- the invention also relates to the use of the cleaning agent according to the invention as a dishwashing detergent, in particular automatic dishwashing detergent.
- inventive detergent formulation E1 (E1 according to Table 1, 2) and a corresponding comparative formulation V1 (V1 according to Table 1, 2) were prepared.
- the amounts indicated in the tables are in% by weight of active substance.
- 15 g of the solid phase were sealed into a first chamber and 5 g each of the liquid phase (E1 or V1) in a chamber next to the first chamber in a two-chamber bag made of polyvinyl alcohol.
- the weight of 1 liter of powder was determined.
- Example E1 according to the invention shows a higher average product density compared to comparative formulation V1 (combination of 15 g of solid phase V1 and 5 g of liquid phase V1).
- the pre-portioned cleaning agent according to the invention fills a smaller volume with the same amount of active substances and thus can also be used in volume-limited metering chambers.
- a pre-proportioned detergent with the same volume of the portion as in the comparison substance a pre-portioned detergent with a higher weight (and thus a higher content of active ingredient per wash) can be used.
- pre-portioned detergents of the following composition E2
- 12 g of the solid phase (E2) were sealed in a first bag of polyvinyl alcohol and 4 g of the liquid phase (E2) were sealed in a second bag of polyvinyl alcohol.
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)
Description
Die vorliegende Erfindung betrifft vorportionierte mehrphasige Reinigungsmittel, insbesondere maschinelle Geschirrspülmittel und deren Verwendung.The present invention relates to pre-portioned multi-phase detergents, in particular automatic dishwashing detergents and their use.
Reinigungsmittel für harte Oberflächen, wie beispielsweise Geschirrspülmittel, stehen dem Verbraucher in einer Vielzahl von Angebotsformen zur Verfügung. Neben den traditionellen festen Mitteln gewinnen in letzter Zeit zunehmend fließfähige und insbesondere flüssige bis gelförmige Reinigungsmittel an Bedeutung. Der Verbraucher schätzt vor allem die schnelle Löslichkeit und die damit einhergehende schnelle Verfügbarkeit der Inhaltsstoffe in der Reinigungsflotte insbesondere auch in Kurzgeschirrspülprogrammen und bei niedrigen Temperaturen.Hard surface cleaners, such as dishwashing detergents, are available to the consumer in a variety of forms. In addition to the traditional solid agents are gaining increasingly increasingly flowable and especially liquid to gel detergent in importance. The consumer particularly appreciates the rapid solubility and the associated rapid availability of the ingredients in the cleaning liquor, especially in short-dishwashing programs and at low temperatures.
Dabei nimmt die Bedeutung von konzentrierten Zusammensetzungen, in denen insbesondere der Wassergehalt gegenüber herkömmlichen Zusammensetzungen vermindert ist, zu. Für den Verbraucher sind somit Zusammensetzungen, deren Wassergehalt möglichst gering ist, besonders wünschenswert.The importance of concentrated compositions, in which in particular the water content is reduced compared to conventional compositions, increases. Thus, for the consumer, compositions whose water content is as low as possible are particularly desirable.
Ferner haben sich die Verbraucher an ein bequemes Dosieren von vorportionierten maschinellen Geschirrspülmitteln gewöhnt und nutzen diese Produkte bisher vor allem in Form von Tabletten. Um ein mehrphasiges Geschirrspülmittel, welches die oben erwähnten Vorteile von festen und flüssigen Zusammensetzungen vereint, in eine vorportionierte Angebotsform zu bringen, bietet sich die Verwendung von wasserlöslichen Folien in der Form von Beuteln oder Mehrkammerformkörpern an.Further, consumers have become accustomed to conveniently dosing pre-portioned automatic dishwashing detergents and have been using these products primarily in the form of tablets. In order to bring a multi-phase dishwashing detergent, which combines the above-mentioned advantages of solid and liquid compositions, into a pre-portioned form, the use of water-soluble films in the form of bags or multi-chamber shaped bodies lends itself.
Einmalportionen, insbesondere wasserlösliche Beutel oder Mehrkammerformkörper aus wasserlöslichem Material, erfreuen sich beim Verbraucher nicht nur deshalb zunehmender Beliebtheit, weil der Verbraucher mit der chemischen Zusammensetzung nicht mehr in Berührung kommt, sondern nicht zuletzt auch wegen der attraktiven Optik der Beutel. Für den Verbraucher ist es somit ein Ärgernis, wenn die Beutel ihre attraktive Optik verlieren.Disposable portions, in particular water-soluble bags or multi-chamber tablets made of water-soluble material, enjoy the consumer not only because of increasing popularity, because the consumer with the chemical composition is no longer in contact, but not least because of the attractive appearance of the bag. For the consumer, it is therefore a nuisance if the bags lose their attractive appearance.
Multifunktionelle automatische Geschirrspülmittel ersparen dem Anwender den separaten Einsatz von Klarspüler und das Nachfüllen des Salzvorrates in der Geschirrspülmaschine. In ihren Formulierungen werden neben geeigneten Tensiden auch bestimmte Builder eingesetzt, die ein gutes Klarspülergebnis erzielen und der Bildung von Belägen auch bei höherer Wasserhärte entgegenwirken.Multifunctional automatic dishwashing detergents save the user the separate use of rinse aid and the refilling of salt in the dishwasher. In addition to suitable surfactants, certain builders are used in their formulations which achieve a good rinse aid result and counteract the formation of coatings even at higher water hardness.
Moderne Geschirrspülmaschinen sehen für die Dosierung von Reinigungsprodukten eine Dosierkammer vor, die sich während des Spülprogrammes automatisch öffnet und das Produkt freigibt. Die Größe der Dosierkammer ist allerdings in ihrem Fassungsvermögen begrenzt.
Für eine gute Reinigungsleistung müssen aber ausreichende Mengen verschiedener Funktionsblöcke der Geschirrspülmittelformulierung wie Builder, Alkalität, Enzyme, Tenside, etc. zur Verfügung gestellt werden. Dies bedeutet, dass das zur Verfügung stehende Volumen der Dosierkammer optimal genutzt werden muss, um eine genügende Menge der aktiven Substanzen und damit eine gute Reinigungsleistung zu erzeugen.Modern dishwashers provide for dosing of cleaning products before a dosing, which automatically opens during the wash program and releases the product. The size of the metering chamber is however limited in its capacity.
For a good cleaning performance, however, sufficient quantities of various functional blocks of the dishwashing detergent formulation, such as builder, alkalinity, enzymes, surfactants, etc., must be made available. This means that the available volume of the dosing chamber must be used optimally in order to produce a sufficient amount of the active substances and thus a good cleaning performance.
Aufgabe der vorliegenden Erfindung war es, ein mehrphasiges vorportioniertes Reinigungsmittel, insbesondere Geschirrspülmittel, bevorzugt Maschinengeschirrspülmittel, mit mindestens einer flüssigen und mindestens einer festen, bevorzugt pulverförmigen Phase bereitzustellen, das in die Einspülkammer der Geschirrspülmaschine passt und trotzdem eine gute Reinigungsleistung zeigt.The object of the present invention was to provide a multi-phase pre-portioned detergent, in particular dishwashing detergent, preferably automatic dishwashing detergent, with at least one liquid and at least one solid, preferably pulverulent phase, which fits into the dispensing compartment of the dishwasher and still exhibits good cleaning performance.
Diese Aufgabe wurde gelöst durch ein vorportioniertes Reinigungsmittel, bevorzugt Maschinengeschirrspülmittel, in einer Verpackung mit mindestens zwei Kompartimenten, umfassend mindestens eine feste, bevorzugt pulverförmige Phase und mindestens eine flüssige Phase, dadurch gekennzeichnet, dass das Reinigungsmittel 2 bis 20 Gew.-%, insbesondere 2 bis 10 Gew.-% (bezogen auf das Gesamtgewicht des Mittels) polymere oder co-polymere Polycarboxylate und/oder Sulfonsäuregruppenhaltige Polymere enthält und die feste Phase (bzw. die festen Phasen) weniger als 1 Gew.-% (bezogen auf das Gewicht der festen Phase), polymere und/oder oder co-polymere Polycarboxylate und/oder Sulfonsäuregruppenhaltige Polymere enthält, wobei das Reinigungsmittel weniger als 1 Gew.-% Phosphat, bezogen auf das Gesamtgewicht des Reinigungsmittels, enthält.This object is achieved by a pre-portioned detergent, preferably machine dishwashing detergent, in a package having at least two compartments, comprising at least one solid, preferably pulverulent phase and at least one liquid phase, characterized in that the detergent contains 2 to 20% by weight, in particular 2 to 10% by weight (based on the total weight of the composition) of polymeric or co-polymeric polycarboxylates and / or sulfonic acid group-containing polymers and the solid phase (or solid phases) less than 1 wt .-% (based on the weight of the solid phase), polymeric and / or co-polymeric polycarboxylates and / or sulfonic acid group-containing polymers, wherein the cleaning agent contains less than 1% by weight of phosphate, based on the total weight of the cleaning agent.
Insbesondere in Reinigungsmitteln, insbesondere in solchen, die nur geringe Mengen Phosphat enthalten bzw. die im Wesentlichen frei von Phosphaten sind, müssen zusätzlich zu den phosphathaltigen und/oder phosphatfreien Buildern auch Cobuilder eingesetzt werden, um eine ausreichend hohe Komplexierung von zweiwertigen Kationen aus dem verwendeten Spülwasser, in der Regel ortsübliches Leitungswasser, zu gewährleisten, die ansonsten auf dem Geschirr Beläge hinterlassen.In particular in cleaning agents, in particular in those which contain only small amounts of phosphate or which are substantially free of phosphates, co-builders must be used in addition to the phosphate-containing and / or phosphate-free builders in order to achieve a sufficiently high complexation of divalent cations from the used Rinse water, usually local tap water to ensure that otherwise leave on the dishes coverings.
Polymere, polycarboxylathaltige Cobuilder werden in der Regel als wässrige Zubereitungen vermarktet. In wässrigen Maschinengeschirrspülmitteln werden sie daher in der Regel direkt in die wässrigen Reinigungsmittel formuliert. Sollen sie in festen Formulierungen eingesetzt werden, müssen sie erst zeit- und energieaufwendig getrocknet und anschließend als Granulat formuliert werden. Dann sind sie insbesondere geeignet für feste, insbesondere granuläre Produkte.Polymeric, polycarboxylate-containing cobuilders are usually marketed as aqueous preparations. In aqueous machine dishwashing detergents, they are therefore usually formulated directly into the aqueous cleaning agents. If they are to be used in solid formulations, they must first be dried time-consuming and energy-intensive and then formulated as granules. Then they are particularly suitable for solid, especially granular products.
Für den Einsatz in flüssigen, nicht wässrigen Reinigungsmitteln, insbesondere in Maschinengeschirrspülmitteln, sind die wässrigen Zubereitungen der Cobuilder aufgrund des hohen Wassereintrags nicht geeignet.For use in liquid, non-aqueous cleaning agents, especially in machine dishwashing detergents, the aqueous preparations of co-builders are not suitable due to the high water input.
In einem mehrphasigen vorportionierten Reinigungsmittel, insbesondere Maschinengeschirrspülmittel, welches mindestens eine feste und eine flüssige Phase enthält, welches in Bezug auf die Dimensionen der Dosierkammer in Geschirrspülern optimiert ist, muss insbesondere eine platzsparende Formulierung eingesetzt werden.In a multi-phase pre-portioned detergent, in particular machine dishwashing detergent, which contains at least one solid and one liquid phase, which is optimized in terms of the dimensions of the metering chamber in dishwashers, a space-saving formulation must be used in particular.
Will man polymere Polycarboxylathaltige Komponenten und/oder Sulfonsäuregruppenhaltige Polymere in flüssigen Reinigungsmitteln, insbesondere flüssigen Maschinengeschirrspülmitteln, einsetzen, die bevorzugt im Wesentlichen frei von Wasser sind, müssen die festen Komponenten in einer organischen Matrix fein verteilt (als Dispersion) vorliegen und auch lagerstabil in der Dispersion verbleiben und dürfen nicht sedimentieren. Am besten wird in solche flüssigen Formulierungen, die im Wesentlichen frei von Wasser sind, die getrockneten (vom Wasser befreiten) Polycarboxylathaltige Komponente und/oder die Sulfonsäuregruppenhaltige Polymere in fein gemahlener Form eingesetzt.If it is desired to use polymeric polycarboxylate-containing components and / or polymers containing sulfonic acid groups in liquid cleaning agents, in particular liquid machine dishwashing detergents, which are preferably essentially free of water, the solid components must be finely distributed (as a dispersion) in an organic matrix and also stable in storage in the dispersion remain and must not sediment. Most preferably, in such liquid formulations that are substantially free of water, the dried (de-watered) polycarboxylate-containing component and / or the sulfonic acid group-containing polymers are used in finely ground form.
Das erfindungsgemäße Reinigungsmittel, insbesondere Maschinengeschirrspülmittel, enthält insgesamt 2 bis 20 Gew.-%, insbesondere 2 bis 10 Gew.-% (jeweils bezogen auf das Gesamtgewicht des Mittels, d.h. des Gesamtgewichts aller Phasen) polymere oder co-polymere Polycarboxylate oder Sulfonsäuregruppen-haltige Polymere.The cleaning agent according to the invention, in particular machine dishwashing detergent, contains a total of 2 to 20 wt .-%, in particular 2 to 10 wt .-% (each based on the total weight of the composition, ie the total weight of all phases) polymeric or co-polymeric polycarboxylates or sulfonic acid-containing polymers.
Die erfindungsgemäßen Reinigungsmittel können insbesondere ein sulfonsäuregruppen-haltige Polymere (im weiteren auch als Sulfopolymer bezeichnet) enthalten. Der Gewichtsanteil des Sulfopolymers am Gesamtgewicht des erfindungsgemäßen Reinigungsmittels beträgt dabei vorzugsweise von 0,1 bis 20 Gew.-%, insbesondere von 0,5 bis 18 Gew.-%, besonders bevorzugt 1,0 bis 15 Gew.-%, ganz besonders bevorzugt 2,0 bis 14 Gew.-%, insbesondere von 4 bis 14 Gew.-%, vor allem von 4,5 bis 12 Gew.-%. Das Sulfopolymer wird hier insbesondere in einer getrockneten, besonders bevorzugt in einer getrockneten und granulierten (festen) Form eingesetzt, wobei diese optional zusätzlich vermahlen sein kann. Als Sulfopolymer wird vorzugsweise ein copolymeres Polysulfonat, beispielsweise ein hydrophob modifiziertes copolymeres Polysulfonat, eingesetzt.
Insbesondere enthält das erfindungsgemäße Reinigungsmittel insgesamt 2 bis 20 Gew.-%, insbesondere 2 bis 10 Gew.-% (jeweils bezogen auf das Gesamtgewicht des Mittels) (co-) polymere Polycarboxylate und Sulfonsäuregruppen-haltige Polymere.The cleaning agents according to the invention may in particular contain a sulfonic acid group-containing polymer (hereinafter also referred to as sulfopolymer). The proportion by weight of the sulfopolymer in the total weight of the cleaning agent according to the invention is preferably from 0.1 to 20 wt .-%, in particular from 0.5 to 18 wt .-%, particularly preferably 1.0 to 15 wt .-%, most preferably 2.0 to 14 wt .-%, in particular from 4 to 14 wt .-%, especially from 4.5 to 12 wt .-%. The sulfopolymer is used here in particular in a dried, particularly preferably in a dried and granulated (solid) form, which may optionally additionally be ground. The sulfopolymer used is preferably a copolymeric polysulfonate, for example a hydrophobically modified copolymeric polysulfonate.
In particular, the inventive cleaning agent contains a total of 2 to 20 wt .-%, in particular 2 to 10 wt .-% (each based on the total weight of the composition) (co) polymeric polycarboxylates and sulfonic acid-containing polymers.
Gemäß einer ganz besonders bevorzugten Ausführungsform ist die feste Phase (sind die festen Phasen) im Wesentlichen frei von polymeren oder co-polymere Polycarboxylaten und/oder Sulfonsäuregruppenhaltige Polymere. Dies bedeutet in diesem Zusammenhang, dass die feste Phase bzw. dass die festen Phasen weniger als 1 Gew.-% (bezogen auf das Gewicht der festen Phase bzw. das Gesamtgewicht aller festen Phasen), polymere oder co-polymere Polycarboxylate und Sulfonsäuregruppen-haltige Polymere enthalten. Bevorzugt enthält dabei das Reinigungsmittel selbst 2 bis 20 Gew.-% (bezogen auf das Gesamtgewicht des Reinigungsmittels (Gesamtgewicht aller Phasen)) polymere oder co-polymere Polycarboxylate und Sulfonsäuregruppen-haltige Polymere.In a most preferred embodiment, the solid phase (s) are substantially free of polymeric or co-polymeric polycarboxylates and / or sulfonic acid group-containing polymers. In this context, this means that the solid phase or phases are less than 1% by weight (based on the weight of the solid phase or the total weight of all solid phases), polymeric or co-polymeric polycarboxylates and sulfonic acid group-containing Contain polymers. The cleaning agent itself preferably contains from 2 to 20% by weight (based on the total weight of the cleaning agent (total weight of all phases)) of polymeric or co-polymeric polycarboxylates and sulfonic acid-containing polymers.
