EP4098727B1 - Viscosity-modified washing up liquid - Google Patents
Viscosity-modified washing up liquid Download PDFInfo
- Publication number
- EP4098727B1 EP4098727B1 EP21177322.1A EP21177322A EP4098727B1 EP 4098727 B1 EP4098727 B1 EP 4098727B1 EP 21177322 A EP21177322 A EP 21177322A EP 4098727 B1 EP4098727 B1 EP 4098727B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- hand dishwashing
- surfactant
- dishwashing composition
- viscosity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000007788 liquid Substances 0.000 title description 5
- 238000005406 washing Methods 0.000 title 1
- 239000000203 mixture Substances 0.000 claims description 104
- 238000004851 dishwashing Methods 0.000 claims description 81
- -1 alkali metal salt Chemical class 0.000 claims description 38
- 239000004094 surface-active agent Substances 0.000 claims description 38
- 102000004190 Enzymes Human genes 0.000 claims description 36
- 108090000790 Enzymes Proteins 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- 150000001412 amines Chemical class 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 19
- 239000003945 anionic surfactant Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 229940071118 cumenesulfonate Drugs 0.000 claims description 7
- JBVOQKNLGSOPNZ-UHFFFAOYSA-N 2-propan-2-ylbenzenesulfonic acid Chemical compound CC(C)C1=CC=CC=C1S(O)(=O)=O JBVOQKNLGSOPNZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 5
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 229960003237 betaine Drugs 0.000 claims description 3
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 2
- 150000008045 alkali metal halides Chemical group 0.000 claims description 2
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims 2
- 235000011164 potassium chloride Nutrition 0.000 claims 1
- 239000001103 potassium chloride Substances 0.000 claims 1
- 239000003599 detergent Substances 0.000 description 38
- 229940088598 enzyme Drugs 0.000 description 33
- 108091005804 Peptidases Proteins 0.000 description 24
- 239000004365 Protease Substances 0.000 description 24
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 18
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 16
- 108091005658 Basic proteases Proteins 0.000 description 13
- 239000000654 additive Substances 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 150000002191 fatty alcohols Chemical class 0.000 description 8
- 239000002736 nonionic surfactant Substances 0.000 description 8
- 239000004711 α-olefin Substances 0.000 description 8
- 241000193422 Bacillus lentus Species 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 102000013142 Amylases Human genes 0.000 description 6
- 108010065511 Amylases Proteins 0.000 description 6
- 102000035195 Peptidases Human genes 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 108010020132 microbial serine proteinases Proteins 0.000 description 6
- 102000004169 proteins and genes Human genes 0.000 description 6
- 108090000623 proteins and genes Proteins 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 108090000787 Subtilisin Proteins 0.000 description 5
- 150000004676 glycans Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920001282 polysaccharide Polymers 0.000 description 5
- 239000005017 polysaccharide Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 150000003871 sulfonates Chemical class 0.000 description 5
- 239000002562 thickening agent 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
- OSCJHTSDLYVCQC-UHFFFAOYSA-N 2-ethylhexyl 4-[[4-[4-(tert-butylcarbamoyl)anilino]-6-[4-(2-ethylhexoxycarbonyl)anilino]-1,3,5-triazin-2-yl]amino]benzoate Chemical compound C1=CC(C(=O)OCC(CC)CCCC)=CC=C1NC1=NC(NC=2C=CC(=CC=2)C(=O)NC(C)(C)C)=NC(NC=2C=CC(=CC=2)C(=O)OCC(CC)CCCC)=N1 OSCJHTSDLYVCQC-UHFFFAOYSA-N 0.000 description 4
- 241000194110 Bacillus sp. (in: Bacteria) Species 0.000 description 4
- 101000740449 Bacillus subtilis (strain 168) Biotin/lipoyl attachment protein Proteins 0.000 description 4
- LVDKZNITIUWNER-UHFFFAOYSA-N Bronopol Chemical compound OCC(Br)(CO)[N+]([O-])=O LVDKZNITIUWNER-UHFFFAOYSA-N 0.000 description 4
- 108010059892 Cellulase Proteins 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000004435 Oxo alcohol Substances 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- 235000019418 amylase Nutrition 0.000 description 4
- 229920001577 copolymer Polymers 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
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000004615 ingredient Substances 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
- YBYRMVIVWMBXKQ-UHFFFAOYSA-N phenylmethanesulfonyl fluoride Chemical compound FS(=O)(=O)CC1=CC=CC=C1 YBYRMVIVWMBXKQ-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 239000003760 tallow Substances 0.000 description 4
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 3
- 239000004382 Amylase Substances 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 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
- 102000004316 Oxidoreductases Human genes 0.000 description 3
- 108090000854 Oxidoreductases Proteins 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000012963 UV stabilizer Substances 0.000 description 3
- 150000008051 alkyl sulfates Chemical class 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 229940106157 cellulase Drugs 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000000645 desinfectant Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000002304 perfume Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-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
