EP3833732A1 - Liquid bleach-precursor containing detergent or cleaning agent - Google Patents
Liquid bleach-precursor containing detergent or cleaning agentInfo
- Publication number
- EP3833732A1 EP3833732A1 EP19750102.6A EP19750102A EP3833732A1 EP 3833732 A1 EP3833732 A1 EP 3833732A1 EP 19750102 A EP19750102 A EP 19750102A EP 3833732 A1 EP3833732 A1 EP 3833732A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- radiation
- weight
- acid
- atoms
- cleaning
- 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.)
- Pending
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 45
- 239000002243 precursor Substances 0.000 title claims abstract description 23
- 239000003599 detergent Substances 0.000 title claims abstract description 20
- 239000012459 cleaning agent Substances 0.000 title claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 238000004140 cleaning Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 239000004753 textile Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 49
- 125000004432 carbon atom Chemical group C* 0.000 claims description 47
- 230000005855 radiation Effects 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 239000004530 micro-emulsion Substances 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 2
- HGASFNYMVGEKTF-UHFFFAOYSA-N octan-1-ol;hydrate Chemical compound O.CCCCCCCCO HGASFNYMVGEKTF-UHFFFAOYSA-N 0.000 claims 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 abstract description 2
- 102000004190 Enzymes Human genes 0.000 description 37
- 108090000790 Enzymes Proteins 0.000 description 37
- 229940088598 enzyme Drugs 0.000 description 37
- -1 alkyl glycol ethers Chemical class 0.000 description 19
- 108090001060 Lipase Proteins 0.000 description 18
- 102000004882 Lipase Human genes 0.000 description 18
- 239000004367 Lipase Substances 0.000 description 18
- 235000019421 lipase Nutrition 0.000 description 18
- 235000014113 dietary fatty acids Nutrition 0.000 description 17
- 239000000194 fatty acid Substances 0.000 description 17
- 229930195729 fatty acid Natural products 0.000 description 17
- 150000002191 fatty alcohols Chemical class 0.000 description 17
- 150000004665 fatty acids Chemical class 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- 108091005804 Peptidases Proteins 0.000 description 12
- 102000035195 Peptidases Human genes 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 11
- 239000004365 Protease Substances 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 239000002736 nonionic surfactant Substances 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 9
- 108010084185 Cellulases Proteins 0.000 description 8
- 102000005575 Cellulases Human genes 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 108010059892 Cellulase Proteins 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 108010056079 Subtilisins Proteins 0.000 description 7
- 102000005158 Subtilisins Human genes 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 238000009463 water soluble packaging Methods 0.000 description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 239000003945 anionic surfactant Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 6
- 239000004382 Amylase Substances 0.000 description 5
- 108010059820 Polygalacturonase Proteins 0.000 description 5
- 239000007844 bleaching agent Substances 0.000 description 5
- 238000007046 ethoxylation reaction Methods 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 241000194110 Bacillus sp. (in: Bacteria) Species 0.000 description 4
- 239000004435 Oxo alcohol Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 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
- 150000001768 cations Chemical class 0.000 description 4
- 229940106157 cellulase Drugs 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 235000019419 proteases Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 102000013142 Amylases Human genes 0.000 description 3
- 108010065511 Amylases Proteins 0.000 description 3
- 102100032487 Beta-mannosidase Human genes 0.000 description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 235000019418 amylase Nutrition 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 108010055059 beta-Mannosidase Proteins 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 108010005400 cutinase Proteins 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 108010002430 hemicellulase Proteins 0.000 description 3
- 239000001814 pectin Substances 0.000 description 3
- 235000010987 pectin Nutrition 0.000 description 3
- 229920001277 pectin Polymers 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N 1-Tetradecanol Natural products CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000193744 Bacillus amyloliquefaciens Species 0.000 description 2
- 241000193422 Bacillus lentus Species 0.000 description 2
- 241000194108 Bacillus licheniformis Species 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
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 101710121765 Endo-1,4-beta-xylanase Proteins 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 241000193385 Geobacillus stearothermophilus Species 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 241001480714 Humicola insolens Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 241000183011 Melanocarpus Species 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 102000004316 Oxidoreductases Human genes 0.000 description 2
- 108090000854 Oxidoreductases Proteins 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 241000223258 Thermomyces lanuginosus Species 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 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
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- 108010093305 exopolygalacturonase Proteins 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229930182478 glucoside Natural products 0.000 description 2
- 150000008131 glucosides Chemical class 0.000 description 2
- 229930182470 glycoside Natural products 0.000 description 2
- 150000002338 glycosides Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 229940100573 methylpropanediol Drugs 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000035772 mutation Effects 0.000 description 2
- 229940043348 myristyl alcohol Drugs 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N n-hexadecyl alcohol Natural products CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 108020004410 pectinesterase Proteins 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 229920005646 polycarboxylate Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000013042 solid detergent Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229940012831 stearyl alcohol Drugs 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 238000003856 thermoforming Methods 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- NPMRPDRLIHYOBW-UHFFFAOYSA-N 1-(2-butoxyethoxy)propan-2-ol Chemical compound CCCCOCCOCC(C)O NPMRPDRLIHYOBW-UHFFFAOYSA-N 0.000 description 1
- QWOZZTWBWQMEPD-UHFFFAOYSA-N 1-(2-ethoxypropoxy)propan-2-ol Chemical compound CCOC(C)COCC(C)O QWOZZTWBWQMEPD-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 1
- GQCZPFJGIXHZMB-UHFFFAOYSA-N 1-tert-Butoxy-2-propanol Chemical compound CC(O)COC(C)(C)C GQCZPFJGIXHZMB-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
- C11D3/391—Oxygen-containing compounds
-
- 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3945—Organic per-compounds
-
- 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
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0017—Multi-phase liquid compositions
- C11D17/0021—Aqueous microemulsions
-
- 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—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
- 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
- C11D2111/12—Soft surfaces, e.g. textile
-
- 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
- C11D2111/40—Specific cleaning or washing processes
- C11D2111/46—Specific cleaning or washing processes applying energy, e.g. irradiation
Definitions
- Liquid detergents are known in the art and have become increasingly popular with consumers in recent years because they offer a number of advantages over solid detergents. These include the simpler dosing and the generally faster dissolution in the wash liquor. In addition, they are often perceived as safer and less aggressive towards textiles and the environment.
- Liquid detergents however, have the disadvantage that not all of the ingredients that are established in solid detergents and cleaning agents and that the user trusts in their performance, can be easily incorporated in a stable manner.
- an effective bleaching system which in solid agents usually consists of a peroxidic bleach and a bleach activator that forms a peroxocarboxylic acid under perhydrolysis conditions, is problematic in liquid agents, because the stability of the bleach activator against hydrolytic attack is usually not adequately guaranteed, especially in aqueous agents can be.
- the presence of oxidative bleaching agents can adversely affect the stability of other detergent and cleaning agent ingredients, such as dyes or fragrances or enzymes.
- a further known embodiment of the separation principle consists in enveloping at least one of the problematic ingredients with a protective layer which surrounds the ingredient during the production and storage of the liquid agent and prevents contact with the negatively interacting other ingredients, but breaks open under application conditions and releases the ingredient , so that he can contribute the desired amount to the washing or cleaning result of the agent.
- concentration differences between the liquid agent and the washing or cleaning liquid are used to dissolve the coating layer only under the conditions in which the agent is used.
- the present invention uses targeted energy input in order to produce a reactive active ingredient from an ingredient that is stable when the liquid agent is stored.
- the invention relates to a water and surfactant-containing liquid washing or cleaning agent which contains a hydrophobic precursor compound in microemulsified form, from which a peroxocarboxylic acid or its salt can be released by UV radiation.
- Such precursor compounds are contained in the agents according to the invention preferably in amounts from 0.1% by weight to 20% by weight, in particular from 1% by weight to 15% by weight.
- Another object of the invention is the use of a combination of an aqueous microemulsion of a hydrophobic precursor compound, from which a peroxocarboxylic acid or its salt can be released by UV radiation, and UV radiation for removing stains when washing textiles or when cleaning hard surfaces.
- the microemulsion mentioned here can be a washing or cleaning agent according to the invention, but conventional components of washing and cleaning agents can also be missing;
- the microemulsion used according to the invention preferably contains from 2% by weight to 12% by weight, in particular from 4% by weight to 10% by weight of the hydrophobic precursor compound, from 2% by weight to 40% by weight, in particular from 4% by weight to 35% by weight of microemulsifier and to 100% by weight of water.
- Another object of the invention is a washing or cleaning process in which a textile surface in need of washing or a hard surface in need of cleaning is brought into contact with a surfactant-containing aqueous washing or cleaning liquid which contains a hydrophobic precursor compound in microemulsified form, from which UV- Irradiation a peroxocarboxylic acid or its salt can be released, and UV radiation can act on the liquid.
- a surfactant-containing aqueous washing or cleaning liquid which contains a hydrophobic precursor compound in microemulsified form, from which UV- Irradiation a peroxocarboxylic acid or its salt can be released, and UV radiation can act on the liquid.
- Such a method can be carried out manually or mechanically, for example with the aid of a washing machine or a dishwasher, the washing machine or dishwasher having a device for UV radiation or the washing or cleaning liquid, in particular when the method is carried out manually, using a UV Radiation source is exposed. Washing machines and dishwashers that have a UV radiation source are well
- the process according to the invention can be carried out at temperatures even below room temperature, in particular when using cold water for preparing the surfactant-containing aqueous washing or cleaning liquid, or is preferably carried out at temperatures in the range from 5 ° C. to 60 ° C., in particular from 10 ° C. up to 40 ° C.
- UV radiation can act on the liquid shortly before it is brought into contact with the object to be cleaned. It is preferred if the action of UV radiation takes place during the contact of the washing or cleaning liquid with the textile to be washed or the hard surface to be cleaned, the UV radiation not during the entire contact period, which is generally 1 minute to 2 Hours, in particular 2 minutes to 1 hour, must act, but the action can, if desired, begin even before the contact.
- UV radiation is electromagnetic radiation, which comprises the wavelengths from 100 nm to 380 nm in the spectrum.
- UV radiation is preferably used which has wavelengths in the range from 100 nm to 300 nm, in particular from 240 nm to 270 nm, it being further preferred if the maximum intensity of the UV radiation is in the range mentioned.
- the particularly preferred range from 240 nm to 270 nm is in the UVC range and is not covered by sunlight, since its UVC component is filtered out by the atmosphere before reaching the earth's surface.
- mercury vapor lamps or light-emitting diodes (LEDs) can be used to generate the UV radiation essential to the invention. UV exposure times in the range from 5 minutes to 40 minutes, in particular from 6 minutes to 30 minutes, are normally completely sufficient.
- Hydrophobic in connection with the precursor compound means that it has an n-octanol / water partition coefficient log K 0 w at 20 ° C. of at least 0.5, preferably in the range from 1 to 30, and in particular from 2 to 20.
- microemulsified refers to the well-known chemical meaning of the term and indicates that at least one liquid is in another with average droplet diameters in the single-digit to double-digit micrometer range is distributed and the normally immiscible liquids are present without visible segregation.
- the (o / w) microemulsions preferred according to the invention contain the precursor which is finely divided in water and is stabilized with the aid of a microemulsifier; they are optically isotropic, microstructured and thermodynamically stable.
- microemulsifiers which can be used include alkyl glycol ethers, alkoxylated fatty alcohols, alkoxylated oxo alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl (poly) glucosides, sulfonates, and in particular alkyl / benzonate sulfonates, mixtures thereof, and / or alkylbenzene sulfonates, mixtures thereof, Alkyl glycol ethers, sulfonates and mixtures thereof are particularly preferred.
- Such microemulsifiers are contained in the agents according to the invention preferably in amounts of 0.01% by weight to 60% by weight, in particular 1% by weight to 50% by weight.
- the precursor compounds which can be used according to the invention are obtained in particular from the peroxoesters of one of the general formulas (I) to (VI),
- R '"(-0 (-A0) -C-00-R) m in which R for a linear or branched chain alkyl group having 1 to 30 C atoms, in particular 2 to 20 C atoms, R ' for a linear or branched chain Alkyl group with 1 to 30 C atoms, in particular 2 to 20 C atoms, R " for a linear or branched chain alkylene group with 1 to 30 C atoms, in particular 2 to 20 C atoms, R"'for an m-bonded linear or branched-chain alkyl group with 2 to 9 carbon atoms, in particular 3 to 5 carbon atoms, A for an alkylene group with 2 to 4 carbon atoms, m for a number from 2 to 6, in particular 3 or 4, and n for a number and their mixtures are selected from 2 to 30, in particular from 3 to 15.
- these peroxoesters presumably give rise to free radical intermediate compounds from the action of UV radiation, which compounds directly on the surfaces to be cleaned or in colored stains in the washing or cleaning liquid react or by reaction with water, for example, to form peroxyacids which develop their bleaching performance.
- Peroxoesters of this type are commercially available under the name Luperox®.
- Another advantage of the invention is that when such microemulsified hydrophobic precursor compounds are used, the stability of enzymes, for example proteases, in liquid media during storage is just as high as if the precursor compound were dispensed with, whereas the same use of H2O2 or phthalimidoperoxohexanoic acid instead Precursor compound leads to significant decreases in enzyme activity.
- enzymes for example proteases
- Liquid when used in relation to the agent according to the invention, includes all compositions which are flowable under standard conditions (20 ° C., 1013 mbar) and in particular also includes gels and pasty compositions. In particular, the term also includes non-Newtonian liquids which have a yield point.
- the amounts stated in connection with the constituents of the liquid agent described herein relate to% by weight, based on the total weight of the agent, unless stated otherwise.
- quantities which relate to at least one component always relate to the total amount of this type of component which is contained in the composition, unless explicitly stated otherwise. This means that such quantities, for example in combination with at least one nonionic surfactant, refer to the total amount of nonionic surfactants contained in the product.
- At least one refers to 1 or more, for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In connection with components of the compositions described herein, this information does not refer to the absolute amount of molecules but to the type of component. "At least one nonionic surfactant” therefore means, for example, one or more different nonionic surfactants, that is to say one or more different types of nonionic surfactants. Together with quantity information, the quantity information relates to the total quantity of the correspondingly designated type of constituent, as already defined above.
- the liquid detergent or cleaning agent according to the present invention preferably contains 1% by weight to 60% by weight, preferably 5% by weight to 45% by weight and, in particular if it is a detergent, 15% by weight. % to 40% by weight of at least one surfactant.
- Nonionic surfactants include all known nonionic surfactants commonly used in detergents or cleaning agents, especially those selected from the group consisting of alkyl glycol ethers, alkoxylated fatty alcohols, alkoxylated oxo alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, Alkylphenol polyglycol ethers, amine oxides, alkyl (poly) glucosides and mixtures thereof.
- the agents contain at least one fatty alcohol alkoxylate of the formula below as the nonionic surfactant
- R 1 -0- (AO) mH in which R 1 is a linear or branched, substituted or unsubstituted alkyl radical, AO is an ethylene oxide (EO) or propylene oxide (PO) group and m is an integer from 1 to 50 ,
- R 1 is a linear or branched alkyl radical having 5 to 30 C atoms, preferably with from 7 to 25 carbon atoms and especially with 10 to 19 carbon atoms.
- Preferred radicals R 1 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl radicals and mixtures thereof, the representatives with an even number of carbon atoms being preferred , Particularly preferred R 1 radicals are derived from fatty alcohols having 12 to 19 carbon atoms, for example coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or oxo alcohols having 10 to 19 carbon atoms.
- AO is an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group.
- the index m is an integer from 1 to 50, preferably 2 to 20 and preferably 2 to 10. In particular, m is 3, 4, 5, 6 or 7.
- the agent according to the invention can contain mixtures of nonionic surfactants which have different degrees of ethoxylation. Surfactants with degrees of alkoxylation / ethoxylation of at least 5 are preferred.
- Such fatty alcohol ethoxylates are available under the trade names Dehydol LT7 ® (BASF SE), Lutensol ® A07 (BASF SE), Lutensol ® M7 (BASF SE) and Neodol ® 45-7 (Shell Chemicals).
- the fatty alcohol ethoxylates mentioned above preferably have degrees of ethoxylation of at least 5, preferably 7.
- Such fatty alcohol ethoxylates can be used alone, as mixtures of such fatty alcohol ethoxylates or as mixtures with low-ethoxylated fatty alcohol ethoxylates such as Lutensol ® A03 (BASF) may be used. In such mixtures it is preferred that the fatty alcohol ethoxylates with degrees of ethoxylation of at least 5, preferably 7, at least 50% by weight, preferably at least 75% by weight make up the total amount of fatty alcohol ethoxylates.
- nonionic surfactants which can be contained in the agents for the purposes of the present invention include, but are not limited to, alkyl (poly) glycosides, alkoxylated fatty acid alkyl esters, fatty acid alkanolamides, hydroxy mixed ethers, sorbitan fatty acid esters and polyhydroxy fatty acid amides.