Die polymeren oder copolymeren Polycarboxylate sind erfindungsgemäß als Builder geeignet, dies sind beispielsweise die Alkalimetallsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer relativen Molekülmasse von 500 bis 70000 g/mol. Das Polyacrylat bzw. die Polyacrylate werden hier insbesondere in einer getrockneten, besonders bevorzugt in einer getrockneten und granulierten (festen) Form eingesetzt, wobei diese optional zusätzlich vermahlen sein kann.The polymeric or copolymeric polycarboxylates are suitable according to the invention as builders, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 500 to 70,000 g / mol. The polyacrylate or the polyacrylates are used here in particular in a dried, particularly preferably in a dried and granulated (solid) form, which may optionally additionally be ground.
Geeignete Polymere sind insbesondere Polyacrylate, die bevorzugt eine Molekülmasse von ca. 1000 bis 20000, insbesondere von 2000 bis 20000 g/mol aufweisen. Aufgrund ihrer überlegenen Löslichkeit können aus dieser Gruppe wiederum die kurzkettigen Polyacrylate, die Molmassen von ca. 1000 bis 10000, von 2000 bis 10000 g/mol, und besonders bevorzugt von 3000 bis 5000 g/mol, aufweisen, bevorzugt sein.Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of about 1000 to 20,000, in particular from 2000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of about 1000 to 10,000, of 2,000 to 10,000 g / mol, and particularly preferably of 3,000 to 5,000 g / mol, may again be preferred from this group.
Geeignet sind weiterhin copolymere Polycarboxylate, insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt im allgemeinen 2000 bis 70000 g/mol, vorzugsweise 20000 bis 50000 g/mol und insbesondere 30000 bis 40000 g/mol.Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
Nicht als polymere Polycarboxylate im Sinne der Erfindung sind Polycarbonsäuren (Carbonsäuren mit mehr als einer Carboxylatfunktion) in monomerer Form aufzufassen.
Insbesondere sind nicht darunter solche Polycarbonsäuren zu verstehen, wie sie weiter unten als organische Co-builder eingehend beschrieben sind und erfindungsgemäß sowohl in der/den flüssigen Phase(n) als auch der/den festen Phase(n) enthalten sein können (d.h. sie sind bei den für polymere Polycarboxylate genannten Mengenangaben nicht umfasst und werden für die Mengenbeschränkungen somit nicht berücksichtigt).For the purposes of the invention, polycarboxylic acids (carboxylic acids having more than one carboxylate function) in monomeric form are not to be understood as polymeric polycarboxylates.
In particular, it does not include those polycarboxylic acids as described in detail below as organic cobuilders and which may be present in the liquid phase (s) as well as the solid phase (s) according to the invention (ie they are is not included in the amounts indicated for polymeric polycarboxylates and are thus not taken into account for the quantitative restrictions).
Die erfindungsgemäßen Reinigungsmittel können wie oben beschrieben, ein sulfonsäuregruppenhaltige Polymere (im weiteren auch als Sulfopolymer bezeichnet), enthalten. Als Sulfopolymer wird vorzugsweise ein copolymeres Polysulfonat, zum Beispiel ein hydrophob modifiziertes copolymeres Polysulfonat, eingesetzt.The cleaning agents according to the invention can, as described above, contain a sulfonic acid group-containing polymer (also referred to below as sulfopolymer). The sulfopolymer used is preferably a copolymeric polysulfonate, for example a hydrophobically modified copolymeric polysulfonate.
Die Copolymere können zwei, drei, vier oder mehr unterschiedliche Monomereinheiten aufweisen.The copolymers may have two, three, four or more different monomer units.
Bevorzugte copolymere Polysulfonate enthalten neben Sulfonsäuregruppen-haltigem(n) Monomer(en) wenigstens ein Monomer aus der Gruppe der ungesättigten Carbonsäuren.Preferred copolymeric polysulfonates contain not only sulfonic acid group-containing monomer (s) but also at least one monomer selected from the group consisting of unsaturated carboxylic acids.
Als ungesättigte Carbonsäure(n) wird/werden mit besonderem Vorzug ungesättigte Carbonsäuren der Formel R1(R2)C=C(R3)COOH eingesetzt, in der R1 bis R3 unabhängig voneinander für -H, -CH3, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH2, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR4 steht, wobei R4 ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist.As unsaturated carboxylic acid (s), it is particularly preferred to use unsaturated carboxylic acids of the formula R 1 (R 2 ) C =C (R 3 ) COOH in which R 1 to R 3, independently of one another, are -H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or -COOH substituted alkyl or alkenyl radicals as above is defined or is -COOH or -COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
Besonders bevorzugte ungesättigte Carbonsäuren sind Acrylsäure, Methacrylsäure, Ethacrylsäure, alpha-Chloroacrylsäure, alpha-Cyanoacrylsäure, Crotonsäure, alpha-Phenyl-Acrylsäure, Maleinsäure, Maleinsäureanhydrid, Fumarsäure, Itaconsäure, Citraconsäure, Methylenmalonsäure, Sorbinsäure, Zimtsäure oder deren Mischungen. Einsetzbar sind selbstverständlich auch die ungesättigten Dicarbonsäuren.Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid, alpha-cyanoacrylic acid, crotonic acid, alpha-phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.
Bei den Sulfonsäuregruppen-haltigen Monomeren sind solche der Formel
R5(R6)C=C(R7)-X-SO3H
bevorzugt, in der R5 bis R7 unabhängig voneinander für -H, -CH3, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH2, -OH oder -COOH substituierte Alkyl- oder Alkenylreste oder für -COOH oder -COOR4 steht, wobei R4 ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH2)n- mit n = 0 bis 4, -COO-(CH2)k- mit k = 1 bis 6, -C(O)-NH-C(CH3)2-, -C(O)-NH-C(CH3)2-CH2- und -C(O)-NH-CH(CH3)-CH2-.In the sulfonic acid-containing monomers are those of the formula
R 5 (R 6 ) C = C (R 7 ) -X-SO 3 H
in which R 5 to R 7 independently of one another are -H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH 2 , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH 2 ) n - with n = 0 to 4, -COO- (CH 2 ) k - with k = 1 to 6, -C (O) -NH-C (CH 3 ) 2 - , -C (O) -NH-C (CH 3 ) 2 -CH 2 - and -C (O) -NH-CH (CH 3 ) -CH 2 -.
Unter diesen Monomeren bevorzugt sind solche der Formeln
H2C=CH-X-SO3H
H2C=C(CH3)-X-SO3H
HO3S-X-(R6)C=C(R7)-X-SO3H,
in denen R6 und R7 unabhängig voneinander ausgewählt sind aus -H, -CH3, -CH2CH3,-CH2CH2CH3 und -CH(CH3)2 und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH2)n- mit n = 0 bis 4, -COO-(CH2)k- mit k = 1 bis 6, -C(O)-NH-C(CH3)2-, -C(O)-NH-C(CH3)2-CH2- und -C(O)-NH-CH(CH3)-CH2-.Preferred among these monomers are those of the formulas
H 2 C = CH-X-SO 3 H
H 2 C = C (CH 3 ) -X-SO 3 H
HO 3 SX- (R 6 ) C = C (R 7 ) -X-SO 3 H,
in which R 6 and R 7 are independently selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 and -CH (CH 3 ) 2 and X is an optional spacer group which is selected from - (CH 2 ) n - with n = 0 to 4, -COO- (CH 2 ) k - with k = 1 to 6, -C (O) -NH-C (CH 3 ) 2 -, - C (O) -NH-C (CH 3 ) 2 -CH 2 - and -C (O) -NH-CH (CH 3 ) -CH 2 -.
Besonders bevorzugte Sulfonsäuregruppen-haltige Monomere sind dabei 1-Acrylamido-1-propansulfonsäure, 2-Acrylamido-2-propansulfonsäure, 2-Acrylamido-2-methyl-1-propansulfonsäure, 2-Methacrylamido-2-methyl-1-propansulfonsäure, 3-Methacrylamido-2-hydroxy-propansulfonsäure, Allylsulfonsäure, Methallylsulfonsäure, Allyloxybenzolsulfonsäure, Methallyloxybenzolsulfonsäure, 2-Hydroxy-3-(2-propenyloxy)propansulfonsäure, 2-Methyl-2-propen1-sulfonsäure, Styrolsulfonsäure, Vinylsulfonsäure, 3-Sulfopropylacrylat, 3-Sulfopropylmethacrylat, Sulfomethacrylamid, Sulfomethylmethacrylamid sowie Mischungen der genannten Säuren oder deren wasserlösliche Salze.Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic 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, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salts.
In den Polymeren können die Sulfonsäuregruppen ganz oder teilweise in neutralisierter Form vorliegen, d.h. dass das acide Wasserstoffatom der Sulfonsäuregruppe in einigen oder allen Sulfonsäuregruppen gegen Metallionen, vorzugsweise Alkalimetallionen und insbesondere gegen Natriumionen, ausgetauscht sein kann. Der Einsatz von teil- oder vollneutralisierten Sulfonsäuregruppen-haltigen Copolymeren ist erfindungsgemäß bevorzugt.In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
Die Monomerenverteilung der erfindungsgemäß bevorzugt eingesetzten Copolymere beträgt bei Copolymeren, die nur Carbonsäuregruppen-haltige Monomere und Sulfonsäuregruppen-haltige Monomere enthalten, vorzugsweise jeweils 5 bis 95 Gew.-%, besonders bevorzugt beträgt der Anteil des Sulfonsäuregruppen-haltigen Monomers 50 bis 90 Gew.-% und der Anteil des Carbonsäuregruppen-haltigen Monomers 10 bis 50 Gew.-%, die Monomere sind hierbei vorzugsweise ausgewählt aus den zuvor genannten.The monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.
Die Molmasse der erfindungsgemäß bevorzugt eingesetzten Sulfo-Copolymere kann variiert werden, um die Eigenschaften der Polymere dem gewünschten Verwendungszweck anzupassen. Bevorzugte Reinigungsmittel sind dadurch gekennzeichnet, dass die Copolymere Molmassen von 2000 bis 200.000 gmol-1, vorzugsweise von 4000 bis 25.000 gmol-1 und insbesondere von 5000 bis 15.000 gmol-1 aufweisen.The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
In einer weiteren bevorzugten Ausführungsform umfassen die Copolymere neben Carboxylgruppen-haltigem Monomer und Sulfonsäuregruppen-haltigem Monomer weiterhin wenigstens ein nichtionisches, vorzugsweise hydrophobes Monomer. Durch den Einsatz dieser hydrophob modifizierten Polymere konnte insbesondere die Klarspülleistung erfindungsgemäßer maschineller Geschirrspülmittel verbessert werden.In a further preferred embodiment, in addition to the carboxyl group-containing monomer and the monomer containing the sulfonic acid group, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer. The use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.
Anionische Copolymere umfassend Carbonsäuregruppen-haltige Monomere, Sulfonsäuregruppenhaltige Monomere und nichtionische Monomere, insbesondere hydrophobe Monomere, werden daher erfindungsgemäß bevorzugt.Anionic copolymers comprising monomers containing carboxylic acid groups, monomers containing sulfonic acid groups and nonionic monomers, in particular hydrophobic monomers, are therefore preferred according to the invention.
Als nichtionische Monomere werden vorzugsweise Monomere der allgemeinen Formel R1(R2)C=C(R3)-X-R4 eingesetzt, in der R1 bis R3 unabhängig voneinander für -H, -CH3 oder -C2H5 steht, X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -CH2-, -C(O)O- und -C(O)-NH-, und R4 für einen geradkettigen oder verzweigten gesättigten Alkylrest mit 1 bis 22 Kohlenstoffatomen oder für einen ungesättigten, vorzugsweise aromatischen Rest mit 6 bis 22 Kohlenstoffatomen steht.The nonionic monomers used are preferably monomers of the general formula R 1 (R 2 ) C =C (R 3 ) -XR 4 , in which R 1 to R 3, independently of one another, are -H, -CH 3 or -C 2 H 5, X is is an optionally present spacer group which is selected from -CH 2 -, -C (O) O- and -C (O) -NH-, and R 4 is a straight-chain or branched saturated alkyl radical having 1 to 22 carbon atoms or a unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.
Besonders bevorzugte nichtionische Monomere sind Buten, Isobuten, Penten, 3-Methylbuten, 2-Methylbuten, Cyclopenten, Hexen, Hexen-1, 2-Methlypenten-1, 3-Methlypenten-1, Cyclohexen, Methylcyclopenten, Cyclohepten, Methylcyclohexen, 2,4,4-Trimethylpenten-1, 2,4,4-Trimethylpenten-2, 2,3-Dimethylhexen-1, 2,4-Diemthylhexen-1, 2,5-Dimethlyhexen-1, 3,5-Dimethylhexen-1, 4,4-Dimehtylhexan-1, Ethylcyclohexyn, 1-Octen, alpha-Olefine mit 10 oder mehr Kohlenstoffatomen wie beispielsweise 1-Decen, 1-Dodecen, 1-Hexadecen, 1-Oktadecen und C22-alpha-Olefin, 2-Styrol, alpha-Methylstyrol, 3-Methylstyrol, 4-Propylstryol, 4-Cyclohexylstyrol, 4-Dodecylstyrol, 2-Ethyl-4-Benzylstyrol, 1-Vinylnaphthalin, 2,Vinylnaphthalin, Acrylsäuremethylester, Acrylsäureethylester, Acrylsäurepropylester, Acrylsäurebutylester, Acrylsäurepentylester, Acrylsäurehexylester, Methacrylsäuremethylester, N-(Methyl)acrylamid, Acrylsäure-2-Ethylhexylester, Methacrylsäure-2-Ethylhexylester, N-(2-Ethylhexyl)acrylamid, Acrylsäureoctylester, Methacrylsäureoctylester, N-(Octyl)acrylamid, Acrylsäurelaurylester, Methacrylsäurelaurylester, N-(Lauryl)acrylamid, Acrylsäurestearylester, Methacrylsäurestearylester, N-(Stearyl)acrylamid, Acrylsäurebehenylester, Methacrylsäurebehenylester und N-(Behenyl)acrylamid oder deren Mischungen.Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyne, 1-octene, alpha-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-alpha-olefin, 2-styrene, alpha Methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2, vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N - (Methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N - (2-ethylhexyl) acrylamide, Acrylsä ureoctylester, Methacrylsäureoctylester, N - (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N - (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, N - (stearyl) acrylamide, behenyl acrylate, and Methacrylsäurebehenylester N- (Behenyl) acrylamide or mixtures thereof.
Die Monomerenverteilung der erfindungsgemäß bevorzugt eingesetzten hydrophob modifizierten Copolymere beträgt in Bezug auf das Sulfonsäuregruppen-haltige Monomer, das hydrophobe Monomer und das Carbonsäuregruppen-haltige Monomer vorzugsweise jeweils 5 bis 80 Gew.-%, besonders bevorzugt beträgt der Anteil des Sulfonsäuregruppen-haltigen Monomers und des hydrophoben Monomers jeweils 5 bis 30 Gew.-% und der Anteil des Carbonsäuregruppen-haltigen Monomers 60 bis 80 Gew.-%, die Monomere sind hierbei vorzugsweise ausgewählt aus den zuvor genannten.The monomer distribution of the hydrophobically modified copolymers preferably used according to the invention is preferably in each case from 5 to 80% by weight, with respect to the sulfonic acid group-containing monomer, the hydrophobic monomer and the carboxylic acid group-containing monomer, the proportion of the sulfonic acid group-containing monomer and of the each hydrophobic monomer 5 to 30 wt .-% and the proportion of the carboxylic acid group-containing monomer 60 to 80 wt .-%, the monomers are in this case preferably selected from the aforementioned.
Als organische Cobuilder sind insbesondere Polycarboxylate / Polycarbonsäuren, Asparaginsäure, Polyacetale, Dextrine, weitere organische Cobuilder sowie Phosphonate zu nennen. Diese Stoffklassen werden nachfolgend beschrieben.Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, aspartic acid, polyacetals, dextrins, other organic cobuilders and phosphonates. These classes of substances are described below.
Brauchbare organische Gerüstsubstanzen sind beispielsweise die in Form der freien Säure und/oder ihrer Natriumsalze einsetzbaren Polycarbonsäuren, wobei unter Polycarbonsäuren solche Carbonsäuren verstanden werden, die mehr als eine Säurefunktion tragen. Beispielsweise sind dies Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Äpfelsäure, Weinsäure, Maleinsäure, Fumarsäure, Zuckersäuren, Nitrilotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Die freien Säuren besitzen neben ihrer Builderwirkung typischerweise auch die Eigenschaft einer Säuerungskomponente und dienen somit auch zur Einstellung eines niedrigeren und milderen pH-Wertes der maschinellen Geschirrspülmittel. Insbesondere sind hierbei Citronensäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Gluconsäure und beliebige Mischungen aus diesen zu nennen.Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. For example Citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures thereof. In addition to their builder effect, the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of the automatic dishwashing detergents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
Eine weitere bedeutende Klasse der Gerüststoffe stellen Aminocarbonsäuren und/oder ihre Salze dar. Besonders bevorzugte Vertreter dieser Klasse sind Methylglycindiessigsäure (MGDA) oder ihre Salze sowie Glutamindiessigsäure (GLDA) oder ihre Salze oder Ethylendiamindiessigsäure oder ihre Salze (EDDS). Ebenfalls geeignet sind Iminodibernsteinsäure (IDS) und Iminodiessigsäure (IDA). Aminocarbonsäuren und ihre Salze können zusammen mit den vorgenannten Gerüststoffen, insbesondere auch mit den phosphatfreien Gerüststoffen eingesetzt werden.Another important class of builders are aminocarboxylic acids and / or their salts. Particularly preferred members of this class are methylglycinediacetic acid (MGDA) or its salts and glutamic diacetic acid (GLDA) or its salts or ethylenediamine diacetic acid or its salts (EDDS). Also suitable are iminodisuccinic acid (IDS) and iminodiacetic acid (IDA). Aminocarboxylic acids and their salts can be used together with the abovementioned builders, in particular also with the phosphate-free builders.