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- 102220560806 Acyl-CoA dehydrogenase family member 11_R99E_mutation Human genes 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 241000193375 Bacillus alcalophilus Species 0.000 description 2
- 241000193744 Bacillus amyloliquefaciens Species 0.000 description 2
- 241001328119 Bacillus gibsonii Species 0.000 description 2
- 241000194108 Bacillus licheniformis Species 0.000 description 2
- 244000303965 Cyamopsis psoralioides Species 0.000 description 2
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 2
- 108010056079 Subtilisins Proteins 0.000 description 2
- 102000005158 Subtilisins Human genes 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- POJWUDADGALRAB-UHFFFAOYSA-N allantoin Chemical compound NC(=O)NC1NC(=O)NC1=O POJWUDADGALRAB-UHFFFAOYSA-N 0.000 description 2
- 108090000637 alpha-Amylases Proteins 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 description 2
- AFYNADDZULBEJA-UHFFFAOYSA-N bicinchoninic acid Chemical compound C1=CC=CC2=NC(C=3C=C(C4=CC=CC=C4N=3)C(=O)O)=CC(C(O)=O)=C21 AFYNADDZULBEJA-UHFFFAOYSA-N 0.000 description 2
- 229960003168 bronopol Drugs 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 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
- 150000002148 esters Chemical class 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229930182470 glycoside Natural products 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 108010002430 hemicellulase Proteins 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 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
- 125000001196 nonadecyl 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])C([H])([H])[H] 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
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000001508 potassium citrate Substances 0.000 description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical class [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000008107 starch 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
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 230000008719 thickening Effects 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
- HFVMEOPYDLEHBR-UHFFFAOYSA-N (2-fluorophenyl)-phenylmethanol Chemical class C=1C=CC=C(F)C=1C(O)C1=CC=CC=C1 HFVMEOPYDLEHBR-UHFFFAOYSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 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 class CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-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
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 1
- DBHODFSFBXJZNY-UHFFFAOYSA-N 2,4-dichlorobenzyl alcohol Chemical compound OCC1=CC=C(Cl)C=C1Cl DBHODFSFBXJZNY-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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 1
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- MUZDXNQOSGWMJJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=C)C(O)=O MUZDXNQOSGWMJJ-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 101710184263 Alkaline serine protease Proteins 0.000 description 1
- POJWUDADGALRAB-PVQJCKRUSA-N Allantoin Natural products NC(=O)N[C@@H]1NC(=O)NC1=O POJWUDADGALRAB-PVQJCKRUSA-N 0.000 description 1
- 244000144927 Aloe barbadensis Species 0.000 description 1
- 235000002961 Aloe barbadensis Nutrition 0.000 description 1
- 101710130006 Beta-glucanase Proteins 0.000 description 1
- 102100032487 Beta-mannosidase Human genes 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 101100400624 Caenorhabditis elegans mbr-1 gene Proteins 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 108010084185 Cellulases Proteins 0.000 description 1
- 102000005575 Cellulases Human genes 0.000 description 1
- 108010008885 Cellulose 1,4-beta-Cellobiosidase Proteins 0.000 description 1
- 108010000659 Choline oxidase Proteins 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241001440269 Cutina Species 0.000 description 1
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- SNPLKNRPJHDVJA-ZETCQYMHSA-N D-panthenol Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCCO SNPLKNRPJHDVJA-ZETCQYMHSA-N 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 108010082495 Dietary Plant Proteins Proteins 0.000 description 1
- 108010059378 Endopeptidases Proteins 0.000 description 1
- 102000005593 Endopeptidases Human genes 0.000 description 1
- FPVVYTCTZKCSOJ-UHFFFAOYSA-N Ethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCCCCCCCC FPVVYTCTZKCSOJ-UHFFFAOYSA-N 0.000 description 1
- 229920002148 Gellan gum Polymers 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 241000208680 Hamamelis mollis Species 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
- 229920001612 Hydroxyethyl starch Polymers 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 108010059820 Polygalacturonase Proteins 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 description 1
- 108010022999 Serine Proteases Proteins 0.000 description 1
- 102000012479 Serine Proteases Human genes 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 101710135785 Subtilisin-like protease Proteins 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Chemical class OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 description 1
- 229930003779 Vitamin B12 Natural products 0.000 description 1