- Suitable alkyl (poly) glycosides are, for example, those of the formula R 2 0- [G] P , in which R 2 is a branched or branched alkyl having 12 to 16 carbon atoms, G is a sugar residue with 5 or 6 carbon atoms, in particular glucose, and the index p is 1 to 10. These can be contained in the agent for example in amounts of up to 5% by weight.
- the liquid composition according to the present invention preferably contains 1% by weight to 30% by weight, in particular 2% by weight to 20% by weight and particularly preferably at least 10% by weight of at least one anionic surfactant.
- the anionic surfactants are preferably surfactants from the group of the sulfonates, in particular alkylbenzenesulfonates and / or secondary alkanesulfonates.
- the agent according to the invention comprises at least one secondary alkane sulfonate.
- the at least one secondary alkanesulfonate can be any known secondary alkanesulfonate which is suitable for the purpose according to the invention.
- the alkanesulfonate further comprises any cation, preferably selected from the group Na + , K + , NFLF, 1 Zn 2+ , 14 Mg 2+ , 14 Ca 2+ , 14 Mn 2+ and their mixtures, particularly preferably Na + .
- the corresponding acid can also be used in various embodiments, ie the cation is H + .
- the at least one secondary alkanesulfonate has the formula R 1 CH (S0 3 X + ) R 2 , where each R 1 and R 2 is independently a linear or branched alkyl having 1 to 20 carbon atoms and forms a linear or branched alkyl group with the carbon atom to which they are attached, preferably having 10 to 30 carbon atoms, preferably having 10 to 20 carbon atoms, and X + is selected from the group Na + , K + , NH 4 + , 1 Zn 2+ , 14 Mg 2+ , 14 Ca 2+ , 14 Mn 2 + and their mixtures, preferably Na + .
- X + can also be H + in various embodiments.
- the at least one secondary alkanesulfonate has the formula below
- M + n is preferably an integer between 7 and 17, preferably 10 to 14 and
- X + is selected from the group Na + , K + , NH 4 + , 14 Zn 2+ , 14 Mg 2+ , 14 Ca 2+ , 14 Mn 2+ and mixtures thereof, preferably Na + .
- X + can also be H + in various embodiments.
- the at least one secondary alkanesulfonate is secondary C 14-1 7 sodium alkanesulfonate or the corresponding acid.
- Such a secondary C14-17 sodium alkane sulfonate is sold, for example, by the Clariant company under the trade name "Hostapur SAS60". At this point, it should be expressly pointed out that the agent described here may contain several secondary alkanesulfonates.
- the agent described herein contains other anionic surfactants that can be used as an alternative or in addition to the secondary alkanesulfonates.
- anionic surfactants preferably include alkylbenzenesulfonates.
- Alkylbenzenesulfonates are preferably selected from linear or branched alkylbenzenesulfonates of the formula
- R ' and R "are independently hydrogen or alkyl and together contain 9 to 19, preferably 9 to 15 and in particular 9 to 13 carbon atoms.
- a very particularly preferred representative is sodium dodecylbenzenesulfonate or the corresponding acid (HLAS).
- Na + can be replaced by a cation selected from K + , NH 4 + , 14 Zn 2+ , 14 Mg 2+ , 14 Ca 2+ , 14 Mn 2+ and mixtures thereof or by H + (corresponding acid) in preferred embodiments the secondary alkanesulfonates and alkylbenzenesulfonates described above are used in combination, in particular in a weight ratio of 2: 1 to 1: 2, preferably 1: 1. It is particularly preferred to use the alkylbenzenesulfonates in the acid form.
- agents can also contain other anionic surfactants, such as, for example, alkyl ether sulfates. Fatty alcohol ether sulfates of the formula below are preferred
- AO in the above formula represents an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide (EO) group and n is an integer from 1 to 50, preferably from 1 to 20 and preferably from Is 2 to 10.
- X + is any cation and is preferably selected from the group Na + , K + , NH 4 + , 1 Zn 2+ , 1 Mg 2+ , 1 Ca 2+ , 1 Mn 2 and mixtures thereof, particularly preferably Na + .
- R 4 is a linear or branched alkyl radical having 5 to 30 carbon atoms, preferably with from 7 to 25 carbon atoms and especially with 10 to 19 carbon atoms.
- R 4 radicals are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl radicals and mixtures thereof, the representatives having an even number of carbon atoms being preferred.
- Particularly preferred radicals R 4 are derived from fatty alcohols with 12 to 19 carbon atoms, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from oxo alcohols with 10 to 19 carbon atoms.
- the agent can contain mixtures of surfactants which have different degrees of alkoxylation n.
- the indicated degree of ethoxylation n represents a statistical mean, which can be an integer or a fraction for a specific product.
- the degrees of alkoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
- Preferred alkoxylates / ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- the liquid agent can contain at least one fatty acid.
- fatty acid refers to branched or unbranched carboxylic acids and their salts, the so-called soaps, having 6 to 22, preferably 12 to 18, carbon atoms.
- the fatty acid soaps can be in the form of their sodium, Potassium or magnesium or ammonium salts are present. In saponified form, they are preferably in the form of their sodium salts and / or ammonium salts.
- Amines which can be replaced for neutralization are preferably choline, triethylamine, monoethanolamine, diethanolamine, triethanolamine, methylethylamine or a mixture thereof, monoethanolamine being preferred.
- the fatty acids are used as such, ie not saponified. They can be dissolved, for example, in one or more components of the composition, preferably the at least one nonionic surfactant, and combined in this dissolved form with the other components of the composition.
- the fatty acid can be emulsified in the final product.
- Preferred liquid detergents also contain water as a solvent.
- the compositions contain 4% by weight to 25% by weight, in particular 6% by weight to 15% by weight, of water; in other embodiments of the invention, the agents contain more than 25% by weight and up to 90% by weight of water, in particular 35% by weight to 65% by weight of water.
- the liquid compositions can additionally contain one or more non-aqueous, organic solvents. Suitable non-aqueous solvents include monohydric or polyhydric alcohols, alkanolamines or glycol ethers.
- the solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, glycols, such as diglycol, propyldiglycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol monoxide -butyl ether, diethylene glycol methyl ether, diethyl englycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol,
- the non-aqueous solvent is selected from the group consisting of ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol and mixtures thereof.
- the non-aqueous solvent contains 1, 2-propanediol, glycerin or a mixture thereof, very particularly preferably glycerin.
- the agents according to the invention preferably have a viscosity (Brookfield rotational viscometer; spindle adapted to the viscosity range) in the range from 1 mPa.s to 1000 mPa.s, in particular from 5 mPa.s to 500 mPa.s.
- An agent according to the invention is also preferably translucent, in particular transparent, that is to say it has no optically perceptible cloudiness.
- the pH of the liquid detergent according to the invention can be adjusted using conventional pH regulators and is preferably in the range from pH 5 to pH 10, in particular from pH 7 to pH 9; these relate to the pH of a 1% (% by weight) solution of the agent in distilled water at 30 ° C.
- Suitable pH adjusters include acids and / or alkalis. Suitable acids are organic acids such as acetic acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid.
- the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof can also be used.
- Suitable bases come from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is preferred.
- Volatile alkali can also be used, for example in the form of ammonia and / or alkanolamines, which can contain up to 9 carbon atoms in the molecule.
- the alkanolamine is preferably selected from the group consisting of mono-, di-, triethanol- and propanolamine and mixtures thereof.
- the agent may contain other ingredients that improve its application technology and / or aesthetic properties.
- the detergent preferably additionally contains one or more substances from the group of enzymes, builders, complexing agents, electrolytes, perfumes, perfume carriers, fluorescent agents, dyes, hydrotropes, foam inhibitors, silicone oils, anti-redeposition agents, graying inhibitors, anti-wrinkle inhibitors, anti-crease agents, color transfer inhibitors. antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, phobing and impregnating agents, swelling and anti-slip agents, softening components and UV absorbers.
- the agents preferably contain at least one enzyme.
- the at least one enzyme can be any enzyme known in the art which can develop a catalytic activity in a washing or cleaning agent and includes, but is not limited to, proteases, amylases, lipases, cellulases, hemicellulases, mannanases, pectin cleaving enzymes, tannases, xylanases, xanthanases, ⁇ -glucosidases, carrageenases, perhydrolases, oxidases, oxidoreductases and mixtures thereof.
- the at least one enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases and mixtures thereof. In principle, these enzymes are of natural origin, but based on the natural molecules, improved variants are available for use in detergents or cleaning agents, which are accordingly preferred.
- subtilisin type those of the subtilisin type are preferred.
- subtilisins BPN 'and Carlsberg the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the enzyme which can no longer be assigned to the subtilisins in the narrower sense Proteases TW3 and TW7.
- Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from Novozymes A / S, Bagsvaerd, Denmark.
- subtilisins 147 and 309 are sold under the trade names Esperase® and Savinase® by Novozymes.
- the protease from Bacillus lentus DSM 5483 is derived from those listed under the name BLAP® Protease variants.
- proteases are, for example, those under the trade names Durazym®, Relase®, Everlase®, Nafizym®, Natalase®, Kannase® and Ovozyme® from Novozymes, which under the trade names, Purafect®, Purafect® OxP, Purafect® Prime, Excellase® and Properase® from Genencor, which under the trade name Protosol® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi® from Wuxi Snyder Bioproducts Ltd., China, under the trade name Proleather ® and Protease P® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzymes available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
- the proteases from Bacillus gibsonii and Bacillus pumilus are also used with particular preference.
- amylases are the a-amylases from Bacillus licheniformis, from B. amyloliquefaciens or from B. stearothermophilus and their further developments for use in detergents or cleaning agents.
- the enzyme from B. licheniformis is available from Novozymes under the name Termamyl® and from Genencor under the name Purasta DST. Further development products of this a-amylase are available from Novozymes under the trade names Duramyl® and TermamyKDultra, from Genencor under the name Purasta DOxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase®.
- amyloliquefaciens is sold by Novozymes under the name BAN®, and derived variants from the a-amylase from B. stearothermophilus under the names BSG® and Novamyl®, also from Novozymes. Furthermore, the a-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948). Fusion products of all of the molecules mentioned can also be used. In addition, the further developments of the a-amylase from Aspergillus niger and A.
- Examples of usable lipases or cutinases which are contained in particular because of their triglyceride-cleaving activities are the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or more developed lipases, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase®, Lipolase®Ultra, LipoPrime®, Lipozyme® and Lipex®. Furthermore, the cutinases, which were originally isolated from Fusarium solani pisi and Humicola insolens, can also be used.
- lipases are available from Amano under the names Lipase CE®, Lipase P®, Lipase B®, or Lipase CES®, Lipase AKG®, Bacillus sp. Lipase®, Lipase AP®, Lipase M-AP® and Lipase AML® available.
- the Genencor company can use, for example, the lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
- cellulases can be present as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously complement one another with regard to their various performance aspects.
- performance aspects include, in particular, the contributions of cellulase to the primary washing performance of the agent (cleaning performance), to the secondary washing performance of the agent (anti-redeposition or graying inhibition), to avivage (tissue effect) or to the exercise of a "stone washed" effect.
- EG fungal endoglucanase
- Novozymes under the trade name Celluzyme®
- the products Endolase® and Carezyme® which are also available from Novozymes, are based on the 50 kD-EG and 43 kD- EG from H. insolens DSM 1800.
- Other usable commercial products from this company are Cellusoft®, Renozyme® and Celluclean®, for example the 20 kD-EG from Melanocarpus, which are available from AB Enzymes, Finland, under the trade names Ecostone® and Biotouch® are available, further commercial products from AB Enzymes are Eco nase® and Ecopulp®.
- cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, where the from Bacillus sp. CBS 670.93 is available from Genencor under the trade name Puradax®.
- Other commercial products from Genencor are "Genencor detergent cellulase L" and IndiAge®Neutra. Variants of these enzymes obtainable by point mutations can also be used according to the invention.
- Particularly preferred cellulases are Thielavia terrestris cellulase variants, cellulases from Melanocarpus, in particular Melanocarpus albomyces, cellulases of the EGIII type from Trichoderma reesei or variants obtainable therefrom.
- hemicellulases can be used in particular to remove certain problem soils.
- these include, for example, mannanases, xanthan lyases, xanthanases, xyloglucanases, xylanases, pullulanases, pectin-cleaving enzymes and ⁇ -glucanases.
- the ⁇ -glucanase obtained from Bacillus subtilis is available under the name Cereflo® from Novozymes.
- Hemicellulases which are particularly preferred according to the invention are mannanases, which are marketed, for example, under the trade names Mannaway® by the company Novozymes or Purabrite® by the company Genencor.
- pectin-degrading enzymes are within the scope of the present invention also counted enzymes with designations of pectinase, pectate lyase, pectin esterase, Pektindemethoxylase, Pektinmethoxylase, pectin methylesterase, pectase, pectin, Pektinoesterase, Pektinpektylhydrolase, pectin depolymerase, endopolygalacturonase, Pektolase, Pektinhydrolase, pectin polygalacturonase, Endo-polygalacturonase, poly-a-1, 4-galacturonide glycanohydrolase, endogalacturonase, endo-D-galacturonase, galacturan 1, 4-a-galacturonidase, exopolygalacturonase, poly (galacturonate) hydrolase, exo-D-
- suitable enzymes in this regard are, for example, under the names Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from Novozymes, under the names Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L®, Rohapect 10L®, Rohapect B1 L® available from AB Enzymes and under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.
- the liquid compositions preferably contain the at least one enzyme in total amounts established in the prior art.
- the at least one enzyme in a total amount of 1 ⁇ 10 8 to 5 wt .-% based on active protein or in a total amount of 0.001 to 3 wt .-%, or 0.01 to 1.5 wt .-% or 0.05 to 1.25% by weight.
- the stated amounts are to be understood such that each enzyme contained can be contained in the stated amounts.
- the enzymes are preferably used as liquid enzyme formulation (s).
- the at least one enzyme that is present in a detergent or cleaning agent supports the cleaning performance of the agent on certain stains or stains.
- An agent according to the invention particularly preferably contains several enzymes, the enzymes being able to belong to the same or different enzyme classes.
- the enzymes particularly preferably show synergistic effects with regard to their action against certain soiling or stains, that is to say the enzymes contained in the composition mutually support one another in their performance.
- Polymers based on terephthalate-PEG can be used in particular as antiredeposition agents.
- (co) polymers based on polyethyleneimine, polyvinyl acetate and polyethylene glycol can also be used.
- Organic builders are particularly suitable as builders, for example the polycarboxylic acids which can be used in the form of their sodium salts or also as acids, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
- these are adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, in particular glutamic acid-N, N-diacetic acid (GLDA) and methylglycine-N, N-diacetic acid (MGDA), and mixtures of these .
- Polymeric polycarboxylates are also suitable as builders.
- alkali metal salts of polyacrylic acid or polymethacrylic acid for example those with a relative molecular weight of 600 to 750,000 g / mol.
- Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights of 1,000 to 10,000 g / mol, and particularly preferably 1,000 to 5,000 g / mol, can in turn be preferred from this group.
- Copolymers of polycarboxylates, in particular those of acrylic acid are also suitable Methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
- the polymers can also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
- Soluble builders such as acrylic polymers with a molecular weight of 1,000 to 5,000 g / mol, are preferably used in liquid detergents.
- the agents can additionally contain phosphonates, such as HEDP (1-hydroxyethane-1,1-diphosphonic acid) or DTPMP (diethylenetriaminepenta (methylenephosphonate), as builders and complexing agents.
- phosphonates such as HEDP (1-hydroxyethane-1,1-diphosphonic acid) or DTPMP (diethylenetriaminepenta (methylenephosphonate), as builders and complexing agents.
- the liquid detergents and cleaning agents can be produced in an analogous application by methods known in the prior art. They can be filled in a water-soluble envelope and thus be part of a water-soluble packaging. If the agent is packaged in a water-soluble envelope, it is preferred that the water content is less than 10% by weight, based on the total agent, and that the anionic surfactants are present in the form of their ammonium salts or as free acids.
- a water-soluble packaging contains a water-soluble envelope. The water-soluble covering is preferably formed by a water-soluble film material. Such water-soluble packaging can be made either by vertical form fill sealing (VFFS) or thermoforming processes.
- VFFS vertical form fill sealing
- the thermoforming process generally includes forming a first layer of a water-soluble sheet material to form bulges for receiving a composition therein, filling the composition into the bulges, covering the bulges filled with the composition with a second layer of a water-soluble sheet material and sealing the first and second layers with each other at least around the bulges.
- the water-soluble covering is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer mixtures.
- the sheath can be formed from 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, can be the same or different.
- the water-soluble package, comprising the agent and the water-soluble envelope can have one or more compartments.