Insbesondere bevorzugt ist der Einsatz von MGDA bzw. GLDA oder deren Salzen. Dabei wird insbesondere MGDA eingesetzt. MGDA kann bevorzugt als Granulat, und insbesondere bevorzugt in der festen Phase eingesetzt werden. Insbesondere bevorzugt sind dabei solche MGDA-Granulate, die möglichst wenig Wasser enthalten und/oder eine geringe Hygroskopizität aufweisen.Particularly preferred is the use of MGDA or GLDA or salts thereof. In particular, MGDA is used. MGDA can be used preferably as granules, and particularly preferably in the solid phase. Particular preference is given to those MGDA granules which contain as little water as possible and / or have low hygroscopicity.
Besonders bevorzugt ist der Einsatz von MGDA oder deren Salzen in einer Gesamtmenge von 3 bis 50 Gew.-% bezogen auf das Gesamtgewicht des Reinigungsmittels.Particularly preferred is the use of MGDA or salts thereof in a total amount of 3 to 50 wt .-% based on the total weight of the cleaning agent.
Die Reinigungsmittel können als Gerüststoff insbesondere auch Phosphonate enthalten. Als Phosphonat-Verbindung wird vorzugsweise ein Hydroxyalkan- und/oder Aminoalkanphosphonat eingesetzt. Unter den Hydroxyalkanphosphonaten ist das 1-Hydroxyethan-1,1-diphosphonat (HEDP) von besonderer Bedeutung. Als Aminoalkanphosphonate kommen vorzugsweise Ethylendiamintetramethylenphosphonat (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) sowie deren höhere Homologe in Frage. Phosphonathaltige Komponenten sind in den Mitteln vorzugsweise in Mengen von 0,1 bis 10 Gew.-%, insbesondere in Mengen von 0,5 bis 8 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Reinigungsmittels, enthalten.
In Bezug auf den Anteil der Phosphonateinheit (unabhängig des Hydroxyalkan- und/oder Aminoalkan-Anteils) enthalten die erfindungsgemäßen Mittel von 0,01 bis zu 25 Gew.-%, bevorzugt 5 bis 20 Gew.-% , 8 bis 15 Gew.-% Phosphonat (jeweils bezogen auf das Gesamtgewicht des Mittels). Erfindungsgemäß sind die Phosphonate bevorzugt in der bzw. den festen Phasen enthalten.The detergents may contain, in particular, phosphonates as builder. The phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. Phosphonate-containing components are contained in the compositions preferably in amounts of 0.1 to 10 wt .-%, in particular in amounts of 0.5 to 8 wt .-%, each based on the total weight of the cleaning agent.
With regard to the proportion of the phosphonate unit (independently of the hydroxyalkane and / or aminoalkane portion), the compositions according to the invention contain from 0.01 to 25% by weight, preferably from 5 to 20% by weight, from 8 to 15% by weight. % Phosphonate (in each case based on the total weight of the composition). According to the invention, the phosphonates are preferably contained in the solid phase (s).
"Im wesentlichen frei von Wasser", wie hierin verwendet, bedeutet, dass eine Zusammensetzung weniger als 7 Gew.-%, insbesondere weniger als 5 Gew.-%, vorzugsweise kleiner 3 Gew.-%, besonders bevorzugt weniger als 1 Gew.-% Wasser enthält. Der Wassergehalt, wie hierin definiert, bezieht sich auf den mittels der Karl Fischer Titration ermittelten Wassergehalt."Substantially free of water" as used herein means that a composition contains less than 7% by weight, in particular less than 5% by weight, preferably less than 3% by weight, more preferably less than 1% by weight. Contains% water. The water content, as defined herein, refers to the water content determined by Karl Fischer titration.
Erfindungsgemäß ist die flüssige Phase gemäß "Im Wesentlichen frei von Wasser", dies bedeutet, dass die flüssige Phase weniger als 7 Gew.-%, insbesondere weniger als 5 Gew.-%, vorzugsweise kleiner 3 Gew.-%, besonders bevorzugt weniger als 1 Gew.-% Wasser enthält. Der Wassergehalt wie hierin definiert bezieht sich auf den mittels der Karl Fischer Titration ermittelten Wassergehalt.According to the invention, the liquid phase is according to "substantially free of water", this means that the liquid phase less than 7 wt .-%, in particular less than 5 wt .-%, preferably less than 3 wt .-%, more preferably less than 1 wt .-% water. The water content as defined herein refers to the water content determined by Karl Fischer titration.
Insbesondere sind alle flüssigen Phasen und alle festen Phasen des erfindungsgemäßen Reinigungsmittels "im Wesentlichen frei von Wasser", d.h. jede der einzelnen Phasen enthält jeweils weniger als 7 Gew.-%, insbesondere weniger als 5 Gew.-%, vorzugsweise kleiner 3 Gew.-%, besonders bevorzugt weniger als 1 Gew.-% Wasser (jeweils bezogen auf das Gesamtgewicht der jeweiligen Phase).In particular, all liquid phases and all solid phases of the detergent of the invention are "substantially free of water", i. each of the individual phases contains in each case less than 7% by weight, in particular less than 5% by weight, preferably less than 3% by weight, particularly preferably less than 1% by weight of water (in each case based on the total weight of the respective phase ).
"Flüssig", wie hierin in Bezug auf das erfindungsgemäße Reinigungsmittel verwendet, schließt alle fließfähigen Zusammensetzungen ein und erfasst insbesondere auch Gele und pastöse Zusammensetzungen. Insbesondere schließt der Begriff auch Nicht-Newtonsche Flüssigkeiten, die eine Fließgrenze besitzen ein."Liquid" as used herein with respect to the cleaning agent of the present invention includes all flowable compositions and, in particular, also encompasses gels and pasty compositions. In particular, the term also includes non-Newtonian fluids having a yield point.
"Mindestens ein", wie hierin verwendet, bedeutet 1 oder mehr, beispielsweise 1, 2, 3, 4, 5, oder mehr."At least one" as used herein means 1 or more, for example, 1, 2, 3, 4, 5, or more.
"fest", wie hierin in Bezug auf das erfindungsgemäße Reinigungsmittel verwendet, schließt alle festen Zusammensetzungen ein und umfasst insbesondere pulverförmige, granulierte, amorphe, komprimierte, insbesondere gepresste, tablettierte Zusammensetzungen. Pulverförmige Zusammensetzungen können dabei auch neben pulverförmigen Bestandteilen zum Teil auch Granulate enthalten."solid" as used herein with respect to the cleaning composition of the invention includes all solid compositions, and includes in particular powdered, granulated, amorphous, compressed, in particular pressed, tabletted compositions. In addition to powdery constituents, powdery compositions may also partially contain granules.
Das erfindungsgemäße Reinigungsmittel liegt in einer wasserlöslichen Verpackung vor.
Die wasserlösliche Verpackung erlaubt dabei eine Portionierung des Reinigungsmittels. Die Menge an Reinigungsmittel in der Portionspackung beträgt vorzugsweise 5 bis 50 g, besonders bevorzugt 10 bis 30 g, vor allem 15 bis 25 g.The cleaning agent according to the invention is present in a water-soluble packaging.
The water-soluble packaging allows a portioning of the detergent. The amount of detergent in the sachet is preferably 5 to 50 g, more preferably 10 to 30 g, especially 15 to 25 g.
Bevorzugt handelt es sich dabei um eine Einmalportion, das Reinigungsmittel liegt dabei bevorzugt in einer ausreichenden Menge zur Durchführung der Reinigung, bei Maschinengeschirrspülmitteln insbesondere eines Zyklus bzw. eines vollständigen Programmdurchlaufs einer Geschirrspülmaschine), vor.Preferably, this is a disposable portion, the detergent is preferably in an amount sufficient to carry out the cleaning, in machine dishwashing detergents in particular a cycle or a complete program run of a dishwasher).
Die wasserlösliche Verpackung weist dabei mindestens zwei oder mehr von einander räumlich getrennte Kompartimente (Kammern) auf, in die räumlich getrennt mindestens ein feste, bevorzugt pulverförmige, und mindestens eine flüssige Phase gefüllt werden.The water-soluble packaging in this case has at least two or more spatially separated compartments (chambers) in which spatially separated at least one solid, preferably pulverulent, and at least one liquid phase are filled.
Insbesondere geeignet sind Zweikammerbeutel oder Zweikammerformkörper, die eine feste und eine flüssige Phase in getrennten Kompartimenten enthalten.Particularly suitable are two-chamber bags or two-chamber tablets which contain a solid and a liquid phase in separate compartments.
Weiterhin sind besonders Mehrkammerverpackungen (Mehrkammerbeutel bzw. Mehrkammerformkörper) geeignet, die in mindestens einem der abgetrennten Kompartimente eine pulverförmige und in mindestens einem anderen Kompartimente eine flüssige Phase enthalten. Als Phase wird hier eine Reinigungsmittel(teil-)zusammensetzung verstanden, die in Kombination mit der bzw. den anderen Phasen ein Reinigungsmittel, insbesondere ein Maschinengeschirrspülmittel, ergibt.Furthermore, particularly multi-chamber packages (multi-chamber bags or multi-chamber shaped bodies) are suitable which contain a powdery phase in at least one of the separated compartments and a liquid phase in at least one other compartment. A phase is understood here to mean a detergent (partial) composition which, in combination with the other phase or phases, results in a cleaning agent, in particular a machine dishwashing detergent.
Das erfindungsgemäße Reinigungsmittel, insbesondere Maschinengeschirrspülmittel, kann auch in einer wasserlöslichen Verpackung vorliegen, die insbesondere mehr als zwei, also beispielsweise drei, vier, fünf oder sechs Kompartimente enthält.The cleaning agent according to the invention, in particular machine dishwashing detergent, can also be present in a water-soluble packaging, which in particular contains more than two, so for example, three, four, five or six compartments.
Bevorzugt enthält die Verpackung zwei, drei oder mehr Kammern (Kompartimente), wobei ein, zwei oder mehrere diese Kammern mit flüssigen Phasen gefüllt sind, die bevorzugt voneinander verschieden sind, und insbesondere ein oder mehrere voneinander verschiedene Inhaltsstoffe aufweisen.Preferably, the package contains two, three or more chambers (compartments), wherein one, two or more of these chambers are filled with liquid phases, which are preferably different from each other, and in particular one or more mutually different ingredients.
Bevorzugt sind vorportionierte Reinigungsmittel, bei denen die wasserlösliche Verpackung zusätzlich zu einer, zwei oder mehr flüssigen Phasen, eine, zwei oder mehr Kammern (Kompartimente) mit festen Phasen beinhaltet. Wenn zwei oder mehr feste Phasen vorgesehen sind, ist es bevorzugt, dass diese von unterschiedlicher Zusammensetzung sind und/oder eine andere feste Form aufweisen.Preferred are pre-portioned detergents in which the water-soluble package contains one, two or more solid phase chambers (compartments) in addition to one, two or more liquid phases. When two or more solid phases are provided, it is preferred that they be of different composition and / or have a different solid form.
Insbesondere bevorzugt sind vorportionierte Reinigungsmittel, die mindestens eine feste, davon bevorzugt mindestens eine pulverförmige Phase und mindestens eine flüssige Phase in getrennten Kompartimenten aufweisen.Particular preference is given to pre-portioned cleaning compositions which have at least one solid, preferably at least one pulverulent phase and at least one liquid phase in separate compartments.
Weiterhin bevorzugt sind vorportionierte Reinigungsmittel, die mindestens eine feste, davon bevorzugt mindestens eine komprimierte Phase und eine flüssige Phase in getrennten Kompartimenten aufweisen.Also preferred are pre-portioned detergents which have at least one solid, preferably at least one compressed phase and one liquid phase in separate compartments.
Bevorzugt kann es auch sein, dass das vorportionierten Reinigungsmittel zwei oder mehr feste Phasen, davon mindestens eine pulverförmige und mindestens eine komprimierte und mindestens eine, auch zwei, drei oder mehr flüssige Phasen in jeweils getrennten Kompartimenten aufweist.It may also be preferable for the pre-portioned cleaning agent to have two or more solid phases, of which at least one powdery and at least one compressed and at least one, also two, three or more liquid phases are in each case separate compartments.
Es ist weiterhin bevorzugt, dass das vorportionierte Reinigungsmittel, insbesondere der Mehrkammerbeutel, eine feste, eine davon unterschiedliche pulverförmige und zwei flüssige Phasen in jeweils getrennten Kompartimenten enthält.It is further preferred that the pre-portioned detergent, in particular the multi-chamber bag, contains a solid, one of which is different powdery and two liquid phases in each separate compartments.
Die mindestens eine flüssige Phase in dem erfindungsgemäßen Reinigungsmittel ist gemäß einer bevorzugten Ausführungsform im Wesentlichen frei von organischen Komponenten, welche ein durchschnittliches Molekulargewicht von kleiner 175 g/mol, bevorzugt von kleiner als 150 g/mol aufweisen, ist;
Im Wesentlichen frei von organischen Komponenten, welche ein durchschnittliches Molekulargewicht von kleiner 175 g/mol, bevorzugt von kleiner als 150 g/mol aufweisen, bedeutet, dass in der flüssigen Phase (bei mehreren flüssigen Phasen in jeder einzelnen flüssigen Phase) jeweils weniger als 5 Gew.-%, bevorzugt weniger als 3 Gew.-% von solchen organischen Verbindungen enthalten sind, welche ein durchschnittliches Molekulargewicht von kleiner 175 g/mol, bevorzugt von kleiner als 150 g/mol aufweisen. Insbesondere soll erfindungsgemäß die Anwesenheit von üblicherweise kurzkettigen organischen Lösungsmitteln, welche ein durchschnittliches Molekulargewicht von kleiner 175 g/mol, wie beispielsweise Dipropylenglykoldimethylether, bevorzugt von kleiner als 150 g/mol aufweisen, wie Decan, Octan, Dipropylenglycole, Glycerin, Propandiole, Monoethanolamin, Diethanolamin vermieden werden, die besonders stark zu einer Migration zwischen den Kompartimenten neigen.According to a preferred embodiment, the at least one liquid phase in the cleaning agent according to the invention is substantially free of organic components which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol;
Substantially free of organic components which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol, means that in the liquid phase (in the case of several liquid phases in each individual liquid phase) less than 5 Wt .-%, preferably less than 3 wt .-% of such organic compounds are contained, which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol. In particular, according to the invention, the presence of usually short-chain organic solvents having an average molecular weight of less than 175 g / mol, such as dipropylene glycol dimethyl ether, preferably less than 150 g / mol, such as decane, octane, dipropylene glycols, glycerol, propanediols, monoethanolamine, diethanolamine be avoided, which are particularly prone to migration between the compartments.
In der (bzw. den flüssigen Phase(n)) sollen die genannten organischen Komponenten, bevorzugt organischen Lösungsmittel, welche ein durchschnittliches Molekulargewicht von kleiner 175 g/mol, bevorzugt von kleiner als 150 g/mol aufweisen, jeweils nur zu einem Mengenanteil von weniger als 5 Gew.-%, bevorzugt von weniger als 3 Gew.-% (jeweils bezogen auf die Zusammensetzung der einzelnen flüssigen Phase) enthalten sein.In the (or the liquid phase (s)), said organic components, preferably organic solvents, which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol, in each case only to a proportion of less be contained as 5 wt .-%, preferably of less than 3 wt .-% (each based on the composition of the individual liquid phase).
Der Gesamtanteil der in der flüssigen Phase bzw. den flüssigen Phasen enthaltenen organischen Komponenten, bevorzugt organischen Lösungsmittel, welche ein durchschnittliches Molekulargewicht von kleiner 175 g/mol, bevorzugt von kleiner als 150 g/mol aufweisen, beträgt maximal 20 Gew.-% (bezogen auf das Gesamtgewicht der einzelnen flüssigen Phase).The total amount of the organic components contained in the liquid phase or the liquid phases, preferably organic solvents, which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol, is not more than 20 wt .-% (relative on the total weight of each liquid phase).
Umfasst das vorportionierte Reinigungsmittel, insbesondere Maschinengeschirrspülmittel, mehrere flüssige Phasen in getrennten Kompartimenten, ist es erfindungsgemäß ganz besonders bevorzugt, dass jede der flüssigen Phasen im Wesentlichen frei von organischen Komponenten, welche ein durchschnittliches Molekulargewicht von kleiner 175 g/mol, bevorzugt von kleiner als 150 g/mol aufweisen, (außer den unter a) genannten) Komponenten ist, da ansonsten eine Migration der Komponenten zwischen den einzelnen flüssigen Phasen in den getrennten Kompartimenten erfolgt.If the pre-portioned cleaning agent, in particular machine dishwashing detergent, comprises a plurality of liquid phases in separate compartments, it is very particularly preferred according to the invention that each of the liquid phases is essentially free of organic components having an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol (except the components mentioned under a), since otherwise there is a migration of the components between the individual liquid phases in the separate compartments.