- 229930003471 Vitamin B2 Natural products 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- RRUDCFGSUDOHDG-UHFFFAOYSA-N acetohydroxamic acid Chemical class CC(O)=NO RRUDCFGSUDOHDG-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 1
- 229960000458 allantoin Drugs 0.000 description 1
- 235000011399 aloe vera Nutrition 0.000 description 1
- 102000004139 alpha-Amylases Human genes 0.000 description 1
- 229940024171 alpha-amylase Drugs 0.000 description 1
- 150000001413 amino acids Chemical group 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Chemical class OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 108010055059 beta-Mannosidase Proteins 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229960001631 carbomer Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- AGVAZMGAQJOSFJ-WZHZPDAFSA-M cobalt(2+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+2].N#[C-].[N-]([C@@H]1[C@H](CC(N)=O)[C@@]2(C)CCC(=O)NC[C@@H](C)OP(O)(=O)O[C@H]3[C@H]([C@H](O[C@@H]3CO)N3C4=CC(C)=C(C)C=C4N=C3)O)\C2=C(C)/C([C@H](C\2(C)C)CCC(N)=O)=N/C/2=C\C([C@H]([C@@]/2(CC(N)=O)C)CCC(N)=O)=N\C\2=C(C)/C2=N[C@]1(C)[C@@](C)(CC(N)=O)[C@@H]2CCC(N)=O AGVAZMGAQJOSFJ-WZHZPDAFSA-M 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 229960004698 dichlorobenzyl alcohol Drugs 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940079919 digestives enzyme preparation Drugs 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229940066758 endopeptidases Drugs 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 108010093305 exopolygalacturonase Proteins 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229940100608 glycol distearate Drugs 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 229940059442 hemicellulase Drugs 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229920013819 hydroxyethyl ethylcellulose Polymers 0.000 description 1
- 229940050526 hydroxyethylstarch Drugs 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013038 irreversible inhibitor Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 239000002502 liposome Substances 0.000 description 1
- 239000008297 liquid dosage form Substances 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920003087 methylethyl cellulose Polymers 0.000 description 1
- 229940100573 methylpropanediol Drugs 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 229940101267 panthenol Drugs 0.000 description 1
- 235000020957 pantothenol Nutrition 0.000 description 1
- 239000011619 pantothenol Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000003531 protein hydrolysate Substances 0.000 description 1
- 229960002477 riboflavin Drugs 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007909 solid dosage form Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 235000015870 tripotassium citrate Nutrition 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- 235000019163 vitamin B12 Nutrition 0.000 description 1
- 239000011715 vitamin B12 Substances 0.000 description 1
- 235000019164 vitamin B2 Nutrition 0.000 description 1
- 239000011716 vitamin B2 Substances 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
- 229940118846 witch hazel Drugs 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 229940071104 xylenesulfonate Drugs 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Images
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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0047—Other compounding ingredients characterised by their effect pH regulated compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- 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
- C11D3/43—Solvents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
Definitions
- Dishwashing detergents in particular liquid dishwashing detergents for manual cleaning, of dishes are known.
- low-viscosity hand dishwashing compositions are perceived by consumers as being of lower quality. Viscosity is therefore an important quality criterion for hand dishwashing compositions.
- modern hand dishwashing detergents should be produced in an environmentally friendly manner and at the same time have the best possible cleaning performance.
- Another special feature of hand dishwashing compositions is the requirement that they should be gentle on the skin.
- EP3670637 A1 discloses hand dishwashing detergent comprising at least one anionic surfactant and at least one amine oxide surfactant, wherein the amount of amine oxide surfactant is at least 20% by weight of the total amount of surfactant, and the composition has a viscosity factor of 0.1 to 50 mPas.
- the object on which the present invention is based is therefore to provide compositions which, on the one hand, are perceived by the consumer as being of high quality and which can also be processed in an environmentally friendly manner and at the same time have good skin compatibility.
- compositions according to the invention in particular have a good viscosity profile in the skin-friendly pH range of at least 7.5 to less than 8.5.
- a “good viscosity profile” means that the viscosity of the compositions is such that the consumer perceives the compositions as being of high quality and the viscosity is within the range
- the relevant pH range has a relatively small change depending on the pH value. It was identified that the viscosity range between 1000 cps and 4000 cps represents a particularly advantageous range in terms of finding a balance between good processability on the one hand and high-quality product properties on the other.