- the liquid agent may be contained in one or more compartments, if any, of the water-soluble enclosure.
- the amount of liquid agent preferably corresponds to the full or half dose required for a washing or cleaning cycle. It is preferred that the water-soluble envelope contain polyvinyl alcohol or a polyvinyl alcohol copolymer.
- Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer, the molecular weight of which is in the range from 10,000 g / mol to 1,000,000 g / mol, preferably from 20,000 g / mol to 500,000 g / mol, particularly preferably from 30,000 g / mol to 100,000 g / mol and in particular from 40,000 g / mol to 80,000 g / mol.
- a film material suitable for producing the water-soluble covering can additionally contain polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers Polylactic acid, and / or mixtures of the above polymers, may be added.
- preferred polyvinyl alcohol copolymers comprise dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, itaconic acid being preferred.
- polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester.
- Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester or mixtures thereof.
- Suitable water-soluble films for use in the wrappings of the water-soluble packaging according to the invention are films which are sold by MonoSol LLC, for example under the name M8630, C8400 or M8900.
- the water-soluble packaging can have an essentially dimensionally stable spherical and pillow-shaped configuration with a circular, elliptical, square or rectangular basic shape.
- the water-soluble packaging can have one or more chambers for storing one or more agents. If the water-soluble packaging has two or more compartments, at least one compartment contains a liquid agent according to the invention, the further compartments may each contain a solid or a differently composed liquid agent, or the contents of the individual chambers together result in a liquid agent according to the Invention.
- the same composition, non-microemulsified preparations were used, which like the preparations according to the invention were used with or without UV radiation.
- white cotton cloths (4 cm x 4 cm) provided with standardized blueberry soiling were each provided with 10 ml of the test formulation and for 15 minutes with a UV-C lamp at a wavelength of 253.7 nm and an energy density of 221 , 4 mJ / cm 2 irradiated at a distance of 3 cm or left in a light-tight box for the same time ("unirradiated").
- the lobules were rinsed with water, dried and their brightness measured.
- the table below shows the difference in L values after and before treatment; negative values mean that the soiling has become darker, positive values mean that the soiling is lightened.
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Abstract
The invention relates to a water and surfactant-containing liquid detergent or cleaning agent containing a hydrophobic precursor compound in microemulsified form from which a peroxocarboxylic acid or salts thereof can be released by UV irradiation. The invention also relates to methods for washing textiles and cleaning hard surfaces with the aid of such precursor compounds.
Description
Flüssiges bleichmittelvorläuferhaltiges Wasch- oder Reinigungsmittel Liquid detergent or cleaning agent containing bleach precursor
Flüssigwaschmittel sind im Stand der Technik bekannt und sind in den letzten Jahren bei den Verbrauchern immer beliebter geworden, da sie eine Reihe von Vorteilen gegenüber festen Waschmitteln bieten. Diese schließen unter anderem die einfachere Dosierung und die in der Regel raschere Auflösung in der Waschflotte ein. Zusätzlich werden sie oft als sicherer und weniger aggressiv gegenüber den Textilien und der Umwelt wahrgenommen. Liquid detergents are known in the art and have become increasingly popular with consumers in recent years because they offer a number of advantages over solid detergents. These include the simpler dosing and the generally faster dissolution in the wash liquor. In addition, they are often perceived as safer and less aggressive towards textiles and the environment.
Flüssige Mittel weisen allerdings den Nachteil auf, dass in ihnen nicht alle Inhaltsstoffe, die in festen Wasch- und Reinigungsmitteln etabliert sind und auf deren Leistung der Anwender vertraut, ohne weiteres stabil einarbeitbar sind. So ist insbesondere die Einarbeitung eines wirksamen Bleichsystems, das in festen Mitteln üblicherweise aus einem peroxidischen Bleichmittel und einem unter Perhydrolysebedingungen eine Peroxocarbonsäure bildenden Bleichaktivator besteht, in flüssige Mittel problematisch, weil insbesondere in wasserhaltigen Mitteln die Stabilität des Bleichaktivators gegen den hydrolytischen Angriff meist nicht ausreichend gewährleistet werden kann. Überdies kann durch die Anwesenheit oxidativer Bleichmittel die Stabilität sonstiger Wasch- und Reinigungsmittelinhaltsstoffe, wie Färb- oder Duftstoffe oder Enzyme, beeinträchtigt werden. Deshalb ist verschiedentlich vorgeschlagen worden, die miteinander wenig verträglichen Komponenten flüssiger Mittel voneinander zu trennen, indem man Mehrkompartimentverpackungen für entsprechende Teilkomponenten des fertigen Mittels vorsieht, zum Beispiel Merkammerflaschen, aus denen die Teilkomponenten gemeinsam dosiert werden, oder Mehrkammerbeutel aus wasserlöslichem Folienmaterial, aus deren einzelnen Kammern die Teilkomponenten gleichzeitig oder nacheinander durch Auflösen der Kammerwände freigesetzt werden. Liquid detergents, however, have the disadvantage that not all of the ingredients that are established in solid detergents and cleaning agents and that the user trusts in their performance, can be easily incorporated in a stable manner. For example, the incorporation of an effective bleaching system, which in solid agents usually consists of a peroxidic bleach and a bleach activator that forms a peroxocarboxylic acid under perhydrolysis conditions, is problematic in liquid agents, because the stability of the bleach activator against hydrolytic attack is usually not adequately guaranteed, especially in aqueous agents can be. In addition, the presence of oxidative bleaching agents can adversely affect the stability of other detergent and cleaning agent ingredients, such as dyes or fragrances or enzymes. For this reason, various proposals have been made to separate the components of liquid agents, which are not very compatible with one another, by providing multi-compartment packaging for corresponding partial components of the finished agent, for example mercury bottles, from which the partial components are metered together, or multi-chamber bags made of water-soluble film material from their individual chambers the sub-components are released simultaneously or in succession by dissolving the chamber walls.
Eine weitere bekannte Ausgestaltung des Trennungsprinzips besteht in der Umhüllung mindestens eines der problematischen Inhaltsstoffe mit einer Schutzschicht, die während der Herstellung und Lagerung des flüssigen Mittels den Inhaltsstoff umgibt und den Kontakt mit den negativ wechselwirkenden übrigen Inhaltsstoffen verhindert, unter Anwendungsbedingungen aber aufbricht und den Inhaltsstoff freisetzt, so dass er den gewünschten Betrag zum Wasch- oder Reinigungsergebnis des Mittels leisten kann. Dabei nutzt man in der Regel Konzentrationsunterschiede zwischen dem flüssigen Mittel und der Wasch- oder Reinigungsflüssigkeit aus, um die Umhüllungsschicht erst unter Anwendungsbedingungen des Mittels aufzulösen. A further known embodiment of the separation principle consists in enveloping at least one of the problematic ingredients with a protective layer which surrounds the ingredient during the production and storage of the liquid agent and prevents contact with the negatively interacting other ingredients, but breaks open under application conditions and releases the ingredient , so that he can contribute the desired amount to the washing or cleaning result of the agent. As a rule, concentration differences between the liquid agent and the washing or cleaning liquid are used to dissolve the coating layer only under the conditions in which the agent is used.
Die vorliegende Erfindung nutzt im Unterschied zu den bekannten im Wesentlichen auf Wasserkonzentrations- oder pH-Wert-Differenzen beruhenden Freisetzungsmechanismen einen gezielten Energieeintrag, um aus einem bei Lagerung des flüssigen Mittels stabilen Inhaltsstoff einen reaktiven Wirkstoff zu erzeugen.
Ein Gegenstand der Erfindung ist ein wasser- und tensidhaltiges flüssiges Wasch- oder Reinigungsmittel, das eine hydrophobe Vorläuferverbindung in mikroemulgierter Form enthält, aus der durch UV-Bestrahlung eine Peroxocarbonsäure oder deren Salz freisetzbar ist. Derartige Vorläuferverbindungen sind in den erfindungsgemäßen Mitteln vorzugsweise in Mengen von 0,1 Gew.-% bis 20 Gew.-%, insbesondere von 1 Gew.-% bis 15 Gew.-% enthalten. In contrast to the known release mechanisms based essentially on water concentration or pH differences, the present invention uses targeted energy input in order to produce a reactive active ingredient from an ingredient that is stable when the liquid agent is stored. The invention relates to a water and surfactant-containing liquid washing or cleaning agent which contains a hydrophobic precursor compound in microemulsified form, from which a peroxocarboxylic acid or its salt can be released by UV radiation. Such precursor compounds are contained in the agents according to the invention preferably in amounts from 0.1% by weight to 20% by weight, in particular from 1% by weight to 15% by weight.
Ein weiterer Gegenstand der Erfindung ist die Verwendung einer Kombination aus einer wässrigen Mikroemulsion einer hydrophoben Vorläuferverbindung, aus der durch UV-Bestrahlung eine Peroxocarbonsäure oder deren Salz freisetzbar ist, und UV-Strahlung zur Entfernung von Anschmutzungen beim Waschen von Textilien oder beim Reinigen harter Oberflächen. Bei der hier genannten Mikroemulsion kann es sich um ein erfindungsgemäßes Wasch- oder Reinigungsmittel handeln, es können aber auch übliche Bestandteile von Wasch- und Reinigungsmitteln fehlen; vorzugsweise enthält die erfindungsgemäß verwendete Mikroemulsion von 2 Gew.-% bis 12 Gew.-%, insbesondere von 4 Gew.-% bis 10 Gew.-% der hydrophoben Vorläuferverbindung, von 2 Gew.-% bis 40 Gew.-%, insbesondere von 4 Gew.-% bis 35 Gew.-% Mikroemulgator und auf 100 Gew.-% Wasser. Another object of the invention is the use of a combination of an aqueous microemulsion of a hydrophobic precursor compound, from which a peroxocarboxylic acid or its salt can be released by UV radiation, and UV radiation for removing stains when washing textiles or when cleaning hard surfaces. The microemulsion mentioned here can be a washing or cleaning agent according to the invention, but conventional components of washing and cleaning agents can also be missing; the microemulsion used according to the invention preferably contains from 2% by weight to 12% by weight, in particular from 4% by weight to 10% by weight of the hydrophobic precursor compound, from 2% by weight to 40% by weight, in particular from 4% by weight to 35% by weight of microemulsifier and to 100% by weight of water.
Ein weiterer Gegenstand der Erfindung ist ein Wasch- oder Reinigungsverfahren, bei dem man eine waschbedürftige textile Oberfläche oder eine reinigungsbedürftige harte Oberfläche mit einer tensidhaltigen wässrigen Wasch- oder Reinigungsflüssigkeit in Kontakt bringt, die eine hydrophobe Vorläuferverbindung in mikroemulgierter Form enthält, aus der durch UV-Bestrahlung eine Peroxocarbonsäure oder deren Salz freisetzbar ist, und UV-Strahlung auf die Flüssigkeit einwirken lässt. Ein derartiges Verfahren kann manuell oder maschinell, beispielsweise mit Hilfe einer Waschmaschine oder einer Geschirrspülmaschine durchgeführt werden, wobei die Wasch- oder Geschirrspülmaschine eine Vorrichtung zur UV-Bestrahlung aufweist oder die Wasch- oder Reinigungsflüssigkeit, insbesondere bei manueller Ausführung des Verfahrens, manuell einer UV-Strahlungsquelle ausgesetzt wird. Wasch- und Geschirrspülmaschinen, die eine UV-Strahlungsquelle aufweisen, sind hinlänglich bekannt. Das erfindungsgemäße Verfahren kann, insbesondere bei Einsatz kalten Wassers zum Ansetzen der tensidhaltigen wässrigen Wasch- oder Reinigungsflüssigkeit, bei Temperaturen sogar noch unterhalb der Raumtemperatur durchgeführt werden oder wird vorzugsweise bei Temperaturen im Bereich von 5 °C bis 60 °C, insbesondere von 10 °C bis 40 °C durchgeführt. Another object of the invention is a washing or cleaning process in which a textile surface in need of washing or a hard surface in need of cleaning is brought into contact with a surfactant-containing aqueous washing or cleaning liquid which contains a hydrophobic precursor compound in microemulsified form, from which UV- Irradiation a peroxocarboxylic acid or its salt can be released, and UV radiation can act on the liquid. Such a method can be carried out manually or mechanically, for example with the aid of a washing machine or a dishwasher, the washing machine or dishwasher having a device for UV radiation or the washing or cleaning liquid, in particular when the method is carried out manually, using a UV Radiation source is exposed. Washing machines and dishwashers that have a UV radiation source are well known. The process according to the invention can be carried out at temperatures even below room temperature, in particular when using cold water for preparing the surfactant-containing aqueous washing or cleaning liquid, or is preferably carried out at temperatures in the range from 5 ° C. to 60 ° C., in particular from 10 ° C. up to 40 ° C.
Das Einwirken von UV-Strahlung auf die Flüssigkeit kann gewünschtenfalls kurz vor deren in Kontakt Bringen mit dem zu reinigenden Gegenstand erfolgen. Bevorzugt ist, wenn die Einwirkung von UV- Strahlung während des Kontakts der Wasch- oder Reinigungsflüssigkeit mit dem zu waschenden Textil oder der zu reinigenden harten Oberfläche stattfindet, wobei die UV-Strahlung nicht während der gesamten Kontaktdauer, die in der Regel 1 Minute bis 2 Stunden, insbesondere 2 Minuten bis 1 Stunde beträgt, einwirken muss, die Einwirkung aber gewünschtenfalls bereits vor dem Kontakt beginnen kann.
UV-Strahlung ist bekanntlich die elektromagnetische Strahlung, die im Spektrum die Wellenlängen von 100 nm bis 380 nm umfasst. Vorzugsweise wird erfindungsgemäß eine UV-Strahlung eingesetzt, die Wellenlängen im Bereich von 100 nm bis 300 nm, insbesondere von 240 nm bis 270 nm aufweist, wobei weiterhin bevorzugt ist, wenn sich das Intensitätsmaximum der UV-Strahlung in dem genannten Bereich befindet. Der besonders bevorzugte Bereich von 240 nm bis 270 nm liegt im UVC-Be- reich und wird von Sonnenlicht nicht abgedeckt, da dessen UVC-Anteil vor Erreichen der Erdoberfläche durch die Atmosphäre ausgefiltert wird. Beispielsweise können Quecksilberdampflampen oder Leuchtdioden (LED) eingesetzt werden, um die erfindungswesentliche UV-Strahlung zu erzeugen. Normalerweise völlig ausreichend sind UV-Bestrahlungsdauern im Bereich von 5 Minuten bis 40 Minuten, insbesondere von 6 Minuten bis 30 Minuten. Dabei sind Energiedichten der UV- Strahlung im Bereich von 150 mJ/cm2 bis 400 mJ/cm2, insbesondere von 200 mJ/cm2 bis 300 mJ/cm2, gemessen auf der Oberfläche der Wasch- oder Reinigungsflüssigkeit, normalerweise völlig ausreichend. If desired, UV radiation can act on the liquid shortly before it is brought into contact with the object to be cleaned. It is preferred if the action of UV radiation takes place during the contact of the washing or cleaning liquid with the textile to be washed or the hard surface to be cleaned, the UV radiation not during the entire contact period, which is generally 1 minute to 2 Hours, in particular 2 minutes to 1 hour, must act, but the action can, if desired, begin even before the contact. As is known, UV radiation is electromagnetic radiation, which comprises the wavelengths from 100 nm to 380 nm in the spectrum. According to the invention, UV radiation is preferably used which has wavelengths in the range from 100 nm to 300 nm, in particular from 240 nm to 270 nm, it being further preferred if the maximum intensity of the UV radiation is in the range mentioned. The particularly preferred range from 240 nm to 270 nm is in the UVC range and is not covered by sunlight, since its UVC component is filtered out by the atmosphere before reaching the earth's surface. For example, mercury vapor lamps or light-emitting diodes (LEDs) can be used to generate the UV radiation essential to the invention. UV exposure times in the range from 5 minutes to 40 minutes, in particular from 6 minutes to 30 minutes, are normally completely sufficient. Energy densities of UV radiation in the range from 150 mJ / cm 2 to 400 mJ / cm 2 , in particular from 200 mJ / cm 2 to 300 mJ / cm 2 , measured on the surface of the washing or cleaning liquid, are normally completely sufficient.
Hydrophob im Zusammenhang mit der Vorläuferverbindung bedeutet, dass sie einen n-Octanol- Wasser-Verteilungskoeffizient log K0w bei 20 °C von mindestens 0,5, vorzugsweise im Bereich von 1 bis 30, und insbesondere von 2 bis 20 aufweist. Hydrophobic in connection with the precursor compound means that it has an n-octanol / water partition coefficient log K 0 w at 20 ° C. of at least 0.5, preferably in the range from 1 to 30, and in particular from 2 to 20.