Gemäß einer bevorzugten Ausführungsform ist die flüssige Phase (sind die flüssigen Phasen) des erfindungsgemäßen Reinigungsmittels, insbesondere Maschinengeschirrspülmittels, im Wesentlichen frei von organischen Komponenten, welche ein durchschnittliches Molekulargewicht von kleiner 175 g/mol, bevorzugt von kleiner als 150 g/mol aufweisen und bei 20 °C und 1 bar flüssig sind.According to a preferred embodiment, the liquid phase (are the liquid phases) of the cleaning agent according to the invention, in particular machine dishwashing, substantially free of organic components having an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol and at 20 ° C and 1 bar are liquid.
Bevorzugt enthalten die erfindungsgemäßen vorportionierten Reinigungsmittel, insbesondere Maschinengeschirrspülmittel, in der flüssigen Phase, in einer der flüssigen Phasen, insbesondere in allen flüssigen Phasen,
mindestens eine, bevorzugt zwei, drei, vier oder mehr alkoxylierte Komponenten gemäß Formel I
R1-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6 (Formel I)
wobei
- R1 ausgewählt ist aus -H, -CH3, geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten,C2-24-Alkyl- oder -Alkenylrest steht;
- R2, R3, R4, R5,jeweils unabhängig voneinander ausgewählt sind aus -H, -CH3,-CH2CH3, -CH2CH2CH3, CH(CH3)2, vorzugsweise -H oder -CH3;
- R6 ausgewählt ist aus -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2-CH2-CH2CH3, -CH2CH(CH3)2, -C(CH3)3, C5-24-Alkyl- oder -Alkenyl, sowie-CH2CH(OH)R7
- mit R7 für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C6-26-Alkyl-oder-Alkenylrest;
und - w, x, y, z jeweils unabhängig voneinander Werte von 1 bis 120 annehmen können und wobei x, y und/oder z =0 sein können,
at least one, preferably two, three, four or more alkoxylated components according to formula I.
R 1 is -O- (CH 2 -CH (R 2 ) -O) w - (CH 2 -CH (R 3 ) -O) x - (CH 2 -CH (R 4 ) -O) y - (CH 2 -CH (R 5 ) -O) z -R 6 (Formula I)
in which
- R 1 is selected from -H, -CH 3 , straight-chain or branched, saturated or mono- or polyunsaturated, C 2-24 alkyl or alkenyl radical;
- R 2 , R 3 , R 4 , R 5 are each independently selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , preferably -H or -CH 3 ;
- R 6 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 -CH 2 -CH 2 CH 3 , -CH 2 CH (CH 3 ) 2 , -C (CH 3 ) 3 , C 5-24 alkyl or alkenyl, and -CH 2 CH (OH) R 7
- with R 7 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-26 alkyl or alkenyl radical;
and - w, x, y, z can each independently of one another assume values of 1 to 120 and where x, y and / or z = 0,
Die flüssige Phase bzw. die flüssigen Phasen der erfindungsgemäßen Reinigungsmittel enthalten mindestens eine Komponente gemäß a).The liquid phase or the liquid phases of the cleaning agents according to the invention contain at least one component according to a).
Bevorzugt enthält die flüssige Phase bzw. enthalten die flüssigen Phasen der erfindungsgemäßen Reinigungsmittel mindestens eine Komponente gemäß a), die ausgewählt ist aus den Polyalkylenglycolen gemäß Formel (I) mit
R'-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6 (Formel I)
R1=H, R6=H; R2, R3, R4, R5, jeweils unabhängig ausgewählt aus H, -CH3, und w, x, y, z= 1 bis 50.Preferably, the liquid phase or contain the liquid phases of the cleaning agent according to the invention at least one component according to a), which is selected from the polyalkylene glycols of formula (I) with
R'-O- (CH 2 -CH (R 2 ) -O) w - (CH 2 -CH (R 3 ) -O) x - (CH 2 -CH (R 4 ) -O) y - (CH 2 -CH (R 5 ) -O) z -R 6 (Formula I)
R 1 = H, R 6 = H; R 2 , R 3 , R 4 , R 5 , each independently selected from H, -CH 3 , and w, x, y, z = 1 to 50.
Unter die o.g. Formel (I) sind auch ein großer Teil der nichtionischen Tenside zu fassen. Bevorzugt werden schwachschäumende alkoxylierte nichtionische Tenside, vor allem ethoxylierte, schwachschäumende nichtionische Tenside bevorzugt eingesetzt. In bevorzugten Ausführungsformen enthalten die maschinellen Geschirrspülmittel nichtionische Tenside aus der Gruppe der alkoxylierten Alkohole.Under the o.g. Formula (I) are also a large part of the nonionic surfactants to grasp. Low-foaming alkoxylated nonionic surfactants, in particular ethoxylated, low-foaming nonionic surfactants, are preferably used with preference. In preferred embodiments, the automatic dishwashing agents contain nonionic surfactants from the group of alkoxylated alcohols.
Bevorzugt einzusetzende Tenside stammen aus den Gruppen der alkoxylierten Niotenside, insbesondere der ethoxylierten primären Alkohole und Mischungen dieser Tenside mit strukturell komplizierter aufgebauten Tensiden wie Polyoxypropylen/Polyoxyethylen/Polyoxypropylen ((PO/EO/PO)-Tenside). Solche (PO/EO/PO)-Niotenside zeichnen sich darüber hinaus durch gute Schaumkontrolle aus.Preferably used surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
Als besonders bevorzugte Niotenside werden schwachschäumende Niotenside eingesetzt, welche alternierende Ethylenoxid- und Alkylenoxideinheiten aufweisen. Unter diesen sind wiederum Tenside mit EO-AO-EO-AO-Blöcken bevorzugt, wobei jeweils eine bis zehn EO- bzw. AO-Gruppen aneinander gebunden sind, bevor ein Block aus den jeweils anderen Gruppen folgt. Hier sind nichtionische Tenside der allgemeinen Formel (I)
R1-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6
bevorzugt, in der R1 für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C6-24-Alkyl- oder -Alkenylrest steht; R2, R4, R6 jeweils = -H; jede Gruppe R3 bzw. R5 unabhängig voneinander ausgewählt ist aus -CH3, -CH2CH3, -CH2CH2-CH3, CH(CH3)2 und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.Particularly preferred nonionic surfactants used are low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nonionic surfactants of the general formula (I)
R 1 is -O- (CH 2 -CH (R 2 ) -O) w - (CH 2 -CH (R 3 ) -O) x - (CH 2 -CH (R 4 ) -O) y - (CH 2 -CH (R 5 ) -O) z -R 6
in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; R 2 , R 4 , R 6 each = -H; each group R 3 or R 5 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently stand for integers from 1 to 6.
Somit sind insbesondere nichtionische Tenside bevorzugt, die einen C9-15-Alkylrest mit 1 bis 4 Ethylenoxideinheiten, gefolgt von 1 bis 4 Propylenoxideinheiten, gefolgt von 1 bis 4 Ethylenoxideinheiten, gefolgt von 1 bis 4 Propylenoxideinheiten aufweisen.Thus, particularly preferred are nonionic surfactants having a C 9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units.
Weitere bevorzugte nichtionische Tenside sind hierbei solche der allgemeinen Formel
R2-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6
Mit
- R1 für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
- R2, R3, R4, R5,jeweils unabhängig voneinander ausgewählt sind aus -H, -CH3,-CH2CH3, -CH2CH2CH3, CH(CH3)2, vorzugsweise -H oder -CH3;
- R6 ausgewählt ist aus -CH2CH(OH)R7
mit R7 für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C6-26-Alkyl- oder -Alkenylrest;
und
R 2 -O- (CH 2 -CH (R 2 ) -O) w - (CH 2 -CH (R 3 ) -O) x - (CH 2 -CH (R 4 ) -O) y - (CH 2 -CH (R 5 ) -O) z -R 6
With
- R 1 is H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
- R 2 , R 3 , R 4 , R 5 are each independently selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , preferably -H or -CH 3 ;
- R 6 is selected from -CH 2 CH (OH) R 7
R 7 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-26 alkyl or alkenyl radical;
and
Mit diesen Tensiden, nachfolgend auch als "Hydroxymischether" bezeichnet, kann die Reinigungsleistung der erfindungsgemäßen Zubereitungen deutlich verbessert werden und zwar sowohl im Vergleich zu Tensid-freien System wie auch im Vergleich zu Systemen, die alternative nichtionischen Tenside, beispielsweise aus der Gruppe der polyalkoxylierten Fettalkohole enthaltenWith these surfactants, also referred to below as "hydroxy mixed ethers", the cleaning performance of the preparations according to the invention can be significantly improved both in comparison to surfactant-free system and in comparison to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols contain
Als besonders wirkungsvoll haben sich schließlich die nichtionischen Tenside der allgemeine Formel (I)
R1-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6
Mit
- R1 für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
- R2=H,
- R6 ausgewählt ist aus -CH2CH(OH)R7
mit R7 für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C6-26-Alkyl- oder -Alkenylrest;
und - w=1 bis 120, vorzugsweise 10 bis 80, insbesondere 15 bis 40; und x,y,z=0 ist.
R 1 is -O- (CH 2 -CH (R 2 ) -O) w - (CH 2 -CH (R 3 ) -O) x - (CH 2 -CH (R 4 ) -O) y - (CH 2 -CH (R 5 ) -O) z -R 6
With
- R 1 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
- R 2 = H,
- R 6 is selected from -CH 2 CH (OH) R 7
R 7 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-26 alkyl or alkenyl radical;
and - w = 1 to 120, preferably 10 to 80, in particular 15 to 40; and x, y, z = 0.
Zur Gruppe dieser nichtionischen Tenside zählen beispielsweise die C4-22 Fettalkohol-(EO)10-80-2-hydroxyalkylether, insbesondere auch die C8-12 Fettalkohol-(EO)22-2-hydroxydecylether und die C4-22 Fettatkohot-(EO)40-80-2-hydroxyalkylether.The group of these nonionic surfactants includes, for example, the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular also the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ethers and the C 4-22 fatty alcohol ethers. (EO) 40-80 -2-hydroxyalkyl ether.
Bevorzugt sind weiterhin auch Tenside der Formel (I)
R1-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6
bei denen R1 für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 18 Kohlenstoffatomen oder Mischungen hieraus steht, y, z=0; R2 = CH3, R3=-H, R6=einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen oder Mischungen hieraus bezeichnet und w für Werte von 1 und 2 (bei Mischungen solcher Produkte auch Zahlenwerte zwischen 1 und 2, z.B. 1,5) sowie x für einen Wert von mindestens 15 steht.Also preferred are also surfactants of the formula (I)
R 1 is -O- (CH 2 -CH (R 2 ) -O) w - (CH 2 -CH (R 3 ) -O) x- (CH 2 -CH (R 4 ) -O) y - (CH 2 -CH (R 5 ) -O) z -R 6
wherein R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, y, z = 0; R 2 = CH 3 , R 3 = -H, R 6 = a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and w for values of 1 and 2 (for mixtures of such products also numerical values between 1 and 2, eg 1.5) and x stands for a value of at least 15.
Zur Gruppe dieser nichtionischen Tenside zählen beispielsweise die C2-26 Fettalkohol-(PO)1-(EO)15-40-2-hydroxyalkylether, insbesondere auch die C8-10 Fettalkohol-(PO)1-(EO)22-2-hydroxydecylether.The group of these nonionic surfactants includes, for example, the C 2-26 fatty alcohol (PO) 1 - (EO) 15-40 -2-hydroxyalkyl ethers, in particular also the C 8-10 fatty alcohol (PO) 1 - (EO) 22 -2 -hydroxydecylether.
Bevorzugt werden weiterhin solche endgruppenverschlossene poly(oxyalkylierten) Niotenside der Formel
R1-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6
- Mit y,z=0 sowie R2=H, R6=-CH2CH(OH)R7
- mit R7 für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C6-26-Alkyl- oder -Alkenylrest;
R 1 is -O- (CH 2 -CH (R 2 ) -O) w - (CH 2 -CH (R 3 ) -O) x - (CH 2 -CH (R 4 ) -O) y - (CH 2 -CH (R 5 ) -O) z -R 6
- With y, z = 0 and R 2 = H, R 6 = -CH 2 CH (OH) R 7
- R 7 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-26 alkyl or alkenyl radical;
Gemäß einer besonderen Ausführungsform weisen bei dem Reinigungsmittel, insbesondere Maschinengeschirrspülmittel, in der flüssigen Phase mindestens eine, bevorzugt mindestens zwei, insbesondere mindestens drei der Komponenten gemäß a) einen Schmelzpunkt (bei 1 bar) von ≤ 30 °C, bevorzugt ≤ 25° C, insbesondere ≤ 20°C auf.According to a particular embodiment, in the case of the cleaning agent, in particular machine dishwashing detergent, at least one, preferably at least two, in particular at least three of the components according to a) have a melting point (at 1 bar) of ≦ 30 ° C., preferably ≦ 25 ° C., in the liquid phase, in particular ≤ 20 ° C on.
Insbesondere sind somit Polyethylenglycole mit einem mittleren Molekulargewicht von 180 bis 600, sowie nichtionische Tenside der allgemeinen Formel (I)
R1-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6
bevorzugt, in der R1 für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C6-20-Alkyl- oder -Alkenylrest steht; R2, R4, R6 jeweils = -H; R3, R5 =CH3 und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.Thus, in particular, polyethylene glycols having an average molecular weight of from 180 to 600, and also nonionic surfactants of the general formula (I)
R 1 is -O- (CH 2 -CH (R 2 ) -O) w - (CH 2 -CH (R 3 ) -O) x - (CH 2 -CH (R 4 ) -O) y - (CH 2 -CH (R 5 ) -O) z -R 6
in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-20 -alkyl or -alkenyl radical; R 2 , R 4 , R 6 each = -H; R 3 , R 5 = CH 3 and the indices w, x, y, z independently represent integers from 1 to 6.
Bevorzugt können zu einer der beiden oder beiden o.g. Komponenten mit einem Schmelzpunkt von ≤ 30 °C, bevorzugt ≤ 25° C, insbesondere ≤ 20°C (bei 1 bar) zusätzlich noch anderen Komponenten gemäß a) enthalten sein, die einen höheren Schmelzpunkt aufweisen, insbesondere mindestens einer der oben als besonders bevorzugt genannten ethoxylierten Hydroxymischether.Preference may be given to one of the two or both o.g. Components having a melting point of ≦ 30 ° C., preferably ≦ 25 ° C., in particular ≦ 20 ° C. (at 1 bar), may additionally contain other components according to a) which have a higher melting point, in particular at least one of those described above as being particularly preferred said ethoxylated hydroxy mixed ethers.
Gemäß einer weiteren besonderen Ausführungsform weist das Reinigungsmittel, insbesondere Maschinengeschirrspülmittel in der flüssigen Phase als eine der Komponente gemäß a) mindestens ein Polyalkylenglycol, bevorzugt mindestens ein Polyethylenglycol oder mindestens ein Polypropylenglycol, insbesondere mindestens ein Polyethylenglycol, mit einem mittleren Molekulargewicht zwischen ca. 180 und ca. 6000, bevorzugt ca. 200 bis ca. 5000, insbesondere zwischen ca. 300 und ca. 4000, beispielsweise ca. 400, enthalten ist.
Besonders bevorzugt ist dabei, wenn eine Komponente gemäß a) mindestens ein Polyalkylenglycol, bevorzugt mindestens ein Polyethylenglycol ist, welches ein mittleren Molekulargewicht zwischen 300 und 600 g/mol aufweist.According to a further particular embodiment, the cleaning agent, in particular machine dishwashing detergent in the liquid phase, has as one of the components according to a) at least one polyalkylene glycol, preferably at least one polyethylene glycol or at least one polypropylene glycol, in particular at least one polyethylene glycol, with an average molecular weight between about 180 and approx 6000, preferably about 200 to about 5000, in particular between about 300 and about 4000, for example about 400, is included.
It is particularly preferred if a component according to a) at least one polyalkylene glycol, preferably at least one polyethylene glycol, which has an average molecular weight between 300 and 600 g / mol.
Weiterhin ist es besonders bevorzugt, wenn die flüssige Phase (mindestens einer der flüssigen Phasen, bevorzugt die flüssigen Phasen) eine Komponente gemäß a) mindestens ein weiteres Polyalkylenglycol, bevorzugt mindestens ein Polyethylenglycol (PEG) ist, welches ein mittleren Molekulargewicht zwischen 2000 und 6000 g/mol, bevorzugt ein mittleres Molekulargewicht zwischen 3500 bis 4500, insbesondere ca. 4000, (INCI: PEG 4000),aufweist.Furthermore, it is particularly preferred if the liquid phase (at least one of the liquid phases, preferably the liquid phases) is a component according to a) at least one further polyalkylene glycol, preferably at least one polyethylene glycol (PEG), which has an average molecular weight between 2000 and 6000 g / mol, preferably an average molecular weight between 3500 to 4500, in particular about 4000, (INCI: PEG 4000).