- the viscosity of the composition is at least 1500 cps to 2500 cps.
- the viscosity of the composition is at least 1800 cps to 2200 cps.
- the viscosity is determined using a Brookfield LVDV II+, spindle 31 at a temperature of 20 ° C, at 12 rpm.
- the hand dishwashing composition is described, wherein the salt is an alkali metal halide and/or an alkaline earth metal halide, preferably sodium chloride.
- the hand dishwashing composition is described, wherein the amount of inorganic salt is at least 2% by weight, preferably at least 4% by weight.
- the hand dishwashing composition is described, wherein the ratio of total surfactant content to solvent is less than 10, preferably between 4 and 6, more preferably 4 or 5.
- the hand dishwashing composition is described, wherein the hand dishwashing composition comprises at least one enzyme.
- the hand dishwashing composition is described, wherein the hand dishwashing composition comprises an anionic surfactant.
- the hand dishwashing composition comprises an amine oxide and/or a betaine surfactant.
- the hand dishwashing composition is described, wherein the total amount of surfactant is at least 8% by weight, more preferably at least 12% by weight, more preferably at least 20% by weight.
- the hand dishwashing composition is described, wherein the hand dishwashing composition comprises at least one enzyme.
- the hand dishwashing composition is described, wherein the hand dishwashing composition comprises an anionic surfactant.
- the total amount of solvent is at least 1% by weight, more preferably at least 2% by weight and more preferably at least 2.5% by weight.
- the use of the composition is for manual cleaning of dishes.
- the amount of total surfactant is at least 5% by weight, 10% by weight based on the total weight of the composition.
- a hand dishwashing composition wherein the proportion of amine oxides having a C16 or longer residue is less than 20%, more preferably less than 10%, based on the total weight of the amine oxides in the composition.
- a hand dishwashing composition wherein the anionic surfactant is present in an amount of at least 4% by weight, preferably at least 10% by weight, based on the total weight of the composition.
- a hand dishwashing composition is described, wherein aminexoid is present in an amount of at least 4% by weight based on the total weight of the composition.
- a hand dishwashing composition wherein betaine is present in an amount of at least 4% by weight based on the total weight of the composition.
- a hand dishwashing composition wherein the composition comprises an organic solvent which is present in at least an amount of 2% by weight.
- a hand dishwashing composition is described, wherein the proportion of amine oxides that have a C12 residue is between 50 and 85% based on the total amount of amine oxide, preferably between 60 and 85%.
- a hand dishwashing composition is described, wherein the proportion of amine oxides which have a C14 residue is between 20 and 35% based on the total amount of amine oxide.
- a hand dishwashing composition wherein the proportion of amine oxides which only have C10 or smaller residues is less than 5% based on the total amount of amine oxide.
- a hand dishwashing composition wherein the surfactant system contains at least one anionic surfactant selected from ether sulfates, alkyl sulfates and mixtures thereof.
- Hand dishwashing composition wherein the dishwashing composition contains at least one additional ingredient selected from the group consisting of water, enzymes, organic solvents, enzymes, additives to improve drainage and drying behavior, to adjust the viscosity and / or for stabilization, UV stabilizers, perfume, pearlescent agents, Dyes, corrosion inhibitors, bitter substances, organic salts, disinfectants, structuring polymers, defoamers, encapsulated ingredients, pH adjusters and additives that improve or care for skin feel.
- the dishwashing composition contains at least one additional ingredient selected from the group consisting of water, enzymes, organic solvents, enzymes, additives to improve drainage and drying behavior, to adjust the viscosity and / or for stabilization, UV stabilizers, perfume, pearlescent agents, Dyes, corrosion inhibitors, bitter substances, organic salts, disinfectants, structuring polymers, defoamers, encapsulated ingredients, pH adjusters and additives that improve or care for skin feel.
- the present invention is further directed to the use of the dishwashing detergent according to the invention for manually cleaning dishes.
- At least one refers to 1 or more, for example 2, 3, 4, 5, 6, 7, 8, 9 or more. In connection with components of the compounds described herein, this information does not refer to the absolute amount of molecules, but rather to the type of component. “At least one surfactant” therefore means, for example, that only one type of surfactant compound or several different types of surfactant compounds can be included, without providing information about the amount of the individual compounds.
- the expression “essentially free of” means that the respective compound can in principle be included, but is then present in an amount that does not impair the function of the other components.