Die hydrophoben Vorläuferverbindungen werden in mikroemulgierter Form eingesetzt.„Mikroemul- giert“, wie hierin verwendet, bezieht sich auf die allgemein bekannte, chemische Bedeutung dieses Begriffs, und zeigt an, dass mindestens eine Flüssigkeit in einer anderen mit mittleren Tröpfchendurchmessern im einstelligen bis zweistelligen Mikrometerbereich verteilt ist und die normalerweise nicht mischbaren Flüssigkeiten ohne sichtbare Entmischung vorliegen. Die erfindungsgemäß bevorzugten (o/w)-Mikroemulsionen enthalten den in Wasser feinverteilten Vorläufer, der mit Hilfe eines Mikroemulgators stabilisiert ist; sie sind optisch isotrop, mikrostrukturiert und thermodynamisch stabil. Zu den brauchbaren Mikroemulgatoren gehören Alkylglykolether, alkoxylierte Fettalkohole, alkoxylierte Oxo-Alkohole, alkoxylierte Fettsäurealkylester, Fettsäureamide, alkoxylierte Fettsäureamide, Polyhydroxyfettsäureamide, Alkylphenolpolyglycolether, Aminoxide, Alkyl(poly)glucoside, Sulfonate, insbesondere Alkylbenzolsulfonate und/oder sekundäre Alkansulfonate, und deren Mischungen. Besonders bevorzugt sind Alkylglykolether, Sulfonate und deren Mischungen. Derartige Mikroemulgatoren sind in den erfindungsgemäßen Mitteln vorzugsweise in Mengen von 0,01 Gew.-% bis 60 Gew.-%, insbesondere von 1 Gew.-% bis 50 Gew.- % enthalten. The hydrophobic precursor compounds are used in microemulsified form. "Microemulsified," as used herein, refers to the well-known chemical meaning of the term and indicates that at least one liquid is in another with average droplet diameters in the single-digit to double-digit micrometer range is distributed and the normally immiscible liquids are present without visible segregation. The (o / w) microemulsions preferred according to the invention contain the precursor which is finely divided in water and is stabilized with the aid of a microemulsifier; they are optically isotropic, microstructured and thermodynamically stable. The microemulsifiers which can be used include alkyl glycol ethers, alkoxylated fatty alcohols, alkoxylated oxo alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl (poly) glucosides, sulfonates, and in particular alkyl / benzonate sulfonates, mixtures thereof, and / or alkylbenzene sulfonates, mixtures thereof, Alkyl glycol ethers, sulfonates and mixtures thereof are particularly preferred. Such microemulsifiers are contained in the agents according to the invention preferably in amounts of 0.01% by weight to 60% by weight, in particular 1% by weight to 50% by weight.
Die erfindungsgemäß einsetzbaren Vorläuferverbindungen werden insbesondere aus den Peroxo- estern einer der allgemeinen Formeln (I) bis (VI),
The precursor compounds which can be used according to the invention are obtained in particular from the peroxoesters of one of the general formulas (I) to (VI),
(VI) (VI)
R’" (-0 (-A0) -C-00-R)m in denen R für eine lineare oder verzweigtkettige Alkylgruppe mit 1 bis 30 C-Atomen, insbesondere 2 bis 20 C-Atomen, R' für eine lineare oder verzweigtkettige Alkylgruppe mit 1 bis 30 C-Atomen, insbesondere 2 bis 20 C-Atomen, R“ für eine lineare oder verzweigtkettige Alkylengruppe mit 1 bis 30 C-Atomen, insbesondere 2 bis 20 C-Atomen, R“‘ für eine m-bindige lineare oder verzweigtkettige Alkylgruppe mit 2 bis 9 C-Atomen, insbesondere 3 bis 5 C-Atomen, A für eine Alkylengruppe mit 2 bis 4 C-Atomen, m für eine Zahl von 2 bis 6, insbesondere 3 oder 4, und n für eine Zahl von 2 bis 30, insbesondere von 3 bis 15, steht, und deren Mischungen ausgewählt. Ohne an diese Theorie gebunden sein zu wollen entstehen aus diesen Peroxoestern durch Einwirkung von UV-Strahlung vermutlich radikalische Zwischenverbindungen, die direkt mit auf den zu reinigenden Oberflächen oder in der Wasch- oder Reinigungsflüssigkeit befindlichen gefärbten Anschmutzungen reagieren oder durch Reaktion mit zum Beispiel Wasser Peroxosäuren ausbilden können, welche ihre Bleichleistung entfalten. Derartige Peroxoester sind unter der Bezeichnung Luperox® kommerziell erhältlich. R '"(-0 (-A0) -C-00-R) m in which R for a linear or branched chain alkyl group having 1 to 30 C atoms, in particular 2 to 20 C atoms, R ' for a linear or branched chain Alkyl group with 1 to 30 C atoms, in particular 2 to 20 C atoms, R " for a linear or branched chain alkylene group with 1 to 30 C atoms, in particular 2 to 20 C atoms, R"'for an m-bonded linear or branched-chain alkyl group with 2 to 9 carbon atoms, in particular 3 to 5 carbon atoms, A for an alkylene group with 2 to 4 carbon atoms, m for a number from 2 to 6, in particular 3 or 4, and n for a number and their mixtures are selected from 2 to 30, in particular from 3 to 15. Without wishing to be bound by this theory, these peroxoesters presumably give rise to free radical intermediate compounds from the action of UV radiation, which compounds directly on the surfaces to be cleaned or in colored stains in the washing or cleaning liquid react or by reaction with water, for example, to form peroxyacids which develop their bleaching performance. Peroxoesters of this type are commercially available under the name Luperox®.
Als weiterer Vorteil der Erfindung ist zu werten, dass bei Einsatz derartiger mikroemulgierter hydrophober Vorläuferverbindungen die Stabilität von Enzymen, beispielsweise Proteasen, in flüssigen Mitteln bei Lagerung ebenso hoch ist wie wenn man auf die Vorläuferverbindung verzichtet, wohingegen der molgleiche Einsatz von H2O2 oder Phthalimidoperoxohexansäure statt der Vorläuferverbindung zu merklichen Enzymaktivitätsabnahmen führt. Another advantage of the invention is that when such microemulsified hydrophobic precursor compounds are used, the stability of enzymes, for example proteases, in liquid media during storage is just as high as if the precursor compound were dispensed with, whereas the same use of H2O2 or phthalimidoperoxohexanoic acid instead Precursor compound leads to significant decreases in enzyme activity.
„Flüssig“, wenn in Bezug auf das erfindungsgemäße Mittel verwendet, schließt alle bei Standardbedingungen (20°C, 1013mbar) fließfähigen Zusammensetzungen ein und erfasst insbesondere auch Gele und pastöse Zusammensetzungen. Insbesondere schließt der Begriff auch Nicht-Newtonsche Flüssigkeiten, die eine Fließgrenze besitzen, ein. Die im Zusammenhang mit den hierin beschriebenen Bestandteilen des flüssigen Mittels angegeben Mengen beziehen sich, sofern nichts anderes angegeben ist, auf Gew.-% jeweils bezogen auf das Gesamtgewicht des Mittels. Des Weiteren beziehen sich Mengenangaben, die sich auf mindestens einen Bestandteil beziehen, immer auf die Gesamtmenge dieser Art von Bestandteil, die in dem Mittel enthalten ist, sofern nicht explizit etwas anderes angegeben ist. Das heißt, dass sich derartige Mengenangaben, beispielsweise im Zusam-
menhang mit„mindestens einem nichtionischen Tensid“, auf die Gesamtmenge von nichtionischen Tensiden beziehen, die im Mittel enthalten ist. “Liquid”, when used in relation to the agent according to the invention, includes all compositions which are flowable under standard conditions (20 ° C., 1013 mbar) and in particular also includes gels and pasty compositions. In particular, the term also includes non-Newtonian liquids which have a yield point. The amounts stated in connection with the constituents of the liquid agent described herein relate to% by weight, based on the total weight of the agent, unless stated otherwise. Furthermore, quantities which relate to at least one component always relate to the total amount of this type of component which is contained in the composition, unless explicitly stated otherwise. This means that such quantities, for example in combination with at least one nonionic surfactant, refer to the total amount of nonionic surfactants contained in the product.
„Mindestens ein“, wie hierin verwendet, bezieht sich auf 1 oder mehr, beispielsweise 1 , 2, 3, 4, 5, 6, 7, 8, 9 oder mehr. Im Zusammenhang mit Bestandteilen der hierin beschriebenen Zusammensetzungen bezieht sich diese Angabe nicht auf die absolute Menge an Molekülen sondern auf die Art des Bestandteils.„Mindestens ein nichtionisches Tensid“ bedeutet daher beispielsweise ein oder mehrere verschiedene nichtionische Tenside, das heißt eine oder mehrere verschiedene Arten von nichtionischen Tensiden. Zusammen mit Mengenangaben beziehen sich die Mengenangaben auf die Gesamtmenge der entsprechend bezeichneten Art von Bestandteil, wie bereits oben definiert. “At least one,” as used herein, refers to 1 or more, for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In connection with components of the compositions described herein, this information does not refer to the absolute amount of molecules but to the type of component. "At least one nonionic surfactant" therefore means, for example, one or more different nonionic surfactants, that is to say one or more different types of nonionic surfactants. Together with quantity information, the quantity information relates to the total quantity of the correspondingly designated type of constituent, as already defined above.
Das flüssige Wasch- oder Reinigungsmittel gemäß der vorliegenden Erfindung enthält bevorzugt 1 Gew.-% bis 60 Gew.-%, vorzugsweise 5 Gew.-% bis 45 Gew.-% und, insbesondere wenn es sich um ein Waschmittel handelt, 15 Gew.-% bis 40 Gew.-% mindestens eines Tensides. The liquid detergent or cleaning agent according to the present invention preferably contains 1% by weight to 60% by weight, preferably 5% by weight to 45% by weight and, in particular if it is a detergent, 15% by weight. % to 40% by weight of at least one surfactant.
Einsetzbare nichtionische Tenside umfassen alle bekannten, in Wasch- oder Reinigungsmitteln üblicherweise eingesetzten nichtionische Tenside, insbesondere solche, die ausgewählt sind aus der Gruppe bestehend aus Alkylglykolethern, alkoxylierten Fettalkoholen, alkoxylierten Oxo-Alkoholen, alkoxylierten Fettsäurealkylestern, Fettsäureamiden, alkoxylierten Fettsäureamiden, Polyhydroxy- fettsäureamiden, Alkylphenolpolyglycolethern, Aminoxiden, Alkyl(poly)glucosiden und Mischungen daraus. In einer bevorzugten Ausführungsform der Erfindung enthalten die Mittel als nichtionisches Tensid mindestens ein Fettalkoholalkoxylat der nachstehenden Formel Usable nonionic surfactants include all known nonionic surfactants commonly used in detergents or cleaning agents, especially those selected from the group consisting of alkyl glycol ethers, alkoxylated fatty alcohols, alkoxylated oxo alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, Alkylphenol polyglycol ethers, amine oxides, alkyl (poly) glucosides and mixtures thereof. In a preferred embodiment of the invention, the agents contain at least one fatty alcohol alkoxylate of the formula below as the nonionic surfactant
R1-0-(AO)m-H, in der R1 ein linearer oder verzweigter, substituierter oder unsubstituierter Alkylrest ist, AO eine Ethylenoxid- (EO) oder Propylenoxid- (PO) Gruppierung ist und m eine ganze Zahl von 1 bis 50 ist. In einer bevorzugten Ausführungsform der vorliegenden Erfindung ist R1 ein linearer oder verzweigter Alkylrest mit 5 bis 30 C-Atomen, vorzugsweise mit 7 bis 25 C-Atomen und insbesondere mit 10 bis 19 C-Atomen. Bevorzugte Reste R1 sind ausgewählt aus Decyl-, Undecyl-, Dodecyl-, Tridecyl-, Tetradecyl, Pentadecyl-, Hexadecyl-, Heptadecyl-, Octadecyl-, Nonadecylresten und deren Mischungen, wobei die Vertreter mit gerader Anzahl an C-Atomen bevorzugt sind. Besonders bevorzugte Reste R1 sind abgeleitet von Fettalkoholen mit 12 bis 19 C-Atomen, beispielsweise von Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder von Oxoalkoholen mit 10 bis 19 C-Atomen. AO ist eine Ethylenoxid- (EO) oder Propylenoxid- (PO) Gruppierung, vorzugsweise eine Ethylenoxidgruppierung. Der Index m ist eine ganze Zahl von 1 bis 50, vorzugsweise 2 bis 20 und bevorzugt 2 bis 10. Insbesondere ist m 3, 4, 5, 6 oder 7. Das erfindungsgemäße Mittel kann Mischungen von nichtionischen Tensiden enthalten, die verschiedene Ethoxylierungsgrade aufweisen. Bevorzugt sind Tenside mit Alkoxylierungs-/Ethoxylierungsgraden von mindestens 5. Zusammenfassend sind besonders bevorzugte Fettalkoholalkoxylate solche der Formel
mit k = 9 bis 17, m = 3, 4, 5, 6, oder 7. Ganz besonders bevorzugte Vertreter sind Fettalkohole mit 10 bis 18 C-Atomen und mit 7 EO (k = 1 1-17, m = 7). Solche Fettalkoholethoxylate sind unter den Verkaufsbezeichnungen Dehydol® LT7 (BASF SE), Lutensol® A07 (BASF SE), Lutensol® M7 (BASF SE) und Neodol® 45-7 (Shell Chemicals) erhältlich. Die oben genannten Fettalkoholethoxylate haben vorzugsweise Ethoxylierungsgrade von mindestens 5, vorzugsweise 7. Derartige Fettalkoholethoxylate können allein, als Mischungen solcher Fettalkoholethoxylate oder auch als Mischungen mit niedriger ethoxylierten Fettalkoholethoxylaten, wie beispielsweise Lutensol® A03 (BASF), eingesetzt werden. In solchen Mischungen ist es bevorzugt, dass die Fettalkoholethoxylate mit Ethoxylierungsgraden von mindestens 5, vorzugsweise 7, mindestens 50 Gew.-%, vorzugsweise mindestens 75 Gew.-% der Gesamtmenge an Fettalkoholethoxylaten ausmachen. R 1 -0- (AO) mH, in which R 1 is a linear or branched, substituted or unsubstituted alkyl radical, AO is an ethylene oxide (EO) or propylene oxide (PO) group and m is an integer from 1 to 50 , In a preferred embodiment of the present invention R 1 is a linear or branched alkyl radical having 5 to 30 C atoms, preferably with from 7 to 25 carbon atoms and especially with 10 to 19 carbon atoms. Preferred radicals R 1 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl radicals and mixtures thereof, the representatives with an even number of carbon atoms being preferred , Particularly preferred R 1 radicals are derived from fatty alcohols having 12 to 19 carbon atoms, for example coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or oxo alcohols having 10 to 19 carbon atoms. AO is an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group. The index m is an integer from 1 to 50, preferably 2 to 20 and preferably 2 to 10. In particular, m is 3, 4, 5, 6 or 7. The agent according to the invention can contain mixtures of nonionic surfactants which have different degrees of ethoxylation. Surfactants with degrees of alkoxylation / ethoxylation of at least 5 are preferred. In summary, particularly preferred fatty alcohol alkoxylates are those of the formula with k = 9 to 17, m = 3, 4, 5, 6, or 7. Very particularly preferred representatives are fatty alcohols with 10 to 18 carbon atoms and with 7 EO (k = 1 1-17, m = 7). Such fatty alcohol ethoxylates are available under the trade names Dehydol LT7 ® (BASF SE), Lutensol ® A07 (BASF SE), Lutensol ® M7 (BASF SE) and Neodol ® 45-7 (Shell Chemicals). The fatty alcohol ethoxylates mentioned above preferably have degrees of ethoxylation of at least 5, preferably 7. Such fatty alcohol ethoxylates can be used alone, as mixtures of such fatty alcohol ethoxylates or as mixtures with low-ethoxylated fatty alcohol ethoxylates such as Lutensol ® A03 (BASF) may be used. In such mixtures it is preferred that the fatty alcohol ethoxylates with degrees of ethoxylation of at least 5, preferably 7, at least 50% by weight, preferably at least 75% by weight make up the total amount of fatty alcohol ethoxylates.