Insbesondere bevorzugt ist es, wenn die flüssige Phase (die flüssigen Phasen) ein PEG mit einem mittleren Molekulargewicht von ca. 400 (INCI: PEG 400) und ein PEG mit einem mittleren Molekulargewicht von ca. 4000 (INCI: PEG 4000) aufweisen.It is particularly preferred if the liquid phase (the liquid phases) has a PEG having an average molecular weight of about 400 (INCI: PEG 400) and a PEG having an average molecular weight of about 4000 (INCI: PEG 4000).
Die flüssige Phase bzw. die mindestens eine flüssige Phasen, bzw. die flüssigen Phasen des erfindungsgemäßen Reinigungsmittels enthalten vorzugsweise zusätzlich mindestens ein nichtionisches Tensid, bevorzugt eines welches ebenfalls eine Komponente nach a) gemäß Formel I darstellt.The liquid phase or the at least one liquid phase, or the liquid phases of the cleaning agent according to the invention preferably additionally contain at least one nonionic surfactant, preferably one which also represents a component according to a) according to formula I.
Gemäß einer weiteren, besonders bevorzugten Ausführungsform ist in der flüssigen Phase als eine der Komponente gemäß a) eine Komponente gemäß Formel (I)
R1-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6
wobei
- R1 ausgewählt ist aus geradkettigen oder verzweigten, gesättigten C8-16-Alkylresten;
- R2 und R4 gleich -H, R3 und R5 gleich -CH3 sind,
- R6 ausgewählt ist aus -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2-CH2-CH2CH3, -CH2CH(CH3)2, -C(CH3)3, C5-20-Alkyl (linear oder verzweigt),
- und unabhängig voneinander ausgewählt sind
- w = 1 bis 6, bevorzugt 1,5 bis 4,5, insbesondere 2 bis 3;
- x = 1 bis 6, bevorzugt 1,5 bis 4,5, insbesondere 2 bis 3;
- y = 0 bis 6, bevorzugt 1,5 bis 4,5, 2 bis 3;
- z = 0 bis 6, bevorzugt 1,5 bis 4,5, 2 bis 3, enthalten ist.
R 1 is -O- (CH 2 -CH (R 2 ) -O) w - (CH 2 -CH (R 3 ) -O) x - (CH 2 -CH (R 4 ) -O) y - (CH 2 -CH (R 5 ) -O) z -R 6
in which
- R 1 is selected from straight-chain or branched, saturated C 8-16 -alkyl radicals;
- R 2 and R 4 are -H, R 3 and R 5 are -CH 3 ,
- R 6 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 -CH 2 -CH 2 CH 3 , -CH 2 CH (CH 3 ) 2 , -C (CH 3 ) 3 , C 5-20 alkyl (linear or branched),
- and are independently selected
- w = 1 to 6, preferably 1.5 to 4.5, in particular 2 to 3;
- x = 1 to 6, preferably 1.5 to 4.5, in particular 2 to 3;
- y = 0 to 6, preferably 1.5 to 4.5, 2 to 3;
- z = 0 to 6, preferably 1.5 to 4.5, 2 to 3, is included.
Diese Komponenten gemäß a) sind insbesondere vorteilhaft, da sie ggf. zusätzlich zu den flüssigen Polyalkylenglycolen eine Grundlage für die flüssige Phase liefern können, ohne das dabei organische Komponenten, insbesondere organische Lösungsmittel, welche ein durchschnittliches Molekulargewicht von kleiner 175 g/mol, bevorzugt von kleiner als 150 g/mol aufweisen, verwendet werden müssen.
Besonders bevorzugt ist es hierbei, wenn zusätzlich zu einer der hier bevorzugten Komponenten gemäß a) als eine weitere bevorzugte Komponente gemäß a) mindestens ein Polyalkylenglycol, bevorzugt mindestens ein Polyethylenglycol ist, welches ein mittleres Molekulargewicht zwischen ca. 300 und ca. 5000, insbesondere ca. 4000 g/mol aufweist, eingesetzt wird.
Weiterhin ist es besonders bevorzugt, wenn die flüssige Phase (die flüssigen Phasen) zusätzlich eine Komponente gemäß a) mindestens ein weiteres Polyalkylenglycol, bevorzugt mindestens ein Polyethylenglycol (PEG) ist, welches ein mittleren Molekulargewicht zwischen 2000 und 6000 g/mol, insbesondere PEG 4000, aufweist.These components according to a) are particularly advantageous because they may optionally provide a basis for the liquid phase in addition to the liquid polyalkylene glycols, without organic components, in particular organic solvents having an average molecular weight of less than 175 g / mol, preferably from less than 150 g / mol, must be used.
It is particularly preferred in this case if in addition to one of the preferred components according to a) as a further preferred component according to a) at least one polyalkylene glycol, preferably at least one polyethylene glycol having an average molecular weight between about 300 and about 5000, in particular approx 4000 g / mol is used.
Furthermore, it is particularly preferred if the liquid phase (the liquid phases) is additionally a component according to a) at least one further polyalkylene glycol, preferably at least one polyethylene glycol (PEG), which has an average molecular weight between 2000 and 6000 g / mol, in particular PEG 4000 , having.
Insbesondere bevorzugt ist es, wenn die flüssige Phase (die flüssigen Phasen) ein PEG mit einem mittleren Molekulargewicht von ca. 400 (INCI: PEG 400) und ein PEG mit einem mittleren Molekulargewicht von ca. 4000 (INCI: PEG 4000) aufweisen.It is particularly preferred if the liquid phase (the liquid phases) has a PEG having an average molecular weight of about 400 (INCI: PEG 400) and a PEG having an average molecular weight of about 4000 (INCI: PEG 4000).
Bei allen vorstehend genannten Ausführungsformen, insbesondere den besonders hervorgehobenen Kombinationen, ist es bevorzugt, dass die Menge aller dabei genannten Komponenten gemäß a) in der flüssigen Phase zwischen 10 bis 80 Gew.-%, bevorzugt zwischen 20 bis 70 Gew.-% (jeweils bezogen auf das Gesamtgewicht der flüssigen Phase) beträgt.In all the abovementioned embodiments, in particular the particularly emphasized combinations, it is preferred that the amount of all components mentioned according to a) in the liquid phase is between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (in each case based on the total weight of the liquid phase).
Gemäß einer besonders bevorzugten Ausführungsform enthält die flüssige Phase (mindestens eine der flüssigen Phase, ggf. alle flüssigen Phasen) jeweils bezogen auf das jeweilige Gesamtgewicht der (einzelnen) flüssigen Phase:
- 0- 40 Gew.-% mindestens einer Komponente a) gemäß Formel (I)
R1-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6
wobei- R1 ausgewählt ist aus geradkettigen oder verzweigten, gesättigten C8-16-Alkylresten;
- R2 und R4 gleich -H, R3 und R5 gleich -CH3 sind,
- R6 ausgewählt ist aus -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2-CH2-CH2CH3, -CH2CH(CH3)2, -C(CH3)3, C5-20-Alkyl (linear oder verzweigt),
- und unabhängig voneinander ausgewählt sind
- w = 1 bis 6, bevorzugt 1,5 bis 4,5, insbesondere 2 bis 3;
- x = 1 bis 6, bevorzugt 1,5 bis 4,5, insbesondere 2 bis 3;
- y = 0 bis 6, bevorzugt 1,5 bis 4,5, 2 bis 3;
- z = 0 bis 6, bevorzugt 1,5 bis 4,5, 2 bis 3, enthalten ist,
- 0-40 Gew.-% mindestens eines ethoxylierter Hydroxymischethers der Formel (I)
R1-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6
mit- ∘ R1 für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
- ∘ R2=H,
- ∘ R6 ausgewählt ist aus -CH2CH(OH)R7
mit R7 für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C6-26-Alkyl- oder-Alkenylrest; und
- w=1 bis 120, vorzugsweise 10 bis 80, insbesondere 15 bis 40; und x,y,z=0 ist.
- 0-50 Gew.% Polyalkylenglycole;
- 0-40% by weight of at least one component a) according to formula (I)
R 1 is -O- (CH 2 -CH (R 2 ) -O) w - (CH 2 -CH (R 3 ) -O) x - (CH 2 -CH (R 4 ) -O) y - (CH 2 -CH (R 5 ) -O) z -R 6
in which- R 1 is selected from straight-chain or branched, saturated C 8-16 -alkyl radicals;
- R 2 and R 4 are -H, R 3 and R 5 are -CH 3 ,
- R 6 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 -CH 2 -CH 2 CH 3 , -CH 2 CH (CH 3 ) 2 , -C (CH 3 ) 3 , C 5-20 alkyl (linear or branched),
- and are independently selected
- w = 1 to 6, preferably 1.5 to 4.5, in particular 2 to 3;
- x = 1 to 6, preferably 1.5 to 4.5, in particular 2 to 3;
- y = 0 to 6, preferably 1.5 to 4.5, 2 to 3;
- z = 0 to 6, preferably 1.5 to 4.5, 2 to 3, is contained,
- 0-40% by weight of at least one ethoxylated hydroxy mixed ether of the formula (I)
R 1 is -O- (CH 2 -CH (R 2 ) -O) w - (CH 2 -CH (R 3 ) -O) x - (CH 2 -CH (R 4 ) -O) y- (CH 2 -CH (R 5 ) -O) z -R 6
With- ∘ R 1 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
- 2 R 2 = H,
- 6 R 6 is selected from -CH 2 CH (OH) R 7
with R 7 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-26 alkyl or alkenyl radical; and
w = 1 to 120, preferably 10 to 80, in particular 15 to 40; and x, y, z = 0.
- 0-50% by weight of polyalkylene glycols;
Dabei ist es bevorzugt, dass die Menge aller der als bevorzugt genannten Komponenten gemäß a) in der flüssigen Phase zwischen 10 bis 80 Gew.-%, bevorzugt zwischen 20 bis 70 Gew.-% (jeweils bezogen auf das Gesamtgewicht der flüssigen Phase) beträgt.It is preferred that the amount of all of the components referred to as preferred according to a) in the liquid phase is between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (each based on the total weight of the liquid phase) ,
Gemäß einer besonders bevorzugten Ausführungsform enthält die flüssige Phase (mindestens eine der flüssigen Phase, ggf. alle flüssigen Phasen) jeweils bezogen auf das jeweilige Gesamtgewicht der (einzelnen) flüssigen Phase:
- 5 bis 30 Gew.-% mindestens einer Komponente a) gemäß Formel (I)
R1-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6
wobei- R1 ausgewählt ist aus geradkettigen oder verzweigten, gesättigten C8-16-Alkylresten;
- R2 und R4 gleich -H, R3 und R5 gleich -CH3 sind,
- R6 ausgewählt ist aus -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2-CH2-CH2CH3, -CH2CH(CH3)2, -C(CH3)3, C5-20-Alkyl (linear oder verzweigt),
- und unabhängig voneinander ausgewählt sind
- w = 1 bis 6, bevorzugt 1,5 bis 4,5, insbesondere 2 bis 3;
- x = 1 bis 6, bevorzugt 1,5 bis 4,5, insbesondere 2 bis 3;
- y = 0 bis 6, bevorzugt 1,5 bis 4,5, 2 bis 3;
- z = 0 bis 6, bevorzugt 1,5 bis 4,5, 2 bis 3, enthalten ist,
- 5 bis 30 Gew.-% mindestens eines ethoxylierter Hydroxymischethers der Formel (I)
R1-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6
mit- ∘ R1 für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
- ∘ R2=H,
- ∘ R6 ausgewählt ist aus -CH2CH(OH)R7
-w=1 bis 120, vorzugsweise 10 bis 80, insbesondere 15 bis 40; und x,y,z=0 ist.
und - 5-40 Gew.-% Polyalkylenglycole;
- 5 to 30% by weight of at least one component a) according to formula (I)
R 1 is -O- (CH 2 -CH (R 2 ) -O) w - (CH 2 -CH (R 3 ) -O) x - (CH 2 -CH (R 4 ) -O) y - (CH 2 -CH (R 5 ) -O) z -R 6
in which- R 1 is selected from straight-chain or branched, saturated C 8-16 -alkyl radicals;
- R 2 and R 4 are -H, R 3 and R 5 are -CH 3 ,
- R 6 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 -CH 2 -CH 2 CH 3 , -CH 2 CH (CH 3 ) 2 , -C (CH 3 ) 3 , C 5-20 alkyl (linear or branched),
- and are independently selected
- w = 1 to 6, preferably 1.5 to 4.5, in particular 2 to 3;
- x = 1 to 6, preferably 1.5 to 4.5, in particular 2 to 3;
- y = 0 to 6, preferably 1.5 to 4.5, 2 to 3;
- z = 0 to 6, preferably 1.5 to 4.5, 2 to 3, is contained,
- 5 to 30% by weight of at least one ethoxylated hydroxy mixed ether of the formula (I)
R 1 is -O- (CH 2 -CH (R 2 ) -O) w - (CH 2 -CH (R 3 ) -O) x - (CH 2 -CH (R 4 ) -O) y - (CH 2 -CH (R 5 ) -O) z -R 6
With- ∘ R 1 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
- 2 R 2 = H,
- 6 R 6 is selected from -CH 2 CH (OH) R 7
-w = 1 to 120, preferably 10 to 80, in particular 15 to 40; and x, y, z = 0.
and - 5-40% by weight of polyalkylene glycols;
Dabei ist es bevorzugt, dass die Menge aller der als bevorzugt genannten Komponenten gemäß a) in der flüssigen Phase zwischen 15 bis 80 Gew.-%, bevorzugt zwischen 20 bis 70 Gew.-% (jeweils bezogen auf das Gesamtgewicht der flüssigen Phase) beträgt.It is preferred that the amount of all of the components referred to as preferred according to a) in the liquid phase is between 15 to 80 wt .-%, preferably between 20 to 70 wt .-% (each based on the total weight of the liquid phase) ,
Gemäß einer besonders bevorzugten Ausführungsform enthält die flüssige Phase (mindestens eine der flüssigen Phase, ggf. alle flüssigen Phasen) jeweils bezogen auf das jeweilige Gesamtgewicht der (einzelnen) flüssigen Phase:
- 5 bis 30 Gew.-% mindestens einer Komponente a) gemäß Formel (I)
R1-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6
wobei- R1 ausgewählt ist aus geradkettigen oder verzweigten, gesättigten C8-16-Alkylresten;
- R2 und R4 gleich -H, R3 und R5 gleich -CH3 sind,
- R6 ausgewählt ist aus -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2-CH2-CH2CH3, -CH2CH(CH3)2, -C(CH3)3, C5-20-Alkyl (linear oder verzweigt),
- und unabhängig voneinander ausgewählt sind
- w = 1 bis 6, bevorzugt 1,5 bis 4,5, insbesondere 2 bis 3;
- x = 1 bis 6, bevorzugt 1,5 bis 4,5, insbesondere 2 bis 3;
- y = 0 bis 6, bevorzugt 1,5 bis 4,5, 2 bis 3;
- z = 0 bis 6, bevorzugt 1,5 bis 4,5, 2 bis 3, enthalten ist,
- 5 bis 30 Gew.-% mindestens eines ethoxylierter Hydroxymischethers der Formel (I)
R1-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6
mit- ∘ R1 für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
- ∘ R2=H,
- ∘ R6 ausgewählt ist aus -CH2CH(OH)R7
- w=1 bis 120, vorzugsweise 10 bis 80, insbesondere 15 bis 40; und x,y,z=0 ist.
und - 5-30 Gew.% Polyethylenglycole mit einem mittleren Molekulargewicht zwischen 300 und 600 g/mol sowie
- 1-20 Gew.-% Polyethylenglycole mit einem Molekulargewicht zwischen 2000 und 6000 g/mol, aufweist.
- 5 to 30% by weight of at least one component a) according to formula (I)
R 1 is -O- (CH 2 -CH (R 2 ) -O) w - (CH 2 -CH (R 3 ) -O) x - (CH 2 -CH (R 4 ) -O) y - (CH 2 -CH (R 5 ) -O) z -R 6
in which- R 1 is selected from straight-chain or branched, saturated C 8-16 -alkyl radicals;
- R 2 and R 4 are -H, R 3 and R 5 are -CH 3 ,
- R 6 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 -CH 2 -CH 2 CH 3 , -CH 2 CH (CH 3 ) 2 , -C (CH 3 ) 3 , C 5-20 alkyl (linear or branched),
- and are independently selected
- w = 1 to 6, preferably 1.5 to 4.5, in particular 2 to 3;
- x = 1 to 6, preferably 1.5 to 4.5, in particular 2 to 3;
- y = 0 to 6, preferably 1.5 to 4.5, 2 to 3;
- z = 0 to 6, preferably 1.5 to 4.5, 2 to 3, is contained,
- 5 to 30% by weight of at least one ethoxylated hydroxy mixed ether of the formula (I)
R 1 is -O- (CH 2 -CH (R 2 ) -O) w - (CH 2 -CH (R 3 ) -O) x - (CH 2 -CH (R 4 ) -O) y - (CH 2 -CH (R 5 ) -O) z -R 6
With- ∘ R 1 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
- 2 R 2 = H,
- 6 R 6 is selected from -CH 2 CH (OH) R 7
w = 1 to 120, preferably 10 to 80, in particular 15 to 40; and x, y, z = 0.
and - 5-30 wt.% Polyethylene glycols having an average molecular weight between 300 and 600 g / mol and
- 1-20 wt .-% polyethylene glycols having a molecular weight between 2000 and 6000 g / mol.