- the property “substantially free of” a particular compound is therefore preferably a total weight of less than 0.1% by weight, more preferably less than 0.001% by weight, in particular free of this, based on the total weight of dishwashing detergent.
- molecular weight refers to the weight-average molecular weight in g/mol, unless the number-average molecular weight is explicitly stated.
- Molecular weights are preferably determined by GPC using polystyrene standards.
- fatty acids or fatty alcohols or their derivatives - unless otherwise stated - represent branched or unbranched carboxylic acids or alcohols or their derivatives with preferably 6 to 22 carbon atoms.
- the oxo alcohols or their derivatives obtainable, for example, by ROELEN's oxo synthesis can also be used accordingly.
- components of the present agents are salts, they are preferably alkali metal or alkaline earth metal salts of the respective compounds, more preferably the alkali metal salts, in particular the sodium or potassium salts, most preferably sodium salts thereof.
- alkaline earth metals are mentioned below as counterions for monovalent anions, this means that the alkaline earth metal is of course only present in half the amount of substance as the anion - which is sufficient to balance the charge.
- the dishwashing detergent according to the invention is preferably essentially free of cationic surfactants.
- the composition has at least one alkyl benzene sulfonate, which preferably has a C2-18 alkyl radical. Cumenesulfonate is particularly preferred.
- alkylbenzenesulfonate refers only to a benzene ring substituted with an alkyl radical and which also carries a sulfonate radical.
- the at least one alkylbenzene sulfonate is contained in 0.5 to 50% by weight, preferably 0.5 to 30% by weight, particularly preferably in 0.5 to 5% by weight, based on the total weight of the dishwashing detergent.
- the at least one fatty alcohol sulfate is preferably selected from C8-18 fatty alcohol sulfates.
- Particularly preferred fatty alcohol sulfates are derived from C12-18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol. Sodium lauryl sulfate is particularly preferred.
- the at least one fatty alcohol sulfate is contained in 0.5 to 45% by weight, preferably 0.5 to 40% by weight, more preferably in 3 to 15% by weight, based on the total weight of the dishwashing detergent.
- the at least one amine oxide is a compound having the formula R1R2R3NO, where each R1, R2 and R3, independently of the others, is an optionally substituted, for example hydroxy-substituted, C1-C30 hydrocarbon chain.
- Particularly preferred amine oxides used are those in which R1 is C10-C16 alkyl and R2 and R3 are each independently C1-C4 alkyl, in particular C10-C16 alkyldimethylamine oxides.
- suitable amine oxides are N-cocoalkyl-N,N-dimethylamine oxide and N-tallow alkyl-N,N-dihydroxyethylamine oxide.
- the at least one amine oxide is preferably selected from C12-16 amine oxides, particularly preferably from low-chain C12-14 alkyldimethylamine oxides.
- the at least one amine oxide is contained in 0.1 to 20 wt.%, preferably 0.3 to 10 wt.%, more preferably 0.5 to 3 wt.%, based on the total weight of the dishwashing detergent .
- alpha-olefin sulfonates are selected from C10-20 alpha-olefin sulfonates, more preferably linear C10-20 alpha-olefin sulfonates. In particular it is selected from C12-14 alpha-olefin sulfonates; most preferably it is a linear C12-14 alpha-olefin sulfonate.
- the at least one alpha-olefin sulfonate is preferably contained in 2.5 to 45% by weight, more preferably 3 to 30% by weight, particularly preferably in 5 to 25% by weight, based on the total weight of the dishwashing detergent.
- a suitable alpha-olefin sulfonate is commercially available, for example, under the trade name Bio- Terge® AS-40 from Stephan.
- the at least one further anionic surfactant is selected from ether sulfates, alkyl sulfates and mixtures thereof.
- Preferred ether sulfates are those of the formula (I) R1-O-(AO)n-SO3- X+ (I).
- R1 represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical.
- Preferred radicals R1 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives having an even number of carbon atoms are preferred.
- radicals R1 are derived from C12-C18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C10-C20 oxo alcohols.
- X stands for a single-quality cation or the n-ten part of an N-quality cation, preferably the alkali metal ions and below Na+ or K+, where Na+ is extremely preferred. Further cations
- AO represents an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group.
- the index n represents an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. Very particularly preferably n represents the numbers 2, 3, 4, 5, 6, 7 or 8.
- alkyl sulfates which are not derived from fatty alcohols, of the formula R2-O-SO3-X+ (II).
- R2 represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical.
- Preferred radicals R2 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives having an even number of carbon atoms are preferred. They are particularly preferably derived from C10-20 oxo alcohols.