Weitere nichtionische Tenside, die im Sinne der vorliegenden Erfindung in den Mitteln enthalten sein können, schließen ein, sind aber nicht beschränkt auf Alkyl(poly)glykoside, alkoxylierte Fettsäurealkylester, Fettsäurealkanolamide, Hydroxymischether, Sorbitanfettsäurester und Polyhydro- xyfettsäureamide. Geeignete Alkyl(poly)glykoside sind beispielsweise solche der Formel R20-[G]P, in der R2 ein es oder verzweigtes Alkyl mit 12 bis 16 Kohlenstoffatomen, G ein Zuckerrest mit 5 oder 6 Kohlenstoffatomen, insbesondere Glucose, und der Index p 1 bis 10 ist. Diese können beispielsweise in Mengen bis zu 5 Gew.-% in dem Mittel enthalten sein. Further nonionic surfactants which can be contained in the agents for the purposes of the present invention include, but are not limited to, alkyl (poly) glycosides, alkoxylated fatty acid alkyl esters, fatty acid alkanolamides, hydroxy mixed ethers, sorbitan fatty acid esters and polyhydroxy fatty acid amides. Suitable alkyl (poly) glycosides are, for example, those of the formula R 2 0- [G] P , in which R 2 is a branched or branched alkyl having 12 to 16 carbon atoms, G is a sugar residue with 5 or 6 carbon atoms, in particular glucose, and the index p is 1 to 10. These can be contained in the agent for example in amounts of up to 5% by weight.
Ferner enthält das flüssige Mittel nach der vorliegenden Erfindung vorzugsweise 1 Gew.-% bis 30 Gew.-%, insbesondere 2 Gew.-% bis 20 Gew.-% und besonders bevorzugt mindestens 10 Gew.-% mindestens eines anionischen Tensids. Die anionischen Tenside sind vorzugsweise Tenside aus der Gruppe der Sulfonate, insbesondere Alkylbenzolsulfonate und/oder sekundäre Alkansulfonate. In einer Ausführungsform umfasst das erfindungsgemäße Mittel mindestens ein sekundäres Alkan- sulfonat. Das mindestens eine sekundäre Alkansulfonat kann jedes bekannte und für den erfindungsgemäßen Zweck geeignete sekundäre Alkansulfonat sein. Sekundär bezieht sich dabei auf die allgemein bekannte, chemische Bedeutung dieses Begriffs, und zeigt an, dass das Kohlenstoffatom, an das die Sulfonat-Gruppe kovalent gebunden ist, weiterhin zwei kovalente Bindungen zu zwei organischen Resten, und eine kovalente Bindung zu einem Wasserstoffatom aufweist. Gemeinsam mit dem Kohlenstoffatom, an das sie gebunden sind, bilden die zwei organischen Reste eine lineare oder verzweigte Alkylgruppe mit 1 bis 50 Kohlenstoffatomen. Um die negative Ladung der Sulfonat-Gruppe auszugleichen, umfasst das Alkansulfonat ferner ein beliebiges Kation, vorzugsweise ausgewählt aus der Gruppe Na+, K+, NFLF, 1 Zn2+, 14 Mg2+, 14 Ca2+, 14 Mn2+ und deren Mischungen, besonders bevorzugt Na+. Alternativ kann in verschiedenen Ausführungsformen auch die korrespondierende Säure eingesetzt werden, das heißt das Kation ist H+. In einer bevorzugten Ausführungsform der vorliegenden Erfindung weist das mindestens eine sekundäre Alkansulfonat die Formel
R1CH(S03 X+) R2 auf, wobei jeweils R1 und R2 unabhängig ein lineares oder verzweigtes Alkyl mit 1 bis 20 Kohlenstoffatomen ist und mit dem Kohlenstoffatom, an das sie gebunden sind, eine lineare oder verzweigte Alkylgruppe bilden, vorzugsweise mit 10 bis 30 Kohlenstoffatomen, bevorzugt mit 10 bis 20 Kohlenstoffatomen, und X+ ausgewählt ist aus der Gruppe Na+, K+, NH4 +, 1 Zn2+, 14 Mg2+, 14 Ca2+, 14 Mn2+ und deren Mischungen, bevorzugt Na+. Wie bereits oben erwähnt, kann in verschiedenen Ausführungsformen X+ auch H+ sein. In einer noch weiteren bevorzugten Ausführungsform weist das mindestens eine sekundäre Alkansulfonat die nachstehende Formel Furthermore, the liquid composition according to the present invention preferably contains 1% by weight to 30% by weight, in particular 2% by weight to 20% by weight and particularly preferably at least 10% by weight of at least one anionic surfactant. The anionic surfactants are preferably surfactants from the group of the sulfonates, in particular alkylbenzenesulfonates and / or secondary alkanesulfonates. In one embodiment, the agent according to the invention comprises at least one secondary alkane sulfonate. The at least one secondary alkanesulfonate can be any known secondary alkanesulfonate which is suitable for the purpose according to the invention. Secondary refers to the well-known chemical meaning of this term, and indicates that the carbon atom to which the sulfonate group is covalently bonded still has two covalent bonds to two organic radicals and one covalent bond to a hydrogen atom. Together with the carbon atom to which they are attached, the two organic radicals form a linear or branched alkyl group with 1 to 50 carbon atoms. In order to balance the negative charge of the sulfonate group, the alkanesulfonate further comprises any cation, preferably selected from the group Na + , K + , NFLF, 1 Zn 2+ , 14 Mg 2+ , 14 Ca 2+ , 14 Mn 2+ and their mixtures, particularly preferably Na + . Alternatively, the corresponding acid can also be used in various embodiments, ie the cation is H + . In a preferred embodiment of the present invention, the at least one secondary alkanesulfonate has the formula R 1 CH (S0 3 X + ) R 2 , where each R 1 and R 2 is independently a linear or branched alkyl having 1 to 20 carbon atoms and forms a linear or branched alkyl group with the carbon atom to which they are attached, preferably having 10 to 30 carbon atoms, preferably having 10 to 20 carbon atoms, and X + is selected from the group Na + , K + , NH 4 + , 1 Zn 2+ , 14 Mg 2+ , 14 Ca 2+ , 14 Mn 2 + and their mixtures, preferably Na + . As already mentioned above, X + can also be H + in various embodiments. In yet another preferred embodiment, the at least one secondary alkanesulfonate has the formula below
H3C-(CH2)n-CH(S03 X+)-(CH2)m-CH3 auf, wobei m und n unabhängig voneinander eine ganze Zahl zwischen 0 und 20 sind. Vorzugsweise ist m + n eine ganze Zahl zwischen 7 und 17, bevorzugt 10 bis 14 und X+ ist ausgewählt aus der Gruppe Na+, K+, NH4 +, 14 Zn2+, 14 Mg2+, 14 Ca2+, 14 Mn2+ und deren Mischungen, bevorzugt Na+. Wie bereits oben erwähnt, kann in verschiedenen Ausführungsformen X+ auch H+ sein. In einer besonders bevorzugten Ausführungsform ist das mindestens eine sekundäre Alkansulfonat sekundäres C 14-17 Natriumalkansulfonat oder die korrespondierende Säure. Ein derartiges sekundäres C14-17 Natriumalkansulfonat wird beispielsweise von der Firma Clariant unter dem Handelsnamen„Hosta- pur SAS60“ vertrieben. Es sei an dieser Stelle ausdrücklich darauf hingewiesen, dass im hierin beschriebenen Mittel mehrere sekundäre Alkansulfonate enthalten sein können. H3C- (CH2) n-CH (S03 X + ) - (CH2) m-CH3, where m and n are independently an integer between 0 and 20. M + n is preferably an integer between 7 and 17, preferably 10 to 14 and X + is selected from the group Na + , K + , NH 4 + , 14 Zn 2+ , 14 Mg 2+ , 14 Ca 2+ , 14 Mn 2+ and mixtures thereof, preferably Na + . As already mentioned above, X + can also be H + in various embodiments. In a particularly preferred embodiment, the at least one secondary alkanesulfonate is secondary C 14-1 7 sodium alkanesulfonate or the corresponding acid. Such a secondary C14-17 sodium alkane sulfonate is sold, for example, by the Clariant company under the trade name "Hostapur SAS60". At this point, it should be expressly pointed out that the agent described here may contain several secondary alkanesulfonates.
Des Weiteren enthält das hierin beschriebene Mittel in verschiedenen Ausführungsformen andere anionische Tenside, die alternativ oder zusätzlich zu den sekundären Alkansulfonaten eingesetzt werden können. Vorzugsweise schließen derartige anionische Tenside Alkylbenzolsulfonate ein. Alkylbenzolsulfonate sind vorzugsweise ausgewählt aus linearen oder verzweigten Alkylbenzolsul- fonaten der Formel Furthermore, in various embodiments, the agent described herein contains other anionic surfactants that can be used as an alternative or in addition to the secondary alkanesulfonates. Such anionic surfactants preferably include alkylbenzenesulfonates. Alkylbenzenesulfonates are preferably selected from linear or branched alkylbenzenesulfonates of the formula
Na
in der R' und R" unabhängig Wasserstoff oder Alkyl sind und zusammen 9 bis 19, vorzugsweise 9 bis 15 und insbesondere 9 bis 13 Kohlenstoffatome enthalten. Ein ganz besonders bevorzugter Vertreter ist Natriumdodecylbenzolsulfonat oder die korrespondierende Säure (HLAS). In anderen Ausführungsformen kann Na+ durch ein Kation ausgewählt aus K+, NH4 +, 14 Zn2+,14 Mg2+,14 Ca2+,14 Mn2+ und deren Mischungen oder auch durch H+ (korrespondierende Säure) ersetzt sein. In bevorzugten Ausführungsformen werden die oben beschriebenen sekundären Alkansulfonate und Alkylbenzolsulfonate in Kombination eingesetzt, insbesondere im Gewichtsverhältnis von 2:1 bis 1 :2,
vorzugsweise 1 : 1. Dabei ist es besonders bevorzugt, die Alkylbenzolsulfonate in der Säureform einzusetzen. N / A in which R ' and R "are independently hydrogen or alkyl and together contain 9 to 19, preferably 9 to 15 and in particular 9 to 13 carbon atoms. A very particularly preferred representative is sodium dodecylbenzenesulfonate or the corresponding acid (HLAS). In other embodiments, Na + can be replaced by a cation selected from K + , NH 4 + , 14 Zn 2+ , 14 Mg 2+ , 14 Ca 2+ , 14 Mn 2+ and mixtures thereof or by H + (corresponding acid) in preferred embodiments the secondary alkanesulfonates and alkylbenzenesulfonates described above are used in combination, in particular in a weight ratio of 2: 1 to 1: 2, preferably 1: 1. It is particularly preferred to use the alkylbenzenesulfonates in the acid form.
Schließlich können die Mittel auch weitere anionische Tenside, wie beispielsweise Alkylethersulfate enthalten. Bevorzugt sind Fettalkoholethersulfate der nachstehenden Formel Finally, the agents can also contain other anionic surfactants, such as, for example, alkyl ether sulfates. Fatty alcohol ether sulfates of the formula below are preferred
R4-0-( AO )n-S03 X+ (V), wobei R4 eine lineare oder verzweigte substituierte oder unsubstituierte Alkylgruppe mit 5 bis 30 Kohlenstoffatomen, vorzugsweise mit 7 bis 25 Kohlenstoffatomen und bevorzugt mit 10 bis 19 Kohlenstoffatomen ist. Des Weiteren steht AO in der obigen Formel für eine Ethylenoxid- (EO) oder Propylenoxid- (PO) Gruppierung, vorzugsweise eine Ethylenoxid- (EO) Gruppierung und n für eine ganze Zahl von 1 bis 50, vorzugsweise von 1 bis 20 und bevorzugt von 2 bis 10 ist. X+ ist ein beliebiges Kation und ist vorzugsweise ausgewählt aus der Gruppe Na+, K+, NH4 +, 1 Zn2+,1 Mg2+,1 Ca2+,1 Mn2 und deren Mischungen, besonders bevorzugt Na+. In einer bevorzugten Ausführungsform ist R4 ein linearer oder verzweigter Alkylrest mit 5 bis 30 Kohlenstoffatomen, vorzugsweise mit 7 bis 25 Kohlenstoffatomen und insbesondere mit 10 bis 19 Kohlenstoffatomen. Bevorzugte Reste R4 sind ausgewählt aus Decyl-, Undecyl-, Dodecyl-, Tridecyl-, Tetradecyl, Pentadecyl-, Hexadecyl-, Heptadecyl-, Octadecyl-, Nonadecylresten und deren Mischungen, wobei die Vertreter mit gerader Anzahl an Kohlenstoffatomen bevorzugt sind. Besonders bevorzugte Reste R4 sind abgeleitet von Fettalkoholen mit 12 bis 19 Kohlenstoffatomen, beispielsweise von Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder von Oxoalkoholen mit 10 bis 19 Kohlenstoffatomen. Das Mittel kann Mischungen von Tensiden enthalten, die verschiedene Alkoxylierungsgrade n aufweisen. Das eingesetzte Fettalkoholethersulfat kann auch eines der Formel
sein, wobei k = 1 1 bis 19, n = 2, 3, 4, 5, 6, 7 oder 8 ist. Ganz besonders bevorzugte Vertreter sind Na Fettalkoholethersulfate mit 12 bis 18 Kohlenstoffatomen und 2 EO (k = 1 1 bis 13, n = 2). Der angegebenen Ethoxylierungsgrad n stellt einen statistischen Mittelwert dar, der für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein kann. Allgemein stellen die angegebenen Alkoxylierungsgrade statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoxylate/Ethoxylate weisen eine eingeengte Homologenverteilung auf (narrow ränge ethoxylates, NRE). R 4 -0- (AO) n -S0 3 X + (V), where R 4 is a linear or branched substituted or unsubstituted alkyl group having 5 to 30 carbon atoms, preferably having 7 to 25 carbon atoms and preferably having 10 to 19 carbon atoms. Furthermore, AO in the above formula represents an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide (EO) group and n is an integer from 1 to 50, preferably from 1 to 20 and preferably from Is 2 to 10. X + is any cation and is preferably selected from the group Na + , K + , NH 4 + , 1 Zn 2+ , 1 Mg 2+ , 1 Ca 2+ , 1 Mn 2 and mixtures thereof, particularly preferably Na + . In a preferred embodiment, R 4 is a linear or branched alkyl radical having 5 to 30 carbon atoms, preferably with from 7 to 25 carbon atoms and especially with 10 to 19 carbon atoms. Preferred R 4 radicals are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl radicals and mixtures thereof, the representatives having an even number of carbon atoms being preferred. Particularly preferred radicals R 4 are derived from fatty alcohols with 12 to 19 carbon atoms, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from oxo alcohols with 10 to 19 carbon atoms. The agent can contain mixtures of surfactants which have different degrees of alkoxylation n. The fatty alcohol ether sulfate used can also be one of the formula be, where k = 1 1 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are Na fatty alcohol ether sulfates with 12 to 18 carbon atoms and 2 EO (k = 1 1 to 13, n = 2). The indicated degree of ethoxylation n represents a statistical mean, which can be an integer or a fraction for a specific product. In general, the degrees of alkoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alkoxylates / ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
Überdies kann das flüssige Mittel, insbesondere wenn es sich um ein Waschmittel handelt mindestens eine Fettsäure enthalten. Der Begriff„Fettsäure“ wie hierin verwendet bezieht sich auf verzweigte oder unverzweigte Carbonsäuren und deren Salze, die sogenannten Seifen, mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen. Die Fettsäureseifen können in Form ihrer Natrium-,
Kalium- oder Magnesium- oder Ammoniumsalze vorliegen. In verseifter Form liegen sie vorzugsweise in Form ihrer Natriumsalze und/oder Ammoniumsalze vor. Zur Neutralisation ersetzbare Amine sind vorzugsweise Cholin, Triethylamin, Monoethanolamin, Diethanolamin, Triethanolamin, Methylethylamin oder eine Mischung daraus, wobei Monoethanolamin bevorzugt ist. In verschiedenen Ausführungsformen werden die Fettsäuren als solche, das heißt nicht verseift, eingesetzt. Dabei können sie beispielsweise in einem oder mehreren Bestandteilen des Mittels, vorzugsweise dem mindestens einen nichtionischen Tensid gelöst und in dieser gelösten Form mit den übrigen Bestandteilen des Mittels kombiniert werden. In dem finalen Produkt kann die Fettsäure emulgiert vorliegen. In addition, the liquid agent, especially if it is a detergent, can contain at least one fatty acid. The term “fatty acid” as used herein refers to branched or unbranched carboxylic acids and their salts, the so-called soaps, having 6 to 22, preferably 12 to 18, carbon atoms. The fatty acid soaps can be in the form of their sodium, Potassium or magnesium or ammonium salts are present. In saponified form, they are preferably in the form of their sodium salts and / or ammonium salts. Amines which can be replaced for neutralization are preferably choline, triethylamine, monoethanolamine, diethanolamine, triethanolamine, methylethylamine or a mixture thereof, monoethanolamine being preferred. In various embodiments, the fatty acids are used as such, ie not saponified. They can be dissolved, for example, in one or more components of the composition, preferably the at least one nonionic surfactant, and combined in this dissolved form with the other components of the composition. The fatty acid can be emulsified in the final product.