Dabei ist es bevorzugt, dass die Menge aller der als bevorzugt genannten Komponenten gemäß a) in der flüssigen Phase zwischen 10 bis 80 Gew.-%, bevorzugt zwischen 20 bis 70 Gew.-% (jeweils bezogen auf das Gesamtgewicht der flüssigen Phase) beträgt.It is preferred that the amount of all of the components referred to as preferred according to a) in the liquid phase is between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (each based on the total weight of the liquid phase) ,
Ganz besonders bevorzugt ist es, wenn hierbei zusätzlich zu den vorstehend genannten Komponenten als weitere Komponente gemäß a) eingesetzt wird mindestens ein ethoxylierter Hydroxymischether der Formel (I)
R1-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6
Mit
- R1 für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
- R2=H,
- R6 ausgewählt ist aus -CH2CH(OH)R7
mit R7 für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C6-26-Alkyl- oder -Alkenylrest;
und
R 1 is -O- (CH 2 -CH (R 2 ) -O) w - (CH 2 -CH (R 3 ) -O) x - (CH 2 -CH (R 4 ) -O) y - (CH 2 -CH (R 5 ) -O) z -R 6
With
- R 1 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
- R 2 = H,
- R 6 is selected from -CH 2 CH (OH) R 7
R 7 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-26 alkyl or alkenyl radical;
and
Besonders bevorzugt sind dabei insbesondere die C4-22 Fettatkohot-(EO)10-80-2-hydroxyalkylether, insbesondere auch die C8-12 Fettalkohol-(EO)22-2-hydroxydecylether und die C4-22 Fettalkohol-(EO)40-80-2-hydroxyalkylether.Particularly preferred are in particular the C 4-22 Fettatkohot- (EO) 10-80 -2-hydroxyalkyl, especially the C 8-12 fatty alcohol (EO) 22 -2-hydroxy decyl ether and the C 4-22 fatty alcohol (EO ) 40-80 -2-hydroxyalkyl ether.
Hierbei ist es bevorzugt, dass die Menge aller dabei als bevorzugt genannten Komponenten gemäß a) in der flüssigen Phase zwischen 10 bis 80 Gew.-%, bevorzugt zwischen 20 bis 70 Gew.-% (jeweils bezogen auf das Gesamtgewicht der flüssigen Phase) beträgt.In this case, it is preferred that the amount of all components mentioned as being preferred according to a) in the liquid phase is between 10 and 80% by weight, preferably between 20 and 70% by weight (in each case based on the total weight of the liquid phase) ,
Gemäß einer weiteren Ausführungsform kann in der flüssigen Phase (den flüssigen Phasen) zusätzlich ein endgruppenverschlossenes nichtionisches Tensid gemäß Formel II
R8O[CH2CH(R9)O]h[CH2]kCH(OH)[CH2]jOR10,
enthalten sein, insbesondere poly(oxyalkylierten) Niotenside der Formel II
in der R8 und R10 für lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 1 bis 30 Kohlenstoffatomen stehen, R9 für H oder einen Methyl-, Ethyl-, n-Propyl-, iso-Propyl, n-Butyl-, 2-Butyl- oder 2-Methyl-2-Butylrest steht, h für Werte zwischen 1 und 30, k und j für Werte zwischen 1 und 12, vorzugsweise zwischen 1 und 5 stehen. Wenn der Wert h ≥ 2 ist, kann jedes R9 in der oben stehenden Formel R8O[CH2CH(R9)O]h[CH2]kCH(OH)[CH2]jOR10 unterschiedlich sein. R8 und R10 sind vorzugsweise lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 6 bis 22 Kohlenstoffatomen, wobei Reste mit 8 bis 18 C-Atomen besonders bevorzugt sind. Für den Rest R9 sind H, -CH3 oder -CH2CH3 besonders bevorzugt. Besonders bevorzugte Werte für h liegen im Bereich von 1 bis 20, insbesondere von 6 bis 15.According to a further embodiment, in the liquid phase (the liquid phases) additionally a end-capped nonionic surfactant according to formula II
R 8 O [CH 2 CH (R 9 ) O] h [CH 2 ] k CH (OH) [CH 2 ] j OR 10 ,
be contained, in particular poly (oxyalkylated) nonionic surfactants of formula II
in which R 8 and R 10 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 9 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, h are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. When the value h ≥ 2, each R 9 in the above formula R 8 O [CH 2 CH (R 9 ) O] h [CH 2 ] k CH (OH) [CH 2 ] j OR 10 may be different. R 8 and R 10 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R 9 , H, -CH 3 or -CH 2 CH 3 are particularly preferred. Particularly preferred values for h are in the range from 1 to 20, in particular from 6 to 15.
Wie vorstehend beschrieben, kann jedes R9 in der oben stehenden Formel unterschiedlich sein, falls h ≥ 2 ist. Hierdurch kann die Alkylenoxideinheit in der eckigen Klammer variiert werden. Steht h beispielsweise für 3, kann der Rest R9 ausgewählt werden, um Ethylenoxid- (R9 = H) oder Propylenoxid- (R9 = CH3) Einheiten zu bilden, die in jedweder Reihenfolge aneinandergefügt sein können, beispielsweise (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) und (PO)(PO)(PO). Der Wert 3 für h ist hierbei beispielhaft gewählt worden und kann durchaus größer sein, wobei die Variationsbreite mit steigenden h-Werten zunimmt und beispielsweise eine große Anzahl (EO)-Gruppen, kombiniert mit einer geringen Anzahl (PO)-Gruppen einschließt, oder umgekehrt.As described above, each R 9 in the above formula may be different if h ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when h is 3, the radical R 9 can be selected to form ethylene oxide (R 9 = H) or propylene oxide (R 9 = CH 3 ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for h has been chosen here by way of example and may well be greater, with the variation range increasing with increasing h values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
Besonders bevorzugte endgruppenverschlossene poly(oxyalkylierte) Alkohole der oben stehenden Formel weisen Werte von k = 1 und j = 1 auf, so dass sich die vorstehende Formel zu R8O[CH2CH(R9)O]hCH2CH(OH)CH2OR10 vereinfacht. In der letztgenannten Formel sind R8, R10 und R9 wie oben definiert und x steht für Zahlen von 1 bis 30, vorzugsweise von 1 bis 20 und insbesondere von 6 bis 18. Besonders bevorzugt sind Tenside, bei denen die Reste R8 und R10 9 bis 14 C-Atome aufweisen, R9 für H steht und h Werte von 6 bis 15 annimmt.Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1 such that the above formula is R 8 O [CH 2 CH (R 9 ) O] h CH 2 CH (OH ) CH 2 OR 10 simplified. In the latter formula, R 8 , R 10 and R 9 are as defined above and x represents numbers of 1 to 30, preferably 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R 8 and R 10 have 9 to 14 C atoms, R 9 is H and h assumes values of 6 to 15.
Gemäß einer weiteren bevorzugten Ausführungsform beträgt die Menge aller Komponenten gemäß a) in der flüssigen Phase zwischen 10 bis 80 Gew.-%, bevorzugt zwischen 20 bis 70 Gew.-% (jeweils bezogen auf das Gesamtgewicht der flüssigen Phase) beträgt.According to a further preferred embodiment, the amount of all components according to a) in the liquid phase is between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (in each case based on the total weight of the liquid phase).
Das Verhältnis des Gewichts von ein oder mehreren festen Phasen (von denen bevorzugt mindestens eine feste Phase pulverförmig ist, (bei mehreren festen/pulverförmigen Phasen das Gesamtgewicht aller festen und pulverförmigen Phasen) zu dem Gewicht ein oder mehreren flüssiger Phasen (bei mehreren flüssigen Phasen ist erfindungsgemäß bevorzugt 1:10 bis 10:1, insbesondere bevorzugt 1:5 bis 5:1, ganz besonders bevorzugt 4:1 bis 1:2.The ratio of the weight of one or more solid phases (of which preferably at least one solid phase is powdery, (in the case of several solid / powder phases the total weight of all solid and powder phases) to the weight of one or more liquid phases (in the case of several liquid phases According to the invention, preferably 1:10 to 10: 1, particularly preferably 1: 5 to 5: 1, very particularly preferably 4: 1 to 1: 2.
Gemäß einer bevorzugten Ausführungsform ist das Reinigungsmittel, insbesondere Maschinengeschirrspülmittel, im Wesentlichen frei von anionischen Tensiden,
Im Wesentlichen frei von anionischen Tensiden, wie hierin verwendet, bedeutet, dass eine Zusammensetzung weniger als 7 Gew.-%, bevorzugt weniger als 5 Gew.-%, insbesondere weniger als 3 Gew.-%, ganz besonders bevorzugt weniger als 1 Gew.-% , insbesondere bevorzugt weniger als 0,1 Gew.-% anionisches Tensid (bezogen auf das Gesamtgewicht des Mittels) enthält. Dies betrifft bevorzugt alle, insbesondere auch die als bevorzugt vorstehend explizit genannten erfindungsgemäßen Kombinationen.According to a preferred embodiment, the cleaning agent, in particular machine dishwashing detergent, is substantially free of anionic surfactants,
Substantially free of anionic surfactants as used herein means that a composition is less than 7% by weight, preferably less than 5% by weight, more preferably less than 3% by weight, most preferably less than 1% by weight. -%, particularly preferably less than 0.1 wt .-% anionic surfactant (based on the total weight of the composition). This preferably applies to all, in particular also the combinations according to the invention explicitly mentioned as preferred above.
Die wasserlösliche Umhüllung des Reinigungsmittels, die Verpackung, wird vorzugsweise aus einem wasserlöslichen Folienmaterial, welches ausgewählt ist aus der Gruppe, bestehend aus Polymeren oder Polymergemischen, gebildet. Die Umhüllung kann aus einer oder aus zwei oder mehr Lagen aus dem wasserlöslichen Folienmaterial gebildet werden. Das wasserlösliche Folienmaterial der ersten Lage und der weiteren Lagen, falls vorhanden, kann gleich oder unterschiedlich sein. Besonders bevorzugt sind Folien, die beispielsweise zu Verpackungen wie Schläuchen oder Kissen verklebt und/oder versiegelt werden können, nachdem sie mit einem Mittel befüllt wurden.The water-soluble coating of the cleaning agent, the packaging, is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends. The wrapper may be formed of one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if present, may be the same or different. Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent.
Es ist bevorzugt, dass die wasserlösliche Umhüllung Polyvinylalkohol oder ein Polyvinylalkoholcopolymer enthält. Wasserlösliche Umhüllungen, die Polyvinylalkohol oder ein Polyvinylalkoholcopolymer enthalten, weisen eine gute Stabilität bei einer ausreichend hohen Wasserlöslichkeit, insbesondere Kaltwasserlöslichkeit, auf.It is preferable that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.
Geeignete wasserlösliche Folien zur Herstellung der wasserlöslichen Umhüllung basieren bevorzugt auf einem Polyvinylalkohol oder einem Polyvinylalkoholcopolymer, dessen Molekulargewicht im Bereich von 10.000 bis 1.000.000 gmol-1, vorzugsweise von 20.000 bis 500.000 gmol-1, besonders bevorzugt von 30.000 bis 100.000 gmol-1 und insbesondere von 40.000 bis 80.000 gmol-1 liegt.Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose Molecular weight in the range of 10,000 to 1,000,000 gmol -1 , preferably from 20,000 to 500,000 gmol -1 , more preferably from 30,000 to 100,000 gmol -1 and in particular from 40,000 to 80,000 gmol -1 .
Die Herstellung von Polyvinylalkohol geschieht üblicherweise durch Hydrolyse von Polyvinylacetat, da der direkte Syntheseweg nicht möglich ist. Ähnliches gilt für Polyvinylalkoholcopolymere, die aus entsprechend aus Polyvinylacetatcopolymeren hergestellt werden. Bevorzugt ist, wenn wenigstens eine Lage der wasserlöslichen Umhüllung einen Polyvinylalkohol umfasst, dessen Hydrolysegrad 70 bis 100 Mol-%, vorzugsweise 80 bis 90 Mol-%, besonders bevorzugt 81 bis 89 Mol-% und insbesondere 82 bis 88 Mol-% ausmacht.The production of polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
Einem zur Herstellung der wasserlöslichen Umhüllung geeignetem Polyvinylalkohol-enthaltendem Folienmaterial kann zusätzlich ein Polymer ausgewählt aus der Gruppe umfassend (Meth)Acrylsäure-haltige (Co)Polymere, Polyacrylamide, Oxazolin-Polymere, Polystyrolsulfonate, Polyurethane, Polyester, Polyether, Polymilchsäure oder Mischungen der vorstehenden Polymere zugesetzt sein. Ein bevorzugtes zusätzliches Polymer sind Polymilchsäuren.In addition, a polymer selected from the group consisting of (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid, or mixtures of the above may be additionally used in a polyvinyl alcohol-containing film material suitable for producing the water-soluble coating Be added polymers. A preferred additional polymer is polylactic acids.
Bevorzugte Polyvinylalkoholcopolymere umfassen neben Vinylalkohol Dicarbonsäuren als weitere Monomere. Geeignete Dicarbonsäure sind Itaconsäure, Malonsäure, Bernsteinsäure und Mischungen daraus, wobei Itaconsäure bevorzugt ist.Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
Ebenfalls bevorzugte Polyvinylalkoholcopolymere umfassen neben Vinylalkohol eine ethylenisch ungesättige Carbonsäure, deren Salz oder deren Ester. Besonders bevorzugt enthalten solche Polyvinylalkoholcopolymere neben Vinylalkohol Acrylsäure, Methacrylsäure, Acrylsäureester, Methacrylsäureester oder Mischungen daraus.Likewise preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.
Es kann bevorzugt sein, dass das Folienmaterial weitere Zusatzstoffe enthält. Das Folienmaterial kann beispielsweise Weichmacher wie Dipropylenglycol, Ethylenglycol, Diethylenglycol, Propylenglycol, Glycerin, Sorbitol, Mannitol oder Mischungen daraus enthalten. Weitere Zusatzstoffe umfassen beispielsweise Freisetzungshilfen, Füllmittel, Vernetzungsmittel, Tenside, Antioxidationsmittel, UV-Absorber, Antiblockmittel, Antiklebemittel oder Mischungen daraus.It may be preferred that the film material contains further additives. The film material may contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof. Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-sticking agents or mixtures thereof.
Geeignete wasserlösliche Folien zum Einsatz in den wasserlöslichen Umhüllungen der wasserlöslichen Verpackungen gemäß der Erfindung sind Folien, die von der Firma MonoSol LLC beispielsweise unter der Bezeichnung M8630, C8400 oder M8900 vertrieben werden. Andere geeignete Folien umfassen Folien mit der Bezeichnung Solublon® PT, Solublon® GA, Solublon® KC oder Solublon® KL von der Aicello Chemical Europe GmbH oder die Folien VF-HP von Kuraray.Suitable water-soluble films for use in the water-soluble casings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900. Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
Die erfindungsgemäßen Reinigungsmittel können als Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel verwendet werden. Die entsprechende Verwendung ist ebenfalls Gegenstand der Erfindung. Ebenso betrifft die Erfindung ein Geschirrspülverfahren, insbesondere maschinelles Geschirrspülverfahren, bei welchem ein Reinigungsmittel gemäß der Erfindung eingesetzt wird. Die vorstehend beschriebenen besonderen Ausführungsformen gelten auch für die Verwendung bzw. das Verfahren.The cleaning agents according to the invention can be used as dishwashing agents, in particular automatic dishwasher detergents. The corresponding use is also the subject of the invention. The invention likewise relates to a dishwashing process, in particular a machine dishwashing process, in which a cleaning agent according to the invention is used. The particular embodiments described above also apply to the use or the method.
Bei den erfindungsgemäßen Reinigungsmitteln handelt es sich vorzugsweise um ein Geschirrspülmittel, insbesondere um ein maschinelles Geschirrspülmittel.The cleaning agents according to the invention are preferably a dishwasher detergent, in particular a machine dishwashing detergent.
Das erfindungsgemäße vorportionierte Reinigungsmittel, insbesondere Maschinengeschirrspülmittel, ist im Wesentlichen frei von Phosphaten. Dies betrifft bevorzugt alle, insbesondere auch die als bevorzugt vorstehend explizit genannten erfindungsgemäßen Kombinationen.The pre-portioned detergent according to the invention, in particular machine dishwashing detergent, is essentially free of phosphates. This preferably applies to all, in particular also the combinations according to the invention explicitly mentioned as preferred above.
Im Wesentlichen frei von Phosphaten bedeutet, dass das gesamte Reinigungsmittel, welches sich aus der Addition aller Phasen (bzw. aller Inhaltsstoffe aller Kompartimente) ergibt, bevorzugt im Wesentlichen frei von phosphathaltigen Komponenten ist. Als Phosphate oder auch phosphathaltige Komponenten im Sinne der vorliegenden Erfindung sind insbesondere Phosphate, Polyphosphate und Pyrophosphate anzusehen. Phosphonate oder Hexafluorophosphat sind aber nicht von diesem Begriff umfasst. Das gesamte Reinigungsmittel enthält somit weniger als 1 Gew.-%, bevorzugt 0,5 Gew.-% , Phosphat bezogen auf das Gesamtgewicht des Reinigungsmittels (d.h. des Gesamtgewichts aller Phasen (d.h. aller flüssigen und festen Phasen).Substantially free of phosphates means that the total cleaning agent resulting from the addition of all phases (or all ingredients of all compartments) is preferably substantially free of phosphate-containing components. Phosphates or else phosphate-containing components in the context of the present invention are in particular phosphates, polyphosphates and pyrophosphates. However, phosphonates or hexafluorophosphate are not covered by this term. The total detergent thus contains less than 1% by weight, preferably 0.5% by weight, of phosphate based on the total weight of the detergent (i.e., the total weight of all phases (i.e., all liquid and solid phases).