- X stands for a single-quality cation or the n-ten part of an N-quality cation, preferably the alkali metal ions and below Na+ or K+, where Na+ is extremely preferred. Further cations
- the at least one further nonionic surfactant is 0.1 to 20 wt.%, preferably 0.5 to 10 wt.%, more preferably 1 to 8 wt.%, based on the total weight of the dishwashing detergent contain.
- nonionic surfactants known for dishwashing detergents are suitable as further nonionic surfactants.
- the at least one further nonionic surfactant is selected from alkoxylated fatty acid alkyl esters, polyhydroxy fatty acid amides, alkyl glycosides and alkoxylated alcohols and mixtures thereof.
- nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
- Suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.
- alkyl glycosides of the general formula RO (G) a glycose unit with 5 or 6 carbon atoms, preferably glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
- the further nonionic surfactants are selected from the group of alkoxylated alcohols.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) or propylene oxide (PO) per mole of alcohol, in which the alcohol residue is linear or preferably in 2 position can be methyl-branched or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
- EO ethylene oxide
- PO propylene oxide
- alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are preferred.
- the preferred ethoxylated alcohols include, for example, C12-14 alcohols with 3 EO or 4 EO, C8-11 alcohol with 7 EO, C13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12-18 Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-14 alcohol with 3 EO and C12-18 alcohol with 5 EO.
- the total amount of surfactants i.e. the surfactant system, based on the weight of the agent, is 2.5 to 70% by weight, preferably 5 to 60% by weight, more preferably 6 to 50% by weight.
- the dishwashing detergent according to the present invention can also contain at least one additional ingredient selected from the group consisting of water, enzymes, additives to improve drainage and drying behavior, to adjust the viscosity and / or for stabilization, UV stabilizers, perfume, pearlescent agents, dyes , corrosion inhibitors, preservatives, bitter substances, organic salts, disinfectants, structuring polymers, defoamers, encapsulated ingredients, pH adjusters and additives that improve or care for skin feel.
- at least one additional ingredient selected from the group consisting of water, enzymes, additives to improve drainage and drying behavior, to adjust the viscosity and / or for stabilization, UV stabilizers, perfume, pearlescent agents, dyes , corrosion inhibitors, preservatives, bitter substances, organic salts, disinfectants, structuring polymers, defoamers, encapsulated ingredients, pH adjusters and additives that improve or care for skin feel.
- the dishwashing detergents according to the present invention are liquid and contain water as the main solvent, i.e. they are aqueous dishwashing detergents.
- the water content of the aqueous agent according to the invention is usually 15 to 90% by weight, preferably 20 to 60% by weight.
- organic solvents can be added to the dishwashing detergent.
- Suitable organic solvents include cumene sulfonate, mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the specified concentration range.
- the solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerin, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, Ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propano
- the solvent comprises cumene sulfonate and ethanol.
- the dishwashing detergents described herein may further contain at least one enzyme, preferably a protease.
- the proteases used are preferably alkaline serine proteases. They act as non-specific endopeptidases, that is, they hydrolyze any acid amide bonds that are inside peptides or proteins and thereby cause the breakdown of protein-containing soils on the items to be cleaned. Their pH optimum is usually in the significantly alkaline range.
- subtilisin 309 examples of the proteases that can be used in the agents described herein are subtilisin 309 or functional fragments/variants thereof and variants of the alkaline protease from Bacillus lentus or variants thereof.
- Subtilisin 309 is sold under the trade name Savinase ® by the Distributed by Novozymes A/S, Bagsvaerd, Denmark.
- Optimized enzyme variants of subtilisin 309 from Bacillus lentus are available from Novozymes under the trade names Blaze® and Ovozyme® , which represent a preferred embodiment of the invention.
- the protease variants known as BLAP ® are derived from the alkaline protease from Bacillus lentus DSM 5483.
- protease variants which, compared to the BLAP wt (wild-type) enzyme, in the count according to BLAP wt, have at least one mutation at R99, in particular R99E or R99D, particularly preferred is R99E, and optionally additionally at least one or two , preferably all three of the amino acid substitutions S3T, V4I and V199I, particularly preferred are the BLAP variants as in SeqlD No 4 or 5 of WO 2014/177430 are described.
- the enzymes to be used can also be formulated together with accompanying substances, for example from fermentation.
- the enzymes are preferably used as enzyme liquid formulation(s).
- the proteases are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations.
- These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and/or mixed with stabilizers or other auxiliaries.