Ferner enthalten bevorzugte Flüssigwaschmittel Wasser als Lösungsmittel. In Ausführungsformen der Erfindung enthalten die Mittel 4 Gew.-% bis 25 Gew.-%, insbesondere 6 Gew.-% bis 15 Gew.-% Wasser; in anderen Ausführungsformen der Erfindung enthalten die Mittel mehr als 25 Gew.-% und bis zu 90 Gew.-% Wasser, insbesondere 35 Gew.-% bis 65 Gew.-% Wasser. Die flüssigen Mittel können zusätzlich ein oder mehrere nichtwässrige, organische Lösungsmittel enthalten. Geeignete nichtwässrige Lösungsmittel umfassen ein- oder mehrwertige Alkohole, Alkanolamine oder Glykolether. Vorzugsweise werden die Lösungsmittel ausgewählt aus Ethanol, n-Propanol, i-Propa- nol, Butanolen, Glykol, Propandiol, Butandiol, Methylpropandiol, Glycerin, Glykolen, wie Diglykol, Propyldiglycol, Butyldiglykol, Hexylenglycol, Ethylenglykolmethylether, Ethylenglykolethylether, Ethylenglykolpropylether, Ethylenglykolmono-n-butylether, Diethylenglykolmethylether, Diethyl- englykolethylether, Propylenglykolmethylether, Propylenglykolethylether, Propylenglykolpropylether, Dipropylenglykolmonomethylether, Dipropylenglykolmonoethylether, Methoxytriglykol,Preferred liquid detergents also contain water as a solvent. In embodiments of the invention, the compositions contain 4% by weight to 25% by weight, in particular 6% by weight to 15% by weight, of water; in other embodiments of the invention, the agents contain more than 25% by weight and up to 90% by weight of water, in particular 35% by weight to 65% by weight of water. The liquid compositions can additionally contain one or more non-aqueous, organic solvents. Suitable non-aqueous solvents include monohydric or polyhydric alcohols, alkanolamines or glycol ethers. The solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, glycols, such as diglycol, propyldiglycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol monoxide -butyl ether, diethylene glycol methyl ether, diethyl englycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol,
Ethoxytriglykol, Butoxytriglykol, 1-Butoxyethoxy-2-propanol, 3-Methyl-3-methoxybutanol, Propylen- glykol-t-butylether, Di-n-octylether sowie niedermolekularen Polyalkylenglykolen, wie PEG 400, sowie deren Mischungen. In einer bevorzugten Ausführungsform wird das nichtwässrige Lösungsmittel ausgewählt aus der Gruppe bestehend aus Ethanol, n-Propanol, i-Propanol, Butanolen, Glykol, Propandiol, Butandiol, Methylpropandiol, Glycerin und deren Mischungen. In einer bevorzugten Ausführungsform enthält das nichtwässrige Lösungsmittel 1 ,2-Propandiol, Glycerin oder eine Mischung davon, ganz besonders bevorzugt Glycerin. Ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and low molecular weight polyalkylene glycols, such as PEG 400, and mixtures thereof. In a preferred embodiment, the non-aqueous solvent is selected from the group consisting of ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol and mixtures thereof. In a preferred embodiment, the non-aqueous solvent contains 1, 2-propanediol, glycerin or a mixture thereof, very particularly preferably glycerin.
Die erfindungsgemäßen Mittel weisen vorzugsweise eine Viskosität (Brookfield Rotationsviskosimeter; dem Viskositätsbereich angepasste Spindel) im Bereich von 1 mPa.s bis 1000 mPa.s, insbesondere von 5 mPa.s bis 500 mPa.s auf. Ein erfindungsgemäßes Mittel ist ferner vorzugsweise transluzent, insbesondere transparent, das heißt es weist keine optisch wahrnehmbaren Trübungen auf. The agents according to the invention preferably have a viscosity (Brookfield rotational viscometer; spindle adapted to the viscosity range) in the range from 1 mPa.s to 1000 mPa.s, in particular from 5 mPa.s to 500 mPa.s. An agent according to the invention is also preferably translucent, in particular transparent, that is to say it has no optically perceptible cloudiness.
Generell kann der pH-Wert des Flüssigwaschmittels gemäß der Erfindung mittels üblicher pH-Re- gulatoren eingestellt werden und liegt vorzugsweise im Bereich von pH 5 bis pH 10, insbesondere von pH 7 bis pH 9; diese beziehen sich auf den pH-Wert einer 1 %igen (Gew.-%) Lösung des Mittels in destilliertem Wasser bei 30 °C.
Geeignete pH-Stellmittel schließen Säuren und/oder Alkalien ein. Geeignete Säuren sind organische Säuren wie die Essigsäure, Glycolsäure, Milchsäure, Bernsteinsäure, Adipinsäure, Äpfelsäure, Weinsäure und Gluconsäure oder auch Amidosulfonsäure. Daneben können aber auch die Mineralsäuren Salzsäure, Schwefelsäure und Salpetersäure bzw. deren Mischungen eingesetzt werden. Geeignete Basen stammen aus der Gruppe der Alkali- und Erdalkalimetallhydroxide und - carbonate, insbesondere der Alkalimetallhydroxide, von denen Kaliumhydroxid und vor allem Natriumhydroxid bevorzugt ist. Auch flüchtiges Alkali kann verwendet werden, beispielsweise in Form von Ammoniak und/oder Alkanolaminen, die bis zu 9 C-Atome im Molekül enthalten können. Das Alkanolamin ist hierbei vorzugsweise ausgewählt aus der Gruppe bestehend aus Mono-, Di-, Triethanol- und -propanolamin und deren Mischungen. In general, the pH of the liquid detergent according to the invention can be adjusted using conventional pH regulators and is preferably in the range from pH 5 to pH 10, in particular from pH 7 to pH 9; these relate to the pH of a 1% (% by weight) solution of the agent in distilled water at 30 ° C. Suitable pH adjusters include acids and / or alkalis. Suitable acids are organic acids such as acetic acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid. In addition, the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof can also be used. Suitable bases come from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is preferred. Volatile alkali can also be used, for example in the form of ammonia and / or alkanolamines, which can contain up to 9 carbon atoms in the molecule. The alkanolamine is preferably selected from the group consisting of mono-, di-, triethanol- and propanolamine and mixtures thereof.
Zusätzlich kann das Mittel weitere Inhaltsstoffe enthalten, die seine anwendungstechnischen und/oder ästhetischen Eigenschaften verbessern. Im Rahmen der vorliegenden Erfindung enthält das Waschmittel vorzugsweise zusätzlich einen oder mehrere Stoffe aus der Gruppe der Enzyme, Gerüststoffe, Komplexbildner, Elektrolyte, Parfüme, Parfümträger, Fluoreszenzmittel, Farbstoffe, Hydrotrope, Schauminhibitoren, Silikonöle, Antiredepositionsmittel, Vergrauungsinhibitoren, Einlaufverhinderer, Knitterschutzmittel, Farbübertragungsinhibitoren, antimikrobielle Wirkstoffe, Germizide, Fungizide, Antioxidantien, Konservierungsmittel, Korrosionsinhibitoren, Antistatika, Bittermittel, Bügelhilfsmittel, Phobier- und Imprägniermittel, Quell- und Schiebefestmittel, weichmachenden Komponenten sowie UV-Absorbern. In addition, the agent may contain other ingredients that improve its application technology and / or aesthetic properties. In the context of the present invention, the detergent preferably additionally contains one or more substances from the group of enzymes, builders, complexing agents, electrolytes, perfumes, perfume carriers, fluorescent agents, dyes, hydrotropes, foam inhibitors, silicone oils, anti-redeposition agents, graying inhibitors, anti-wrinkle inhibitors, anti-crease agents, color transfer inhibitors. antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, phobing and impregnating agents, swelling and anti-slip agents, softening components and UV absorbers.
Die Mittel enthalten vorzugsweise mindestens ein Enzym. Das mindestens eine Enzym kann jedes im Stand der Technik bekannte Enzym sein, das in einem Wasch- oder Reinigungsmittel eine katalytische Aktivität entfalten kann, und umfasst, ohne darauf beschränkt zu sein, beispielsweise Proteasen, Amylasen, Lipasen, Cellulasen, Hemicellulasen, Mannanasen, Pektin-spaltende Enzyme, Tannasen, Xylanasen, Xanthanasen, ß-Glucosidasen, Carrageenasen, Perhydrolasen, Oxidasen, Oxidoreduktasen sowie deren Gemische. In einer bevorzugten Ausführungsform ist das mindestens eine Enzym ausgewählt aus der Gruppe bestehend aus Proteasen, Amylasen, Lipasen, Cellulasen und deren Mischungen. Diese Enzyme sind im Prinzip natürlichen Ursprungs, ausgehend von den natürlichen Molekülen stehen für den Einsatz in Wasch- oder Reinigungsmitteln aber verbesserte Varianten zur Verfügung, die entsprechend bevorzugt eingesetzt werden. The agents preferably contain at least one enzyme. The at least one enzyme can be any enzyme known in the art which can develop a catalytic activity in a washing or cleaning agent and includes, but is not limited to, proteases, amylases, lipases, cellulases, hemicellulases, mannanases, pectin cleaving enzymes, tannases, xylanases, xanthanases, β-glucosidases, carrageenases, perhydrolases, oxidases, oxidoreductases and mixtures thereof. In a preferred embodiment, the at least one enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases and mixtures thereof. In principle, these enzymes are of natural origin, but based on the natural molecules, improved variants are available for use in detergents or cleaning agents, which are accordingly preferred.
Unter den Proteasen sind solche vom Subtilisin-Typ bevorzugt. Beispiele hierfür sind die Subtilisine BPN' und Carlsberg, 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. Subtilisin Carlsberg ist in weiterentwickelter Form unter dem Handelsnamen Alcalase® von der Firma No- vozymes A/S, Bagsvaerd, Dänemark, erhältlich. Die Subtilisine 147 und 309 werden unter den Handelsnamen Esperase®, beziehungsweise Savinase® von der Firma Novozymes vertrieben. Von der Protease aus Bacillus lentus DSM 5483 leiten sich die unter der Bezeichnung BLAP® geführten
Protease-Varianten ab. Weitere brauchbare Proteasen sind beispielsweise die unter den Handelsnamen Durazym®, Relase®, Everlase®, Nafizym®, Natalase®, Kannase® und Ovozyme® von der Firma Novozymes, die unter den Handelsnamen, Purafect®, Purafect® OxP, Purafect® Prime, Excellase® und Properase® von der Firma Genencor, das unter dem Handelsnamen Protosol® von der Firma Advanced Biochemicals Ltd., Thane, Indien, das unter dem Handelsnamen Wuxi® von der Firma Wuxi Snyder Bioproducts Ltd., China, die unter den Handelsnamen Proleather® und Protease P® von der Firma Amano Pharmaceuticals Ltd., Nagoya, Japan, und das unter der Bezeichnung Proteinase K-16 von der Firma Kao Corp., Tokyo, Japan, erhältlichen Enzyme. Besonders bevorzugt eingesetzt werden auch die Proteasen aus Bacillus gibsonii und Bacillus pumilus. Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the enzyme which can no longer be assigned to the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase® and Savinase® by Novozymes. The protease from Bacillus lentus DSM 5483 is derived from those listed under the name BLAP® Protease variants. Further usable proteases are, for example, those under the trade names Durazym®, Relase®, Everlase®, Nafizym®, Natalase®, Kannase® and Ovozyme® from Novozymes, which under the trade names, Purafect®, Purafect® OxP, Purafect® Prime, Excellase® and Properase® from Genencor, which under the trade name Protosol® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi® from Wuxi Snyder Bioproducts Ltd., China, under the trade name Proleather ® and Protease P® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzymes available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan. The proteases from Bacillus gibsonii and Bacillus pumilus are also used with particular preference.
Beispiele für Amylasen sind die a-Amylasen aus Bacillus licheniformis, aus B. amyloliquefaciens oder aus B. stearothermophilus sowie deren für den Einsatz in Wasch- oder Reinigungsmitteln verbesserte Weiterentwicklungen. Das Enzym aus B. licheniformis ist von der Firma Novozymes unter dem Namen Termamyl® und von der Firma Genencor unter dem Namen Purasta DST erhältlich. Weiterentwicklungsprodukte dieser a- Amylase sind von der Firma Novozymes unter den Handelsnamen Duramyl® und TermamyKDultra, von der Firma Genencor unter dem Namen Purasta DOxAm und von der Firma Daiwa Seiko Inc., Tokyo, Japan, als Keistase® erhältlich. Die a-Amylase von B. amyloliquefaciens wird von der Firma Novozymes unter dem Namen BAN® vertrieben, und abgeleitete Varianten von der a- Amylase aus B. stearothermophilus unter den Namen BSG® und No- vamyl®, ebenfalls von der Firma Novozymes. Des Weiteren sind für diesen Zweck die a-Amylase aus Bacillus sp. A 7-7 (DSM 12368) und die Cyclodextrin-Glucanotransferase (CGTase) aus B. aga- radherens (DSM 9948) hervorzuheben. Ebenso sind Fusionsprodukte aller genannten Moleküle ein- setzbar. Darüber hinaus sind die unter den Handelsnamen Fungamyl® von dem Unternehmen Novozymes erhältlichen Weiterentwicklungen der a-Amylase aus Aspergillus niger und A. oryzae geeignet. Weitere vorteilhaft einsetzbare Handelsprodukte sind beispielsweise die Amylase-LT® und Stainzyme® oder Stainzyme ultra® oder Stainzyme plus®, letztere ebenfalls von dem Unternehmen Novozymes. Auch durch Punktmutationen erhältliche Varianten dieser Enzyme können erfindungsgemäß eingesetzt werden. Examples of amylases are the a-amylases from Bacillus licheniformis, from B. amyloliquefaciens or from B. stearothermophilus and their further developments for use in detergents or cleaning agents. The enzyme from B. licheniformis is available from Novozymes under the name Termamyl® and from Genencor under the name Purasta DST. Further development products of this a-amylase are available from Novozymes under the trade names Duramyl® and TermamyKDultra, from Genencor under the name Purasta DOxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase®. The a-amylase from B. amyloliquefaciens is sold by Novozymes under the name BAN®, and derived variants from the a-amylase from B. stearothermophilus under the names BSG® and Novamyl®, also from Novozymes. Furthermore, the a-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948). Fusion products of all of the molecules mentioned can also be used. In addition, the further developments of the a-amylase from Aspergillus niger and A. oryzae available under the trade names Fungamyl® from the company Novozymes are suitable. Other commercial products that can be used advantageously include the Amylase-LT® and Stainzyme® or Stainzyme ultra® or Stainzyme plus®, the latter also from Novozymes. Variants of these enzymes obtainable by point mutations can also be used according to the invention.
Beispiele für verwendbare Lipasen oder Cutinasen, die insbesondere wegen ihrer Triglycerid-spal- tenden Aktivitäten enthalten sind, sind die ursprünglich aus Humicola lanuginosa (Thermomyces la- nuginosus) erhältlichen, beziehungsweise weiterentwickelten Lipasen, insbesondere solche mit dem Aminosäureaustausch D96L. Sie werden beispielsweise von der Firma Novozymes unter den Handelsnamen Lipolase®, Lipolase®Ultra, LipoPrime®, Lipozyme® und Lipex® vertrieben. Des Weiteren sind beispielsweise die Cutinasen einsetzbar, die ursprünglich aus Fusarium solani pisi und Humicola insolens isoliert worden sind. Ebenso brauchbare Lipasen sind von der Firma Amano unter den Bezeichnungen Lipase CE®, Lipase P®, Lipase B®, beziehungsweise Lipase CES®, Lipase AKG®, Bacillus sp. Lipase®, Lipase AP®, Lipase M-AP® und Lipase AML® erhältlich. Von der Firma Genencor sind beispielsweise die Lipasen beziehungsweise Cutinasen einsetzbar, deren Ausgangsenzyme ursprünglich aus Pseudomonas mendocina und Fusarium solanii isoliert worden sind.
Als weitere wichtige Handelsprodukte sind die ursprünglich von der Firma Gist-Brocades vertriebenen Präparationen M1 Lipase® und Lipomax® und die von der Firma Meito Sangyo KK, Japan, unter den Namen Lipase MY-30®, Lipase OF® und Lipase PL® vertriebenen Enzyme zu erwähnen, ferner das Produkt Lumafast® von der Firma Genencor. Examples of usable lipases or cutinases which are contained in particular because of their triglyceride-cleaving activities are the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or more developed lipases, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase®, Lipolase®Ultra, LipoPrime®, Lipozyme® and Lipex®. Furthermore, the cutinases, which were originally isolated from Fusarium solani pisi and Humicola insolens, can also be used. Likewise usable lipases are available from Amano under the names Lipase CE®, Lipase P®, Lipase B®, or Lipase CES®, Lipase AKG®, Bacillus sp. Lipase®, Lipase AP®, Lipase M-AP® and Lipase AML® available. The Genencor company can use, for example, the lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products include the M1 Lipase® and Lipomax® preparations originally sold by Gist-Brocades and the enzymes sold by Meito Sangyo KK, Japan, under the names Lipase MY-30®, Lipase OF® and Lipase PL® to mention, also the product Lumafast® from Genencor.