Die erfindungsgemäßen Reinigungsmittel, insbesondere Maschinengeschirrspülmittel enthalten Gerüststoffe, wie beispielsweise Zeolithe, Silikate, Carbonate, insbesondere die Alkalicarbonate, beispielsweise Natriumcarbonat, Natriumhydrogencarbonat oder Natriumsesquicarbonat, und organische Cobuilder.The detergents according to the invention, in particular machine dishwashing detergents, comprise builders, such as, for example, zeolites, silicates, carbonates, in particular the alkali metal carbonates, for example sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, and organic cobuilders.
Als Silikate kommen insbesondere kristalline schichtförmige Silikate der allgemeinen Formel NaMSixO2x+1 · y H2O, worin M Natrium oder Wasserstoff darstellt, x eine Zahl von 1,9 bis 22, vorzugsweise von 1,9 bis 4, wobei besonders bevorzugte Werte für x 2, 3 oder 4 sind, und y für eine Zahl von 0 bis 33, vorzugsweise von 0 bis 20 steht, in Betracht. Einsetzbar sind auch amorphe Natriumsilikate mit einem Modul Na2O : SiO2 von 1:2 bis 1:3,3, vorzugsweise von 1:2 bis 1:2,8 und insbesondere von 1:2 bis 1:2,6, welche vorzugsweise löseverzögert sind und Sekundärwascheigenschaften aufweisen.Particularly suitable silicates are crystalline layered silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred Values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20, into consideration. It is also possible to use amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.
In bevorzugten Reinigungsmitteln wird der Gehalt an Silikaten, bezogen auf das Gesamtgewicht des Reinigungsmittels, auf Mengen unterhalb 10 Gew.-%, vorzugsweise unterhalb 5 Gew.-%.In preferred cleaning agents, the content of silicates, based on the total weight of the cleaning agent, to amounts below 10 wt .-%, preferably below 5 wt .-%.
In verschiedenen Ausführungsformen liegt der pH-Wert einer wässrigen Lösung bei 20°, enthaltend 10 Gew.-% des gesamten Reinigungsmittels, in einem Bereich von 7 bis 14, insbesondere größer 7, insbesondere in einem Bereich von 8 bis 13, vorzugsweise 9 bis 12.In various embodiments, the pH of an aqueous solution at 20 °, containing 10 wt .-% of the total cleaning agent, in a range of 7 to 14, in particular greater than 7, in particular in a range of 8 to 13, preferably 9 to 12 ,
Die erfindungsgemäßen Mittel enthalten vorzugsweise mindestens einen weiteren Bestandteil, vorzugsweise ausgewählt aus der Gruppe bestehend aus kationischen und amphoteren Tensiden, Bleichmitteln, Bleichaktivatoren, Bleichkatalysatoren, Enzymen, Verdickern, Sequestrierungsmitteln, Elektrolyten, Korrosionsinhibitoren, insbesondere Silberschutzmitteln, Glaskorrosionsinhibitoren, Schauminhibitoren, Farbstoffen, Duftstoffen, Bitterstoffen, und antimikrobiellen Wirkstoffen.The compositions according to the invention preferably comprise at least one further constituent, preferably selected from the group consisting of cationic and amphoteric surfactants, bleaching agents, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances, bitter substances , and antimicrobial agents.
In den Reinigungsmitteln, bevorzugt Geschirrspülmitteln, insbesondere maschinellen Geschirrspülmitteln können ferner Bleichmittel eingesetzt werden. Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen haben das Natriumpercarbonat, das Natriumperborattetrahydrat und das Natriumperboratmonohydrat besondere Bedeutung. Weitere brauchbare Bleichmittel sind beispielsweise Peroxypyrophosphate, Citratperhydrate sowie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Peroxophthalate, Diperazelainsäure, Phthaloiminopersäure oder Diperdodecandisäure. Einsetzbar sind außerdem alle weiteren dem Fachmann aus dem Stand der Technik bekannten anorganischen oder organischen Peroxybleichmittel.In the detergents, preferably dishwashing detergents, in particular automatic dishwashing detergents, bleaching agents can also be used. Among the compounds serving as bleaches in water H 2 O 2 , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. It is also possible to use all other inorganic or organic peroxy bleaches known to the person skilled in the art.
Als Bleichmittel können auch Chlor oder Brom freisetzende Substanzen eingesetzt werden. Unter den geeigneten Chlor oder Brom freisetzenden Materialien kommen beispielsweise heterozyklische N-Brom- und N-Chloramide, beispielsweise Trichlorisocyanursäure, Tribromisocyanursäure, Dibromisocyanursäure und/oder Dichlorisocyanursäure (DICA) und/oder deren Salze mit Kationen wie Kalium und Natrium in Betracht. Hydantoinverbindungen, wie 1,3-Dichlor-5,5-dimethylhydanthoin sind ebenfalls geeignet.As a bleaching agent and chlorine or bromine releasing substances can be used. Among the suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
Es werden Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel bevorzugt, die 1 bis 35 Gew.-%, vorzugsweise 2,5 bis 30 Gew.-%, besonders bevorzugt 3,5 bis 25 Gew.-%, ganz besonders bevorzugt 4,0 bis 20 Gew.-%und insbesondere 5 bis 18 Gew.-% (bezogen auf das Gesamtgewicht des Reinigungsmittels) Bleichmittel, vorzugsweise Natriumpercarbonat, enthalten.
Gemäß einer besonders bevorzugten Ausführungsform ist in der festen Phase (bzw. in einer der festen Phasen) Bleichmittel, vorzugsweise Natriumpercarbonat, bevorzugt in einer Menge von 5 bis 40 Gew.-%, bevorzugt von 10 bis 20 Gew.-% (bezogen auf das Gesamtgewicht der festen Phasen) enthalten.Preference is given to detergents, preferably dishwashing agents, in particular automatic dishwasher detergents, which contain 1 to 35% by weight, preferably 2.5 to 30% by weight, particularly preferably 3.5 to 25% by weight, very particularly preferably 4.0 to 20 wt .-% and in particular 5 to 18 wt .-% (based on the total weight of the cleaning agent) bleach, preferably sodium percarbonate.
According to a particularly preferred embodiment, in the solid phase (or in one of the solid phases) is bleach, preferably sodium percarbonate, preferably in an amount of 5 to 40 wt .-%, preferably from 10 to 20 wt .-% (based on the total weight of the solid phases).
Ferner können die Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittel Bleichkatalysatoren enthalten. Die einsetzbaren Bleichkatalysatoren schließen ein, sind aber nicht beschränkt auf die Gruppe der bleichverstärkenden Übergangsmetallsalze und Übergangsmetallkomplexe, vorzugsweise der Mn-, Fe-, Co-, Ru - oder Mo-Komplexe, besonders bevorzugt aus der Gruppe der Mangan und/oder Cobaltsalze und/oder -komplexe, insbesondere der Cobalt(ammin)-Komplexe, der Cobalt(acetat)-Komplexe, der Cobalt(Carbonyl)-Komplexe, der Chloride des Cobalts oder Mangans, des Mangansulfats und der Komplexe des Mangans mit 1,4,7-trimethyl-1,4,7-triazacyclononan (Mn3-TACN) oder 1,2,4,7-tetramethyl-1,4,7-triazacyclononan (Mn4-TACN).Furthermore, the cleaning agents, preferably dishwashing detergents, in particular automatic dishwashing detergents, may contain bleach catalysts. Useful bleach catalysts include, but are not limited to, the group of bleach-enhancing transition metal salts and transition metal complexes, preferably Mn, Fe, Co, Ru or Mo complexes, more preferably from the group of manganese and / or cobalt salts and / or or complexes, in particular the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, the manganese sulfate and the complexes of manganese with 1,4,7- trimethyl-1,4,7-triazacyclononane (Mn 3 -TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Mn 4 -TACN).
Es werden Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel bevorzugt, die 0,001 bis 1 Gew.-%, vorzugsweise 0,01 bis 0,1 Gew.-% (jeweils bezogen auf das Gesamtgewicht des Reinigungsmittels) Bleichkatalysator, vorzugsweise einen Mn-Komplex, insbesondere einen Komplex des Mangans mit 1,4,7-trimethyl-1,4,7-triazacyclononan (Mn3-TACN) oder 1,2,4,7-tetramethyl-1,4,7-tri-azacyclononan (Mn4-TACN), enthalten.Preference is given to detergents, preferably dishwashing agents, in particular automatic dishwasher detergents, which contain from 0.001 to 1% by weight, preferably from 0.01 to 0.1% by weight (based in each case on the total weight of the cleaning agent) of bleach catalyst, preferably a Mn complex. in particular a complex of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Mn 3 -TACN) or 1,2,4,7-tetramethyl-1,4,7-tri-azacyclononane (Mn 4 -TACN).
In verschiedenen Ausführungsformen der Erfindung enthalten die Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittel zusätzlich mindestens einen Bleichaktivator. Als Bleichaktivatoren können Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen, und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, eingesetzt werden. Von allen dem Fachmann aus dem Stand der Technik bekannten Bleichaktivatoren werden mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Triazinderivate, insbesondere 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin (DADHT), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, insbesondere n-Nonanoyl- oder Isononanoyloxybenzolsulfonat (n- bzw. iso-NOBS) besonders bevorzugt eingesetzt. Auch Kombinationen konventioneller Bleichaktivatoren können eingesetzt werden. Diese Bleichaktivatoren werden vorzugsweise in Mengen bis 10 Gew.-%, insbesondere 0,1 Gew.-% bis 8 Gew.-%, besonders 2 bis 8 Gew.-% und besonders bevorzugt 2 bis 6 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Reinigungsmittel, eingesetzt.In various embodiments of the invention, the cleaning agents, preferably dishwashing agents, in particular automatic dishwasher detergents, additionally comprise at least one bleach activator. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Of all the bleach activators known to the person skilled in the art, polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), are acylated Glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferably used. Combinations of conventional bleach activators can also be used. These bleach activators are preferably used in amounts of up to 10% by weight, in particular from 0.1% by weight to 8% by weight, especially from 2 to 8% by weight and more preferably from 2 to 6% by weight, based in each case on the total weight of the detergents used.
Das Bleichmittel sowie Bleichkatalysatoren und/oder Bleichaktivatoren sind bevorzugt in der/den festen Phasen enthalten.The bleaching agent and also bleach catalysts and / or bleach activators are preferably contained in the solid phase (s).
Geeignete Amphotenside sind beispielsweise Betaine der Formel (Riii)(Riv)(Rv)N+CH2COO-, in der Riii einen gegebenenfalls durch Heteroatome oder Heteroatomgruppen unterbrochenen Alkylrest mit 8 bis 25, vorzugsweise 10 bis 21 Kohlenstoffatomen und Riv sowie Rv gleichartige oder verschiedene Alkylreste mit 1 bis 3 Kohlenstoffatomen bedeuten, insbesondere C10-C18-Alkyldimethylcarboxymethylbetain und C11-C17-Alkylamidopropyl-dimethylcarboxymethylbetain.Suitable amphoteric surfactants are, for example, betaines of the formula (R iii ) (R iv ) (R v ) N + CH 2 COO - , in which R iii is an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R iv and R v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C 10 -C 18 -Alkyldimethylcarboxymethylbetain and C 11 -C 17 -Alkylamidopropyl-dimethylcarboxymethylbetain.
Geeignete Kationtenside sind u.a. die quartären Ammoniumverbindungen der Formel (Rvi)(Rvii)(Rviii)(Rix)N+ X-, in der Rvi bis Rix für vier gleich- oder verschiedenartige, insbesondere zwei lang- und zwei kurzkettige, Alkylreste und X- für ein Anion, insbesondere ein Halogenidion, stehen, beispielsweise Didecyl-dimethyl-ammoniumchlorid, Alkyl-benzyl-didecyl-ammoniumchlorid und deren Mischungen. Weitere geeignete kationische Tenside sind die quaternären oberflächenaktiven Verbindungen, insbesondere mit einer Sulfonium-, Phosphonium-, Jodonium- oder Arsoniumgruppe, die auch als antimikrobielle Wirkstoffe bekannt sind. Durch den Einsatz von quaternären oberflächenaktiven Verbindungen mit antimikrobieller Wirkung kann das Mittel mit einer antimikrobiellen Wirkung ausgestaltet werden bzw. dessen gegebenenfalls aufgrund anderer Inhaltsstoffe bereits vorhandene antimikrobielle Wirkung verbessert werden.Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R vi ) (R vii ) (R viii ) (R ix ) N + X - , in which R vi to R ix are four identical or different, in particular two long and two short-chain, alkyl radicals and X - are an anion, in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof. Further suitable cationic surfactants are the quaternary surface-active compounds, in particular having a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents. Through the use of quaternary surface-active compounds with antimicrobial action, the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.
Zu den Enzymen gehören insbesondere Proteasen, Amylasen, Lipasen, Hemicellulasen, Cellulasen, Perhydrolasen oder Oxidoreduktasen, sowie vorzugsweise deren Gemische. Diese Enzyme sind im Prinzip natürlichen Ursprungs; ausgehend von den natürlichen Molekülen stehen für den Einsatz in Reinigungsmitteln verbesserte Varianten zur Verfügung, die entsprechend bevorzugt eingesetzt werden. Erfindungsgemäße Reinigungsmittel enthalten Enzyme vorzugsweise in Gesamtmengen von 1 x 10-6 bis 5 Gew.-% bezogen auf aktives Protein. Die Proteinkonzentration kann mit Hilfe bekannter Methoden, zum Beispiel dem BCA-Verfahren oder dem Biuret-Verfahren bestimmt werden.The enzymes include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents, which are preferably used accordingly. Detergents according to the invention preferably contain enzymes in total amounts of from 1 × 10 -6 to 5% by weight, based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
Unter den Proteasen sind solche vom Subtilisin-Typ bevorzugt. Beispiele hierfür sind die Subtilisine BPN' und Carlsberg sowie deren weiterentwickelte Formen, die Protease PB92, die Subtilisine 147 und 309, die Alkalische Protease aus Bacillus lentus, Subtilisin DY und die den Subtilasen, nicht mehr jedoch den Subtilisinen im engeren Sinne zuzuordnenden Enzyme Thermitase, Proteinase K und die Proteasen TW3 und TW7.Among the proteases, those of the subtilisin type are preferable. Examples of these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
Beispiele für erfindungsgemäß einsetzbare Amylasen sind die α-Amylasen aus Bacillus licheniformis, aus B. amyloliquefaciens, aus B. stearothermophilus, aus Aspergillus niger und A. oryzae sowie die für den Einsatz in Reinigungsmitteln verbesserten Weiterentwicklungen der vorgenannten Amylasen. Desweiteren sind für diesen Zweck die α-Amylase aus Bacillus sp. A 7-7 (DSM 12368) und die Cyclodextrin-Glucanotransferase (CGTase) aus B. agaradherens (DSM 9948) hervorzuheben.Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the further developments of the aforementioned amylases which are improved for use in cleaning agents. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
Erfindungsgemäß einsetzbar sind weiterhin Lipasen oder Cutinasen, insbesondere wegen ihrer Triglycerid-spaltenden Aktivitäten, aber auch, um aus geeigneten Vorstufen in situ Persäuren zu erzeugen. Hierzu gehören beispielsweise die ursprünglich aus Humicola lanuginosa (Thermomyces lanuginosus) erhältlichen, beziehungsweise weiterentwickelten Lipasen, insbesondere solche mit einem oder mehreren der folgenden Aminosäureaustausche ausgehend von der genannten Lipase in den Positionen D96L, T213R und/oder N233R, besonders bevorzugt alle der Austausche D96L, T213R und N233R.Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from, or further developed, Humicola lanuginosa ( Thermomyces lanuginosus ), in particular those having one or more of the following amino acid exchanges starting from said lipase in positions D96L, T213R and / or N233R, most preferably all of the exchanges D96L, T213R and N233R.
Weiterhin können Enzyme eingesetzt werden, die unter dem Begriff Hemicellulasen zusammengefasst werden. Hierzu gehören beispielsweise Mannanasen, Xanthanlyasen, Pektinlyasen (=Pektinasen), Pektinesterasen, Xyloglucanasen (=Xylanasen), Pullulanasen und β-Glucanasen.Furthermore, enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, xyloglucanases (= xylanases), pullulanases and β-glucanases.
Zur Erhöhung der bleichenden Wirkung können erfindungsgemäß Oxidoreduktasen, beispielsweise Oxidasen, Oxygenasen, Katalasen, Peroxidasen, wie Halo-, Chloro-, Bromo-, Lignin-, Glucose- oder Mangan-peroxidasen, Dioxygenasen oder Laccasen (Phenoloxidasen, Polyphenoloxidasen) eingesetzt werden. Vorteilhafterweise werden zusätzlich vorzugsweise organische, besonders bevorzugt aromatische, mit den Enzymen wechselwirkende Verbindungen zugegeben, um die Aktivität der betreffenden Oxidoreduktasen zu verstärken (Enhancer) oder um bei stark unterschiedlichen Redoxpotentialen zwischen den oxidierenden Enzymen und den Anschmutzungen den Elektronenfluss zu gewährleisten (Mediatoren).Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.