- the enzymes can be encapsulated for both the solid and liquid dosage forms, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is covered with a water-, air- and/or chemical-impermeable protective layer.
- Additional active ingredients such as stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers.
- Such capsules are applied using methods known per se, for example by shaking or rolling granulation or in fluid bed processes. Such granules are advantageously low-dust, for example by applying polymeric film formers, and are storage-stable due to the coating.
- Dishwashing detergents according to the invention can alternatively or in addition to the at least one protease contain one or more further enzymes, in particular from the following group: amylases, hemicellulases, cellulases, lipases and oxidoreductases.
- the dishwashing detergent according to the invention particularly preferably also contains at least one amylase.
- the amylase(s) is preferably an ⁇ -amylase.
- the hemicellulase is preferably a ⁇ -glucanase, a pectinase, a pullulanase and/or a mannanase.
- the cellulase is preferably a cellulase mixture or a single-component cellulase, preferably or predominantly an endoglucanase and/or a cellobiohydrolase.
- the oxidoreductase is preferably an oxidase, in particular a choline oxidase, or a perhydrolase.
- the enzymes mentioned can all be formulated as described above for the proteases.
- the at least one enzyme preferably the at least one protease and/or at least one amylase, is present in an amount of 0.01 - 1.6% by weight, preferably 0.05 - 1.2% by weight on the total weight of the dishwashing detergent contained in it.
- the enzyme(s) may be preformulated with enzyme stabilizers in an enzyme composition.
- the enzyme protein usually only forms a fraction of the total weight of the enzyme preparation.
- Enzyme preparations used with preference contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0.8 and 10% by weight. % of enzyme protein.
- an enzyme stabilizer may be included in an amount of 0.05-35% by weight, preferably 0.05-10% by weight, based on the total weight, in the enzyme composition.
- This enzyme composition can then be used in dishwashing detergents according to the invention in amounts which lead to the final concentrations in the dishwashing detergent specified above. Suitable enzyme stabilizers are known in the art.
- the agent according to the invention can accordingly additionally have one or more enzyme stabilizers.
- the protein concentration can be determined using known methods, for example the BCA method (bicinchoninic acid; 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method.
- the active protein concentration is determined by titrating the active protein Centers using a suitable irreversible inhibitor (for proteases, for example phenylmethylsulfonyl fluoride (PMSF)) and determining the residual activity (cf. M. Bender et al., J. Am. Chem. Soc. 88, 24 (1966), pp. 5890-5913 ).
- a suitable irreversible inhibitor for proteases, for example phenylmethylsulfonyl fluoride (PMSF)
- the agent according to the invention can contain one or more additives from the group of polymers and builders, usually in an amount of 0.001 to 5% by weight, preferably 0.01 to 4 % by weight, in particular 0.1 to 3% by weight, particularly preferably 0.2 to 2% by weight, most preferably 0.5 to 1.5% by weight, for example 1% by weight.
- Polymeric thickeners in the context of the present invention are the polycarboxylates, which act as polyelectrolytes and have a thickening effect, preferably homo and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, in particular heteropolysaccharides, as well as other common thickening polymers.
- Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacantum, gellan, ramsan, dextran or xanthan gum and their derivatives, for example propoxylated guar, as well as their mixtures.
- Other polysaccharide thickeners such as starches or cellulose derivatives, can be used alternatively, but preferably in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, e.g.
- hydroxyethyl starch starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.
- Acrylic acid polymers suitable as polymeric thickeners are, for example, high molecular weight homopolymers of acrylic acid (INCI carbomer) crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyvinyl polymers.
- a polyalkenyl polyether in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyvinyl polymers.
- acrylic acid copolymers are the following acrylic acid copolymers: (i) copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters, preferably formed with C1 4 alkanols (INCI Acrylates Copolymer), which include the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate ( CAS 25035 69 2) or from butyl acrylate and methyl methacrylate ( CAS 25852 37 3 ) belong; (ii) crosslinked high molecular weight acrylic acid copolymers, which include, for example, the copolymers of C10 30 alkyl acrylates crosslinked with an allyl ether of sucrose or pentaerythritol with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably formed with C1 4 alkanols, esters (INCI Acrylates/C10-30 Alkyl Acrylates Crosspolymer).
- the content of polymeric thickener is usually not more than 8% by weight, preferably between 0.1 and 7% by weight, particularly preferably between 0.5 and 6% by weight, in particular between 1 and 5% by weight. and most preferably between 1.5 and 4% by weight, for example between 2 and 2.5% by weight, based on the total weight of the dishwashing detergent.