Cellulasen können je nach Zweck als reine Enzyme, als Enzympräparationen oder in Form von Mischungen, in denen sich die einzelnen Komponenten vorteilhafterweise hinsichtlich ihrer verschiedenen Leistungsaspekte ergänzen, vorhanden sein. Zu diesen Leistungsaspekten zählen insbesondere die Beiträge der Cellulase zur Primärwaschleistung des Mittels (Reinigungsleistung), zur Sekundärwaschleistung des Mittels (Antiredepositionswirkung oder Vergrauungsinhibition), zur Avi- vage (Gewebewirkung) oder zur Ausübung eines "stone washed' -Effekts. Eine brauchbare pilzliche, Endoglucanase(EG)-reiche Cellulase-Präparation, beziehungsweise deren Weiterentwicklungen wird von der Firma Novozymes unter dem Handelsnamen Celluzyme® angeboten. Die ebenfalls von der Firma Novozymes erhältlichen Produkte Endolase® und Carezyme® basieren auf der 50 kD-EG, beziehungsweise der 43 kD-EG aus H. insolens DSM 1800. Weitere einsetzbare Handelsprodukte dieser Firma sind Cellusoft®, Renozyme® und Celluclean®. Weiterhin einsetzbar sind beispielsweise die 20 kD-EG aus Melanocarpus, die von der Firma AB Enzymes, Finnland, unter den Handelsnamen Ecostone® und Biotouch® erhältlich sind. Weitere Handelsprodukte der Firma AB Enzymes sind Econase® und Ecopulp®. Weitere geeignete Cellulasen sind aus Bacillus sp. CBS 670.93 und CBS 669.93, wobei die aus Bacillus sp. CBS 670.93 von der Firma Genencor unter dem Handelsnamen Puradax® erhältlich ist. Weitere Handelsprodukte der Firma Genencor sind "Genencor detergent cellulase L" und lndiAge®Neutra. Auch durch Punktmutationen erhältliche Varianten dieser Enzyme können erfindungsgemäß eingesetzt werden. Besonders bevorzugte Cellulasen sind Thielavia terrestris Cellulasevarianten, Cellulasen aus Melanocarpus, insbesondere Melanocarpus albomyces, Cellulasen vom EGIII-Typ aus Trichoderma reesei oder hieraus erhältliche Varianten. Depending on the purpose, cellulases can be present as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously complement one another with regard to their various performance aspects. These performance aspects include, in particular, the contributions of cellulase to the primary washing performance of the agent (cleaning performance), to the secondary washing performance of the agent (anti-redeposition or graying inhibition), to avivage (tissue effect) or to the exercise of a "stone washed" effect. A useful fungal endoglucanase (EG) -rich cellulase preparation and its further developments are offered by Novozymes under the trade name Celluzyme® The products Endolase® and Carezyme®, which are also available from Novozymes, are based on the 50 kD-EG and 43 kD- EG from H. insolens DSM 1800. Other usable commercial products from this company are Cellusoft®, Renozyme® and Celluclean®, for example the 20 kD-EG from Melanocarpus, which are available from AB Enzymes, Finland, under the trade names Ecostone® and Biotouch® are available, further commercial products from AB Enzymes are Eco nase® and Ecopulp®. Other suitable cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, where the from Bacillus sp. CBS 670.93 is available from Genencor under the trade name Puradax®. Other commercial products from Genencor are "Genencor detergent cellulase L" and IndiAge®Neutra. Variants of these enzymes obtainable by point mutations can also be used according to the invention. Particularly preferred cellulases are Thielavia terrestris cellulase variants, cellulases from Melanocarpus, in particular Melanocarpus albomyces, cellulases of the EGIII type from Trichoderma reesei or variants obtainable therefrom.
Ferner können insbesondere zur Entfernung bestimmter Problemanschmutzungen weitere Enzyme eingesetzt sein, die unter dem Begriff Hemicellulasen zusammengefasst werden. Hierzu gehören beispielsweise Mannanasen, Xanthanlyasen, Xanthanasen, Xyloglucanasen, Xylanasen, Pullulana- sen, Pektin-spaltende Enzyme und ß-Glucanasen. Die aus Bacillus subtilis gewonnene ß-Glucanase ist unter dem Namen Cereflo® von der Firma Novozymes erhältlich. Erfindungsgemäß besonders bevorzugte Hemicellulasen sind Mannanasen, welche beispielsweise unter den Handelsnamen Mannaway® von dem Unternehmen Novozymes oder Purabrite® von dem Unternehmen Genencor vertrieben werden. Zu den Pektin-spaltenden Enzymen werden im Rahmen der vorliegenden Erfindung ebenfalls Enzyme gezählt mit den Bezeichnungen Pektinase, Pektatlyase, Pektinesterase, Pektindemethoxylase, Pektinmethoxylase, Pektinmethylesterase, Pektase, Pektinmethylesterase, Pektinoesterase, Pektinpektylhydrolase, Pektindepolymerase, Endopolygalacturonase, Pektolase, Pektinhydrolase, Pektin-Polygalacturonase, Endo-Polygalacturonase, Poly-a-1 ,4-Galacturonid Gly- canohydrolase, Endogalacturonase, Endo-D-galacturonase, Galacturan 1 ,4-a-Galacturonidase, Exopolygalacturonase, Poly(galacturonat) Hydrolase, Exo-D-Galacturonase, Exo-D-Galacturona-
nase, Exopoly-D-Galacturonase, Exo-poly-a-Galacturonosidase, Exopolygalacturonosidase oder Exopolygalacturanosidase. Beispiele für diesbezüglich geeignete Enzyme sind beispielsweise unter den Namen Gamanase®, Pektinex AR®, X-Pect® oder Pectaway® von dem Unternehmen Novozy- mes, unter dem Namen Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L®, Rohapect 10L®, Rohapect B1 L® von dem Unternehmen AB Enzymes und unter dem Namen Pyrolase® von dem Unternehmen Diversa Corp., San Diego, CA, USA erhältlich. Furthermore, further enzymes, which are summarized under the term hemicellulases, can be used in particular to remove certain problem soils. These include, for example, mannanases, xanthan lyases, xanthanases, xyloglucanases, xylanases, pullulanases, pectin-cleaving enzymes and β-glucanases. The β-glucanase obtained from Bacillus subtilis is available under the name Cereflo® from Novozymes. Hemicellulases which are particularly preferred according to the invention are mannanases, which are marketed, for example, under the trade names Mannaway® by the company Novozymes or Purabrite® by the company Genencor. To pectin-degrading enzymes are within the scope of the present invention also counted enzymes with designations of pectinase, pectate lyase, pectin esterase, Pektindemethoxylase, Pektinmethoxylase, pectin methylesterase, pectase, pectin, Pektinoesterase, Pektinpektylhydrolase, pectin depolymerase, endopolygalacturonase, Pektolase, Pektinhydrolase, pectin polygalacturonase, Endo-polygalacturonase, poly-a-1, 4-galacturonide glycanohydrolase, endogalacturonase, endo-D-galacturonase, galacturan 1, 4-a-galacturonidase, exopolygalacturonase, poly (galacturonate) hydrolase, exo-D-galacturonase D-Galacturona- nose, exopoly-D-galacturonase, exo-poly-a-galacturonosidase, exopolygalacturonosidase or exopolygalacturanosidase. Examples of suitable enzymes in this regard are, for example, under the names Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from Novozymes, under the names Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L®, Rohapect 10L®, Rohapect B1 L® available from AB Enzymes and under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.
Die flüssigen Mittel enthalten das mindestens eine Enzym vorzugsweise in im Stand der Technik etablierten Gesamtmengen. So kann das mindestens eine Enzym in einer Gesamtmenge von 1 x 10 8 bis 5 Gew.-% bezogen auf aktives Protein oder auch in einer Gesamtmenge von 0,001 bis 3 Gew.-%, oder 0,01 bis 1 ,5 Gew.-% oder 0,05 bis 1 ,25 Gew.-% enthalten sein. Die angegebenen Mengen sind so zu verstehen, dass jedes enthaltene Enzym in den genannten Mengen enthalten sein kann. Die Enzyme werden bevorzugt als Enzymflüssigformulierung(en) eingesetzt. The liquid compositions preferably contain the at least one enzyme in total amounts established in the prior art. Thus, the at least one enzyme in a total amount of 1 × 10 8 to 5 wt .-% based on active protein or in a total amount of 0.001 to 3 wt .-%, or 0.01 to 1.5 wt .-% or 0.05 to 1.25% by weight. The stated amounts are to be understood such that each enzyme contained can be contained in the stated amounts. The enzymes are preferably used as liquid enzyme formulation (s).
Das mindestens eine Enzym, das in einem Wasch- oder Reinigungsmittel vorhanden ist, unterstützt die Reinigungsleistung des Mittels auf bestimmten Anschmutzungen oder Flecken. Besonders bevorzugt enthält ein erfindungsgemäßes Mittel mehrere Enzyme, wobei die Enzyme den gleichen oder verschiedenen Enzymklassen angehören können. Besonders bevorzugt zeigen die Enzyme synergistische Effekte hinsichtlich ihrer Wirkung gegenüber bestimmten Anschmutzungen oder Flecken, das heißt die in der Zusammensetzung enthaltenen Enzyme unterstützen sich in ihrer Leistung gegenseitig. The at least one enzyme that is present in a detergent or cleaning agent supports the cleaning performance of the agent on certain stains or stains. An agent according to the invention particularly preferably contains several enzymes, the enzymes being able to belong to the same or different enzyme classes. The enzymes particularly preferably show synergistic effects with regard to their action against certain soiling or stains, that is to say the enzymes contained in the composition mutually support one another in their performance.
Als Antiredepositionsmittel sind insbesondere Polymere auf Terephthalat-PEG Basis einsetzbar. Alternativ sind auch (Co)Polymere auf Basis von Polyethylenimin, Polyvinylacetat und Polyethylenglykol einsetzbar. Polymers based on terephthalate-PEG can be used in particular as antiredeposition agents. Alternatively, (co) polymers based on polyethyleneimine, polyvinyl acetate and polyethylene glycol can also be used.
Als Gerüststoffe sind insbesondere organische Gerüststoffe geeignet, beispielsweise die in Form ihrer Natriumsalze oder auch als Säuren einsetzbaren Polycarbonsäuren, wobei unter Polycarbonsäuren solche Carbonsäuren verstanden werden, die mehr als eine Säurefunktion tragen. Beispielsweise sind dies Adipinsäure, Bernsteinsäure, Glutarsäure, Äpfelsäure, Weinsäure, Maleinsäure, Fumarsäure, Zuckersäuren, Aminocarbonsäuren, insbesondere Glutaminsäure-N,N-Di- essigsäure (GLDA) und Methylglycin-N,N-Diessigsäure (MGDA), sowie Mischungen aus diesen. Als Gerüststoffe sind weiter polymere Polycarboxylate geeignet. Dies sind beispielsweise die Alkalimetallsalze der Polyacrylsäure oder der Polymethacrylsäure, zum Beispiel solche mit einer relativen Molekülmasse von 600 bis 750.000 g/mol. Geeignete Polymere sind insbesondere Polyacrylate, die bevorzugt eine Molekülmasse von 1.000 bis 15.000 g/mol aufweisen. Aufgrund ihrer überlegenen Löslichkeit können aus dieser Gruppe wiederum die kurzkettigen Polyacrylate, die Molmassen von 1 .000 bis 10.000 g/mol, und besonders bevorzugt von 1.000 bis 5.000 g/mol, aufweisen, bevorzugt sein. Geeignet sind weiterhin Copolymere Polycarboxylate, insbesondere solche der Acrylsäure mit
Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Zur Verbesserung der Wasserlöslichkeit können die Polymere auch Allylsulfonsäuren, wie Allyloxybenzolsulfonsäure und Methallylsulfonsäure, als Monomer enthalten. In flüssigen Waschmitteln werden bevorzugt lösliche Gerüststoffe, wie Acrylpolymere mit einer Molmasse von 1.000 bis 5.000 g/mol eingesetzt. Organic builders are particularly suitable as builders, for example the polycarboxylic acids which can be used in the form of their sodium salts or also as acids, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, in particular glutamic acid-N, N-diacetic acid (GLDA) and methylglycine-N, N-diacetic acid (MGDA), and mixtures of these , Polymeric polycarboxylates are also suitable as builders. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 600 to 750,000 g / mol. Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights of 1,000 to 10,000 g / mol, and particularly preferably 1,000 to 5,000 g / mol, can in turn be preferred from this group. Copolymers of polycarboxylates, in particular those of acrylic acid, are also suitable Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. To improve water solubility, the polymers can also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers. Soluble builders, such as acrylic polymers with a molecular weight of 1,000 to 5,000 g / mol, are preferably used in liquid detergents.
Die Mittel können zusätzlich Phosphonate, wie beispielsweise HEDP (1-Hydroxyethan-1 , 1-diphos- phonsäure) oder DTPMP (Diethylentriaminpenta(methylenphosphonat), als Gerüststoffe und Komplexbildner enthalten. The agents can additionally contain phosphonates, such as HEDP (1-hydroxyethane-1,1-diphosphonic acid) or DTPMP (diethylenetriaminepenta (methylenephosphonate), as builders and complexing agents.
Die flüssigen Wasch- und Reinigungsmittel können in analoger Anwendung von im Stand der Technik bekannten Verfahren hergestellt werden. Sie können in eine wasserlösliche Umhüllung gefüllt werden und somit Bestandteil einer wasserlöslichen Verpackung sein. Ist das Mittel in einer wasserlöslichen Umhüllung verpackt, ist es bevorzugt, dass der Gehalt an Wasser weniger als 10 Gew.-%, bezogen auf das gesamte Mittel, beträgt und dass die anionischen Tenside in Form ihrer Ammoniumsalze oder als freie Säuren vorliegen. Eine wasserlösliche Verpackung enthält neben dem Mittel eine wasserlösliche Umhüllung. Die wasserlösliche Umhüllung wird vorzugsweise durch ein wasserlösliches Folienmaterial gebildet. Solche wasserlöslichen Verpackungen können entweder durch Verfahren des vertikalen Formfüllversiegelns (VFFS) oder Warmformverfahren hergestellt werden. Das Warmformverfahren schließt im Allgemeinen das Formen einer ersten Lage aus einem wasserlöslichen Folienmaterial zum Bilden von Ausbuchtungen zum Aufnehmen einer Zusammensetzung darin, Einfüllen der Zusammensetzung in die Ausbuchtungen, Bedecken der mit der Zusammensetzung gefüllten Ausbuchtungen mit einer zweiten Lage aus einem wasserlöslichen Folienmaterial und Versiegeln der ersten und zweiten Lagen miteinander zumindest um die Ausbuchtungen herum ein. Die wasserlösliche Umhüllung wird vorzugsweise aus einem wasserlöslichen Folienmaterial ausgewählt 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. Die wasserlösliche Verpackung, umfassend das Mittel und die wasserlösliche Umhüllung, kann eine oder mehr Kammern aufweisen. Das flüssige Mittel kann in einer oder mehreren Kammern, falls vorhanden, der wasserlöslichen Umhüllung enthalten sein. Die Menge an flüssigem Mittel entspricht vorzugsweise der vollen oder halben Dosis, die für einen Wasch- oder Reinigungsgang benötigt wird. Es ist bevorzugt, dass die wasserlösliche Umhüllung Polyvinylalkohol oder ein Polyvinylalkoholcopolymer enthält. Geeignete wasserlösliche Folien zur Herstellung der wasserlöslichen Umhüllung basieren bevorzugt auf einem Polyvinylalkohol oder einem Polyvinylalkoholcopolymer, dessen Molekulargewicht im Bereich von 10.000 g/mol bis 1 .000.000 g/mol, vorzugsweise von 20.000 g/mol bis 500.000 g/mol, besonders bevorzugt von 30.000 g/mol bis 100.000 g/mol und insbesondere von 40.000 g/mol bis 80.000 g/mol liegt. Ein zur Herstellung der wasserlöslichen Umhüllung geeignetes Folienmaterial kann zusätzlich Polymere, ausgewählt aus der Gruppe umfassend Acrylsäure-haltige Polymere, Polyacrylamide, Oxazolin-Polymere, Polystyrolsulfonate, Polyurethane, Polyester, Polyether
Polymilchsäure, und/oder Mischungen der vorstehenden Polymere, zugesetzt sein. Bevorzugte Polyvinylalkoholcopolymere umfassen neben Vinylalkohol Dicarbonsäuren als weitere Monomere. Geeignete Dicarbonsäure sind Itaconsäure, Malonsäure, Bernsteinsäure und Mischungen daraus, wobei Itaconsäure bevorzugt ist. Ebenso bevorzugte Polyvinylalkoholcopolymere umfassen neben Vinylalkohol eine ethylenisch ungesättigte Carbonsäure, deren Salz oder deren Ester. Besonders bevorzugt enthalten solche Polyvinylalkoholcopolymere neben Vinylalkohol Acrylsäure, Methacrylsäure, Acrylsäureester, Methacrylsäureester oder Mischungen daraus. Geeignete wasserlösliche Folien zum Einsatz in den 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. Die wasserlöslichen Verpackungen können eine im Wesentlichen formstabile kugelförmige und kissenförmige Ausgestaltung mit einer kreisförmigen, elliptischen, quadratischen oder rechteckigen Grundform aufweisen. Die wasserlösliche Verpackung kann eine oder mehrere Kammern zur Bevorratung eines oder mehrerer Mittel aufweisen. Weist die wasserlösliche Verpackung zwei oder mehr Kammern auf, enthält mindestens eine Kammer ein flüssiges Mittel gemäß der Erfindung, wobei die weiteren Kammern jeweils ein festes oder ein anders zusammengesetztes flüssiges Mittel enthalten können, oder die Inhalte der einzelnen Kammern ergeben zusammen ein flüssiges Mittel gemäß der Erfindung.