Ein Protein und/oder Enzym kann besonders während der Lagerung gegen Schädigungen wie beispielsweise Inaktivierung, Denaturierung oder Zerfall etwa durch physikalische Einflüsse, Oxidation oder proteolytische Spaltung geschützt werden. Bei mikrobieller Gewinnung der Proteine und/oder Enzyme ist eine Inhibierung der Proteolyse besonders bevorzugt, insbesondere wenn auch die Mittel Proteasen enthalten. Reinigungsmittel können zu diesem Zweck Stabilisatoren enthalten; die Bereitstellung derartiger Mittel stellt eine bevorzugte Ausführungsform der vorliegenden Erfindung dar.A protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
Reinigungsaktive Proteasen und Amylasen werden in der Regel nicht in Form des reinen Proteins sondern vielmehr in Form stabilisierter, lager- und transportfähiger Zubereitungen bereitgestellt. Zu diesen vorkonfektionierten Zubereitungen zählen beispielsweise die durch Granulation, Extrusion oder Lyophilisierung erhaltenen festen Präparationen oder, insbesondere bei flüssigen oder gelförmigen Mitteln, Lösungen der Enzyme, vorteilhafterweise möglichst konzentriert, wasserarm und/oder mit Stabilisatoren oder weiteren Hilfsmitteln versetzt.Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage and transportable preparations. These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or Gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or other auxiliaries.
Alternativ können die Enzyme sowohl für die feste als auch für die flüssige Darreichungsform verkapselt werden, beispielsweise durch Sprühtrocknung oder Extrusion der Enzymlösung zusammen mit einem vorzugsweise natürlichen Polymer oder in Form von Kapseln, beispielsweise solchen, bei denen die Enzyme wie in einem erstarrten Gel eingeschlossen sind oder in solchen vom Kern-Schale-Typ, bei dem ein enzymhaltiger Kern mit einer Wasser-, Luft- und/oder Chemikalien-undurchlässigen Schutzschicht überzogen ist. In aufgelagerten Schichten können zusätzlich weitere Wirkstoffe, beispielsweise Stabilisatoren, Emulgatoren, Pigmente, Bleich- oder Farbstoffe aufgebracht werden. Derartige Kapseln werden nach an sich bekannten Methoden, beispielsweise durch Schüttel- oder Rollgranulation oder in Fluid-bed-Prozessen aufgebracht. Vorteilhafterweise sind derartige Granulate, beispielsweise durch Aufbringen polymerer Filmbildner, staubarm und aufgrund der Beschichtung lagerstabil.Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
Weiterhin ist es möglich, zwei oder mehrere Enzyme zusammen zu konfektionieren, so dass ein einzelnes Granulat mehrere Enzymaktivitäten aufweist.Furthermore, it is possible to assemble two or more enzymes together so that a single granule has several enzyme activities.
Wie aus der vorherigen Ausführungen ersichtlich, bildet das Enzym-Protein nur einen Bruchteil des Gesamtgewichts üblicher Enzym-Zubereitungen. Erfindungsgemäß bevorzugt eingesetzte Protease- und Amylase-Zubereitungen enthalten zwischen 0,1 und 40 Gew.-%, bevorzugt zwischen 0,2 und 30 Gew.-%, besonders bevorzugt zwischen 0,4 und 20 Gew.-% und insbesondere zwischen 0,8 und 10 Gew.-% des Enzymproteins.As can be seen from the previous comments, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10 wt .-% of the enzyme protein.
Bevorzugt werden insbesondere solche Reinigungsmittel, die, jeweils bezogen auf ihr Gesamtgewicht, 0,1 bis 12 Gew.-%, vorzugsweise 0,2 bis 10 Gew.-% und insbesondere 0,5 bis 8 Gew.-% Enzym-Zubereitungen enthalten.Particular preference is given to detergents which, based in each case on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight, of enzyme preparations.
Bevorzugt sind die Enzyme, insbesondere die Amylase(n) und/oder Protease(n), in (einer) der festen Phase(n), bevorzugt als Granulat bzw. Granulate, enthalten.The enzymes, in particular the amylase (s) and / or protease (s), are preferably present in (one) of the solid phase (s), preferably as granules or granules.
Als Glaskorrosionsinhibitoren werden Metallsalze, insbesondere Zink- oder Bismuthsalze, vorzugsweise Zinksalze, insbesondere Zinkacetat, eingesetzt. Als Glaskorrosionsinhibitoren werden vorzugsweise auch Polyethylenimine und Polyvinylamine, wie beispielsweise unter dem Namen Lupasol® bzw. Lupamin® von BASF erhältlich, insbesondere nicht alkoxylierte Polyethylenimine, eingesetzt. Glaskorrosionsinhibitoren sind in erfindungsgemäßen Mitteln vorzugsweise in einer Menge von 0,05 bis 5 Gew.-%, insbesondere in einer Menge von 0,1 bis 2 Gew.-%, enthalten.Glass corrosion inhibitors used are metal salts, in particular zinc salts or bismuth salts, preferably zinc salts, in particular zinc acetate. Polyethyleneimines and polyvinylamines, which are obtainable for example under the name Lupasol® or Lupamin® from BASF, in particular non-alkoxylated polyethyleneimines, are also preferably used as glass corrosion inhibitors. Glass corrosion inhibitors are preferably present in compositions according to the invention in an amount of from 0.05 to 5% by weight, in particular in an amount of from 0.1 to 2% by weight.
Die erfindungsgemäßen Reinigungsmittel zeichnen sich dadurch aus, dass sie lagerstabil sind und selbst nach einem längeren Zeitraum keine Phasentrennung auftritt.The cleaning agents according to the invention are characterized in that they are stable on storage and even after a prolonged period, no phase separation occurs.
Weiterer Gegenstand der vorliegenden Erfindung ist auch ein maschinelles Geschirrspülverfahren, bei welchem ein erfindungsgemäßes Reinigungsmittel zum Einsatz kommt.A further subject of the present invention is also a machine dishwashing process in which a cleaning agent according to the invention is used.
In noch einem Aspekt betrifft die Erfindung auch die Verwendung des erfindungsgemäßen Reinigungsmittels als Geschirrspülmittel, insbesondere maschinelles Geschirrspülmittel.In yet another aspect, the invention also relates to the use of the cleaning agent according to the invention as a dishwashing detergent, in particular automatic dishwashing detergent.
Es wurden die erfindungsgemäße Reinigungsmittelformulierung E1 (E1 gemäß Tabellen 1,2) sowie eine entsprechende Vergleichsrezeptur V1 (V1 gemäß Tabellen 1,2) hergestellt. Die in den Tabellen angegebenen Mengen sind dabei in Gew.-% Aktivsubstanz. Es wurden jeweils 15 g der festen Phase in eine erste Kammer sowie je 5 g der flüssigen Phase (E1 bzw. V1) in eine neben der ersten Kammer befindliche Kammer in einem Zweikammerbeutel aus Polyvinylalkohol eingeschweißt.The inventive detergent formulation E1 (E1 according to Table 1, 2) and a corresponding comparative formulation V1 (V1 according to Table 1, 2) were prepared. The amounts indicated in the tables are in% by weight of active substance. In each case, 15 g of the solid phase were sealed into a first chamber and 5 g each of the liquid phase (E1 or V1) in a chamber next to the first chamber in a two-chamber bag made of polyvinyl alcohol.
Als Schüttdichte der Pulverphasen wurde das Gewicht von 1 l Pulver bestimmt.As the bulk density of the powder phases, the weight of 1 liter of powder was determined.
Die Dichte der Flüssigphasen wurde über ein Pyknometer bestimmt. Aus beiden Werten ergibt sich rechnerisch die mittlere Dichte des zusammengesetzten Produkts.
Das erfindungsgemäße Beispiel E1 (Kombination aus 15 g fester Phase E1 und 5 g flüssiger Phase E1) zeigt gegenüber der Vergleichsformulierung V1 (Kombination aus 15 g fester Phase V1 und 5 g flüssiger Phase V1) eine höhere mittlere Produktdichte. Dies bedeutet, dass das vorportionierte erfindungsgemäße Reinigungsmittel bei gleicher Menge an Aktivstoffen eine geringeres Volumen ausfüllt und somit auch in volumenbeschränkten Dosierkammern eingesetzt werden kann. Alternativ kann so ein vorproportioniertes Reinigungsmittel bei gleichem Volumen der Portion wie bei der Vergleichssubstanz ein vorportioniertes Reinigungsmittel mit einem höheren Gewicht (und damit einem höheren Gehalt an Aktivstoff pro Spülgang) eingesetzt werden.Example E1 according to the invention (combination of 15 g of solid phase E1 and 5 g of liquid phase E1) shows a higher average product density compared to comparative formulation V1 (combination of 15 g of solid phase V1 and 5 g of liquid phase V1). This means that the pre-portioned cleaning agent according to the invention fills a smaller volume with the same amount of active substances and thus can also be used in volume-limited metering chambers. Alternatively, such a pre-proportioned detergent with the same volume of the portion as in the comparison substance, a pre-portioned detergent with a higher weight (and thus a higher content of active ingredient per wash) can be used.
Ebenfalls geeignet sind vorportionierte Reinigungsmittel der folgenden Zusammensetzung (E2). Es wurden dazu 12 g der festen Phase (E2) in einen ersten Beutel aus Polyvinylalkohol eingeschweißt sowie 4 g der flüssigen Phase (E2) in einen zweiten Beutel aus Polyvinylalkohol eingeschweißt.
Claims (11)
- A pre-portioned cleaning agent, preferably an automatic dishwashing agent, in a packaging having at least two compartments, comprising at least one solid, preferably powdered, phase and at least one liquid phase, characterized in that the cleaning agent contains from 2 to 20 wt.%, in particular from 2 to 10 wt.% (based on the total weight of the agent), of polymeric or co-polymeric polycarboxylates and/or sulfonic acid group-containing polymers, and the solid phase (or solid phases) contains less than 1 wt.% (based on the total weight of the solid phase) of the polymeric or co-polymeric polycarboxylates and/or sulfonic acid group-containing polymers, the cleaning agent containing less than 1 wt.% of phosphate, based on the total weight of the cleaning agent.
- The cleaning agent according to claim 1, characterized in that the ratio of the weight of the solid phase, optionally of all the solid phases, to the weight of the liquid phase, optionally of all the liquid phases, is from 1:10 to 10:1, preferably from 1:5 to 5:1.
- The cleaning agent according to one of the preceding claims, characterized in that at least one polyalkylene glycol, preferably polyethylene glycol, having an average molecular weight of between 160 and 6000, preferably between 200 and 5000, in particular between 300 and 4000, for example 400, is contained in the liquid phase.
- The cleaning agent according to one of the preceding claims, characterized in that a bleaching agent, preferably in an amount of from 5 to 40 wt.%, more preferably from 10 to 20 wt.% (based on the total weight of the solid phases) is contained in the solid phase.
- The cleaning agent according to one of the preceding claims, characterized in that the liquid phase is substantially free of water.
- The cleaning agent according to one of the preceding claims, characterized in that at least one, preferably two or more, nonionic surfactants are contained in the liquid phase.
- The cleaning agent according to one of the preceding claims, characterized in that the cleaning agent contains phosphonate in amounts of from 0.01 to 25 wt.%, preferably from 5 to 20 wt.%, 8 to 15 wt.% (in each case based on the total weight of the agent).
- The cleaning agent according to one of the preceding claims, characterized in that it is a water-soluble packaging, in particular a multi-chamber pouch, in particular having two, three, four or more chambers.
- The cleaning agent according to one of claims 1 to 8, characterized in that it is a water-soluble or water-dispersible packaging consisting of a polyvinyl alcohol-containing film.
- The use of a cleaning agent according to one of the preceding claims 1 to 9 in a cleaning process in an automatic dishwasher.
- A method for cleaning dishes, preferably in an automatic dishwasher, characterized in that a cleaning agent according to one of claims 1 to 9 is used.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL15702291T PL3102660T3 (en) | 2014-02-06 | 2015-02-04 | Multi-phase pre-portioned detergent |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102014202222.3A DE102014202222A1 (en) | 2014-02-06 | 2014-02-06 | Multiphase pre-portioned detergent II |
PCT/EP2015/052298 WO2015118010A1 (en) | 2014-02-06 | 2015-02-04 | Multi-phase pre-portioned detergent |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3102660A1 EP3102660A1 (en) | 2016-12-14 |
EP3102660B1 true EP3102660B1 (en) | 2018-12-19 |
Family
ID=52444314
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP15702291.4A Active EP3102660B1 (en) | 2014-02-06 | 2015-02-04 | Multi-phase pre-portioned detergent |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP3102660B1 (en) |
DE (1) | DE102014202222A1 (en) |
PL (1) | PL3102660T3 (en) |
WO (1) | WO2015118010A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
PL3124587T3 (en) * | 2015-07-29 | 2019-08-30 | The Procter And Gamble Company | Multi-phase unit-dose cleaning product |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020142931A1 (en) * | 2000-07-19 | 2002-10-03 | The Procter & Gamble Company | Gel form automatic dishwashing compositions, methods of preparation and use thereof |
EP1378563B1 (en) * | 2002-07-03 | 2007-01-03 | The Procter & Gamble Company | Detergent Composition |
GB0509377D0 (en) * | 2005-05-09 | 2005-06-15 | Reckitt Benckiser Nv | Detergent composition |
DE602006020324D1 (en) * | 2005-10-28 | 2011-04-07 | Procter & Gamble | COMPOSITION COMPRISING A SUBSTITUTED BENZENE SULPHONATE |
US8066818B2 (en) * | 2008-02-08 | 2011-11-29 | The Procter & Gamble Company | Water-soluble pouch |
GB201101547D0 (en) * | 2011-01-31 | 2011-03-16 | Reckitt Benckiser Nv | Container for use in a washing process |
-
2014
- 2014-02-06 DE DE102014202222.3A patent/DE102014202222A1/en not_active Withdrawn
-
2015
- 2015-02-04 WO PCT/EP2015/052298 patent/WO2015118010A1/en active Application Filing
- 2015-02-04 PL PL15702291T patent/PL3102660T3/en unknown
- 2015-02-04 EP EP15702291.4A patent/EP3102660B1/en active Active
Non-Patent Citations (1)
Title |
---|
None * |
Also Published As
Publication number | Publication date |
---|---|
PL3102660T3 (en) | 2019-07-31 |
WO2015118010A1 (en) | 2015-08-13 |
DE102014202222A1 (en) | 2015-08-06 |
EP3102660A1 (en) | 2016-12-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2366010B1 (en) | Machine dishwashing detergent | |
EP3209762B1 (en) | Dishwasher detergent containing metal complexes | |
EP3102658B1 (en) | Multi-phase pre-portioned cleaning agent | |
EP2814932B1 (en) | Sulfopolymer-containing liquid cleaning agent with low water content | |
EP3080242B1 (en) | Phosphate-free liquid dish soap | |
DE102012222266A1 (en) | Process for the preparation of low-water to anhydrous liquid washing or cleaning agents | |
EP3114198B1 (en) | Pre-portioned cleaning agent comprising at least two separate liquid preparations | |
EP3102657B1 (en) | Preportioned cleaning product | |
EP3102660B1 (en) | Multi-phase pre-portioned detergent | |
EP3431575A1 (en) | Dishwashing detergent compositions containing citrate dihydrate and anhydrate | |
DE102015213939A1 (en) | A multi-phase dishwashing detergent comprising a surfactant core | |
EP3481936A1 (en) | Dishwasher agent containing saccharic acid and amino carboxylic acid | |
EP3194552B1 (en) | Cleaning composition | |
EP3102659B1 (en) | Use of amino carboxylic acids for stabilising low-water, liquid detergents or cleaning agents | |
EP2943560B1 (en) | Low-water to water-free liquid cleaning agent | |
DE102014202226A1 (en) | Use of at least one polyalkylene glycol having an average molecular weight of between 1500 and 8000, in particular between 2000 and 6000, in particular between 3000 and 4500, for improving the brilliance of liquid, low-water washing or cleaning agents | |
DE102012222268A1 (en) | Low-water to anhydrous liquid detergents | |
DE102012222267A1 (en) | Low-water to anhydrous liquid detergents | |
WO2018002178A1 (en) | Cleaning agent with reduced glass corrosion | |
DE102014226904A1 (en) | Copolymers to improve the rinse performance |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20160713 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20171122 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20180808 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502015007315 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1078702 Country of ref document: AT Kind code of ref document: T Effective date: 20190115 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20181219 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190319 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190319 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190320 Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190419 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190419 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502015007315 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190204 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20190228 |
|
26N | No opposition filed |
Effective date: 20190920 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190228 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190228 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190204 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190228 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 1078702 Country of ref document: AT Kind code of ref document: T Effective date: 20200204 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20210226 Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200204 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20150204 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220228 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230530 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240219 Year of fee payment: 10 Ref country code: GB Payment date: 20240219 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PL Payment date: 20240125 Year of fee payment: 10 |