The liquid detergents and cleaning agents can be produced in an analogous application by methods known in the prior art. They can be filled in a water-soluble envelope and thus be part of a water-soluble packaging. If the agent is packaged in a water-soluble envelope, it is preferred that the water content is less than 10% by weight, based on the total agent, and that the anionic surfactants are present in the form of their ammonium salts or as free acids. In addition to the agent, a water-soluble packaging contains a water-soluble envelope. The water-soluble covering is preferably formed by a water-soluble film material. Such water-soluble packaging can be made either by vertical form fill sealing (VFFS) or thermoforming processes. The thermoforming process generally includes forming a first layer of a water-soluble sheet material to form bulges for receiving a composition therein, filling the composition into the bulges, covering the bulges filled with the composition with a second layer of a water-soluble sheet material and sealing the first and second layers with each other at least around the bulges. The water-soluble covering is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer mixtures. The sheath can be formed from 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, can be the same or different. The water-soluble package, comprising the agent and the water-soluble envelope, can have one or more compartments. The liquid agent may be contained in one or more compartments, if any, of the water-soluble enclosure. The amount of liquid agent preferably corresponds to the full or half dose required for a washing or cleaning cycle. It is preferred that the water-soluble envelope contain polyvinyl alcohol or a polyvinyl alcohol copolymer. Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer, the molecular weight of which is in the range from 10,000 g / mol to 1,000,000 g / mol, preferably from 20,000 g / mol to 500,000 g / mol, particularly preferably from 30,000 g / mol to 100,000 g / mol and in particular from 40,000 g / mol to 80,000 g / mol. A film material suitable for producing the water-soluble covering can additionally contain polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers Polylactic acid, and / or mixtures of the above polymers, may be added. In addition to vinyl alcohol, preferred polyvinyl alcohol copolymers comprise dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, itaconic acid being preferred. Likewise preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester or mixtures thereof. Suitable water-soluble films for use in the wrappings of the water-soluble packaging according to the invention are films which are sold by MonoSol LLC, for example under the name M8630, C8400 or M8900. Other suitable films include films with the designation Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray. The water-soluble packaging can have an essentially dimensionally stable spherical and pillow-shaped configuration with a circular, elliptical, square or rectangular basic shape. The water-soluble packaging can have one or more chambers for storing one or more agents. If the water-soluble packaging has two or more compartments, at least one compartment contains a liquid agent according to the invention, the further compartments may each contain a solid or a differently composed liquid agent, or the contents of the individual chambers together result in a liquid agent according to the Invention.
Beispiele: Examples:
Durch einfaches Schütteln des Mischgefäßes wurde aus 10 Gew.-Teilen eines der nachfolgend angegebenen Peroxoester A, B und C, 10 Gew.-Teilen 4-fach ethoxyliertem Cio-Guerbetalkohol (Lutensol® XL40) und 75 Gew.-Teilen Wasser bei Raumtemperatur Mikroemulsionen hergestellt. By simply shaking the mixing vessel, 10 parts by weight of one of the peroxoesters A, B and C given below, 10 parts by weight of 4-fold ethoxylated Cio-Guerbet alcohol (Lutensol® XL40) and 75 parts by weight of water became microemulsions at room temperature manufactured.
Als Referenz dienten ansonsten gleich zusammengesetzte, nicht mikroemulgierte Zubereitungen, die wie die erfindungsgemäßen Zubereitungen mit oder ohne UV Bestrahlung eingesetzt wurden. Dafür wurden mit einer standardisierten Blaubeer-Anschmutzung versehene weiße Baumwollläpp- chen (4 cm x 4 cm) mit jeweils 10 ml der Testformulierung versehen und 15 min lang mit einer UV- C Lampe bei einer Wellenlänge von 253,7 nm und einer Energiedichte von 221 ,4 mJ/cm2 im Abstand von 3 cm bestrahlt oder die gleiche Zeit in einer lichtdichten Box liegengelassen („unbestrahlt“). Nach der Bestrahlung wurden die Läppchen mit Wasser abgespült, getrocknet und ihre Helligkeit gemessen. In der nachfolgenden Tabelle angegeben ist die Differenz der L-Werte nach und vor der Behandlung; negative Werte bedeuten, dass die Anschmutzung dunkler wurde, positive Werte bedeuten eine Aufhellung der Anschmutzung. Otherwise, the same composition, non-microemulsified preparations were used, which like the preparations according to the invention were used with or without UV radiation. For this, white cotton cloths (4 cm x 4 cm) provided with standardized blueberry soiling were each provided with 10 ml of the test formulation and for 15 minutes with a UV-C lamp at a wavelength of 253.7 nm and an energy density of 221 , 4 mJ / cm 2 irradiated at a distance of 3 cm or left in a light-tight box for the same time ("unirradiated"). After the irradiation, the lobules were rinsed with water, dried and their brightness measured. The table below shows the difference in L values after and before treatment; negative values mean that the soiling has become darker, positive values mean that the soiling is lightened.
Tabelle: Helligkeitsdifferenzen Table: Differences in brightness
n.b.: nicht bestimmt
nb: not determined
Claims
1. Wasser- und tensidhaltiges flüssiges Wasch- oder Reinigungsmittel, das eine hydrophobe Vorläuferverbindung in mikroemulgierter Form enthält, aus der durch UV-Bestrahlung eine Peroxocarbonsäure oder deren Salz freisetzbar ist. 1. Water and surfactant-containing liquid detergent or cleaning agent which contains a hydrophobic precursor compound in microemulsified form, from which a peroxocarboxylic acid or its salt can be released by UV radiation.
2. Mittel nach Anspruch 1 , dadurch gekennzeichnet, dass es die Vorläuferverbindung in Mengen von 0,1 Gew.-% bis 20 Gew.-%, insbesondere von 1 Gew.-% bis 15 Gew.-% enthält, und/oder Mikroemulgator in Mengen von 0,01 Gew.-% bis 60 Gew.-%, insbesondere von 1 Gew.-% bis 50 Gew.-% enthält. 2. Composition according to claim 1, characterized in that it contains the precursor compound in amounts of 0.1 wt .-% to 20 wt .-%, in particular from 1 wt .-% to 15 wt .-%, and / or microemulsifier contains in amounts of from 0.01% by weight to 60% by weight, in particular from 1% by weight to 50% by weight.
3. Verwendung einer Kombination aus einer wässrigen Mikroemulsion einer hydrophoben Vorläuferverbindung, aus der durch UV-Bestrahlung eine Peroxocarbonsäure oder deren Salz freisetzbar ist, und UV-Strahlung zur Entfernung von Anschmutzungen beim Waschen von Textilien oder beim Reinigen harter Oberflächen. 3. Use of a combination of an aqueous microemulsion of a hydrophobic precursor compound, from which a peroxocarboxylic acid or its salt can be released by UV radiation, and UV radiation to remove stains when washing textiles or when cleaning hard surfaces.
4. Verwendung nach Anspruch 3, dadurch gekennzeichnet, dass die Mikroemulsion 2 Gew.-% bis 12 Gew.-%, insbesondere von 4 Gew.-% bis 10 Gew.-% der hydrophoben Vorläuferverbindung, 2 Gew.-% bis 40 Gew.-%, insbesondere von 4 Gew.-% bis 35 Gew.-% Mikroemulgator und auf 100 Gew.-% Wasser enthält. 4. Use according to claim 3, characterized in that the microemulsion 2 wt .-% to 12 wt .-%, in particular from 4 wt .-% to 10 wt .-% of the hydrophobic precursor compound, 2 wt .-% to 40 wt .-%, in particular from 4 wt .-% to 35 wt .-% microemulsifier and per 100 wt .-% water.
5. Wasch- oder Reinigungsverfahren, bei dem man eine waschbedürftige textile Oberfläche oder eine reinigungsbedürftige harte Oberfläche mit einer tensidhaltigen wässrigen Wasch- oder Reinigungsflüssigkeit in Kontakt bringt, die eine hydrophobe Vorläuferverbindung in mikroemulgierter Form enthält, aus der durch UV-Bestrahlung eine Peroxocarbonsäure oder deren Salz freisetzbar ist, und UV-Strahlung auf die Flüssigkeit einwirken lässt. 5. washing or cleaning method, in which one brings a textile surface in need of washing or a hard surface in need of cleaning into contact with a surfactant-containing aqueous washing or cleaning liquid which contains a hydrophobic precursor compound in microemulsified form, from which a peroxocarboxylic acid or the like thereof is produced by UV radiation Salt can be released and UV radiation can act on the liquid.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass man es bei Temperaturen noch unterhalb der Raumtemperatur oder bei Temperaturen im Bereich von 5 °C bis 60 °C, insbesondere von 10 °C bis 40 °C durchführt. 6. The method according to claim 5, characterized in that it is carried out at temperatures below room temperature or at temperatures in the range from 5 ° C to 60 ° C, in particular from 10 ° C to 40 ° C.
7. Verfahren nach Anspruch 5 oder 6, dadurch gekennzeichnet, dass der Kontakt der Wasch- oder Reinigungsflüssigkeit mit dem zu waschenden Textil oder der zu reinigenden harten Oberfläche während einer Dauer von 1 Minute bis 2 Stunden, insbesondere 2 Minuten bis 1 Stunde stattfindet, und/oder dass die UV-Bestrahlungsdauer im Bereich von 5 Minuten bis 40 Minuten, insbesondere von 6 Minuten bis 30 Minuten liegt, und/oder dass die Energiedichte der UV- Strahlung im Bereich von 150 mJ/cm2 bis 400 mJ/cm2, insbesondere von 200 mJ/cm2 bis 300 mJ/cm2 liegt.
7. The method according to claim 5 or 6, characterized in that the contact of the washing or cleaning liquid with the textile to be washed or the hard surface to be cleaned takes place for a period of 1 minute to 2 hours, in particular 2 minutes to 1 hour, and / or that the UV radiation duration is in the range from 5 minutes to 40 minutes, in particular from 6 minutes to 30 minutes, and / or that the energy density of the UV radiation is in the range from 150 mJ / cm 2 to 400 mJ / cm 2 , is in particular from 200 mJ / cm 2 to 300 mJ / cm 2 .
8. Mittel, Verwendung oder Verfahren gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die UV-Strahlung Wellenlängen im Bereich von 100 nm bis 300 nm, insbesondere von 240 nm bis 270 nm aufweist. 8. Means, use or method according to one of the preceding claims, characterized in that the UV radiation has wavelengths in the range from 100 nm to 300 nm, in particular from 240 nm to 270 nm.
9. Mittel, Verwendung oder Verfahren gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Vorläuferverbindung einen n-Octanol-Wasser- Verteilungskoeffizient log Kow bei 20 °C von mindestens 0,5, vorzugsweise im Bereich von 1 bis 30, und insbesondere von 2 bis 20 aufweist. 9. Means, use or method according to one of the preceding claims, characterized in that the precursor compound has an n-octanol-water distribution coefficient log Kow at 20 ° C of at least 0.5, preferably in the range from 1 to 30, and in particular from 2 to 20.
10. Mittel, Verwendung oder Verfahren gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Vorläuferverbindung aus den Peroxoestern einer der allgemeinen Formeln (I) bis (VI), i? 10. Agent, use or method according to any one of the preceding claims, characterized in that the precursor compound from the peroxoesters of one of the general formulas (I) to (VI), i?
R’-C-OO-R (I) R’-C-OO-R (I)
(II) (II)
(III)(III)
H 9 ff (IV)H 9 ff (IV)
O- C-RR"’'-0C-OO-R ff ff (V) O-C-RR "’ '- 0C-OO-R ff ff (V)
FH30 -OFT-G- OO-R FH30 -OFT-G- OO-R
(VI) (VI)
' (-O(-AO) -C-OO-R ) in denen R für eine lineare oder verzweigtkettige Alkylgruppe mit 1 bis 30 C-Atomen, insbesondere 2 bis 20 C-Atomen, R' für eine lineare oder verzweigtkettige Alkylgruppe mit 1 bis 30 C- Atomen, insbesondere 2 bis 20 C-Atomen, R“ für eine lineare oder verzweigtkettige Alkylengruppe mit 1 bis 30 C-Atomen, insbesondere 2 bis 20 C-Atomen, R“‘ für eine m-bindige lineare oder verzweigtkettige Alkylgruppe mit 2 bis 9 C-Atomen, insbesondere 3 bis 5 C-Atomen, A für eine Alkylengruppe mit 2 bis 4 C-Atomen, m für eine Zahl von 2 bis 6, insbesondere 3 oder 4, und n für eine Zahl von 2 bis 30, insbesondere von 3 bis 15, steht, '(-O (-AO) -C-OO-R) in which R for a linear or branched chain alkyl group having 1 to 30 C atoms, in particular 2 to 20 C atoms, R ' for a linear or branched chain alkyl group having 1 up to 30 C atoms, in particular 2 to 20 C atoms, R " for a linear or branched chain alkylene group with 1 to 30 C atoms, in particular 2 to 20 C atoms, R"'for an m-binding linear or branched chain alkyl group with 2 to 9 carbon atoms, in particular 3 to 5 carbon atoms, A for an alkylene group with 2 to 4 carbon atoms, m for a number from 2 to 6, in particular 3 or 4, and n for a number from 2 to 30, in particular from 3 to 15,
und deren Mischungen ausgewählt wird.
and their mixtures is selected.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102018213192.9A DE102018213192A1 (en) | 2018-08-07 | 2018-08-07 | Liquid detergent or cleaning agent containing bleach precursor |
| PCT/EP2019/070745 WO2020030517A1 (en) | 2018-08-07 | 2019-08-01 | Liquid bleach-precursor containing detergent or cleaning agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP3833732A1 true EP3833732A1 (en) | 2021-06-16 |
Family
ID=67551369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19750102.6A Pending EP3833732A1 (en) | 2018-08-07 | 2019-08-01 | Liquid bleach-precursor containing detergent or cleaning agent |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20210179976A1 (en) |
| EP (1) | EP3833732A1 (en) |
| DE (1) | DE102018213192A1 (en) |
| WO (1) | WO2020030517A1 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2258948T3 (en) * | 1995-03-27 | 2006-09-16 | THE PROCTER & GAMBLE COMPANY | ACTIVATED LIQUID WHITENING COMPOSITIONS. |
| US5681805A (en) * | 1995-05-25 | 1997-10-28 | The Clorox Company | Liquid peracid precursor colloidal dispersions: microemulsions |
| AU5709598A (en) * | 1997-12-22 | 1999-07-12 | Procter & Gamble Company, The | Improved oxygen bleaching system |
| WO2007005471A2 (en) * | 2005-06-29 | 2007-01-11 | Jr Chem, Llc | Stable organic peroxide compositions |
| DE102005063180A1 (en) * | 2005-12-30 | 2007-07-05 | Henkel Kgaa | Aqueous surfactant- and bleaching agent containing liquid washing or cleaning agent, comprises particulate peroxycarboxylic acid, preferably phthalimidoperoxohexanoic acid and magnesium sulfate |
-
2018
- 2018-08-07 DE DE102018213192.9A patent/DE102018213192A1/en not_active Withdrawn
-
2019
- 2019-08-01 WO PCT/EP2019/070745 patent/WO2020030517A1/en unknown
- 2019-08-01 EP EP19750102.6A patent/EP3833732A1/en active Pending
-
2021
- 2021-02-08 US US17/170,234 patent/US20210179976A1/en active Pending
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| Publication number | Publication date |
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| WO2020030517A1 (en) | 2020-02-13 |
| US20210179976A1 (en) | 2021-06-17 |
| DE102018213192A1 (en) | 2020-02-13 |
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