- one or more dicarboxylic acids and/or their salts can be added, in particular a composition of Na salts of adipic, succinic and glutaric acid, such as those available under the trade name Sokalan® DSC is. It is advantageously used in amounts of 0.1 to 8% by weight, preferably 0.5 to 7% by weight, in particular 1.3 to 6% by weight and particularly preferably 2 to 4% by weight, based on the total weight of the dishwashing detergent.
- the agent according to the invention is preferably free of dicarboxylic acid (salts).
- one or more other - especially in hand dishwashing detergents - common auxiliaries and additives, in particular UV stabilizers, perfume, pearlescent agents (INCI opacifying agents; for example glycol distearate, for example Cutina ® AGS from Cognis, or mixtures containing this, for example Euperlane ® from Cognis), dyes, corrosion inhibitors, preservatives (e.g.
- bronopol the technical 2-bromo-2-nitropropane-1,3-diol, also known as bronopol ( CAS 52-51-7 ), which is commercially available, for example, as Myacide ® BT or as Boots Bronopol BT from Boots) or Acticide MBR 1 or Acticide CMB 2, organic salts, disinfectants, pH adjusters and additives that improve skin feel or care for the skin (e.g. dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D panthenol, sericerin, collagen partial hydrolyzate, various vegetable protein partial hydrolysates, protein hydrolyzate fatty acid condensates, liposomes, cholesterol, vegetable and animal oils such as e.g.
- dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D panthenol, sericerin, collagen partial hydrolyzate, various vegetable protein partial hydrolysates, protein hydrolyzate fatty acid condensates
- lecithin soybean oil, etc.
- plant extracts such as aloe vera, azulene, witch hazel extracts, algae extracts, etc., allantoin, AHA complexes, glycerin, urea, quaternized hydroxyethyl cellulose), in amounts usually not more than 8% by weight based on the total weight of the dishwashing detergent.
- Na-xylenesulfonate can be used as an additive.
- the pH value of the agent according to the invention can be adjusted using conventional pH regulators, for example acids such as mineral acids or citric acid and/or alkalis such as sodium or potassium hydroxide, with a range of 4 to 9 - particularly if hand tolerance is desired.
- acids such as mineral acids or citric acid
- alkalis such as sodium or potassium hydroxide
- the agent according to the invention can contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5% by weight, preferably 0.005 to 3% by weight, in particular 0 .01 to 2% by weight, particularly preferably 0.05 to 1% by weight, most preferably 0.1 to 0.5% by weight, for example 0.2% by weight.
- buffer substances that are also complexing agents or even chelating agents (chelators, INCI chelating agents) are preferred.
- Particularly preferred buffer substances are citric acid or citrates, in particular sodium and potassium citrates, for example trisodium citrate 2 H2O and tripotassium citrate H2O.
- Table 1 The example compositions shown in Table 1 were provided using a basic formulation comprising 6.4% by weight anionic surfactant and 1.6% amine oxide surfactant. The total amount of surfactant is therefore 8% by weight. The recipe also contained smaller amounts of fragrances and dyes as well as protease and amylase enzymes. Table 1 Example Reference symbols EtOH C.S AM / LM total NaCl C1 10 0 0.6 13 4.4 E1 50 1.5 0.6 4 6.7 E2 30 0.75 0.6 6 5.27 E3 40 1,125 0.6 5 6 E4 80 1.5 0.6 4 7.65 E5 70 1.5 0.6 4 7.2
- compositions result from the values in Table 1 and the basic recipe.
- the solvent includes ethanol and cumene sulfonate, CS.
- the table also shows the ratio of the total amount of surfactant to the total amount of solvent.
- the viscosity curves are in Figure 1 shown.
- the example recipes E1 to E5 according to the invention show that the compositions according to the invention in particular have a good viscosity profile in the skin-friendly pH range of at least 7.
- the viscosities of the compositions are such that the consumer perceives the compositions to be of high quality and the viscosity within the relevant pH range has a relatively small/stable change depending on the pH value.
- the homogeneous mixing of the components using stirring tools was possible sufficiently well.
- the comparison formulation C1 showed an unsuitable viscosity profile. High viscosity values could be achieved. In contrast to the example recipes according to the invention, however, these were not sufficiently constant/stable depending on the pH value. The manufacturing process of such a composition is made considerably more difficult or even impossible due to the viscosity peaks, since sufficient mixing of the composition using stirring tools is prevented.
- composition E2 has a slight peak in viscosity.
- the ratio of total surfactant content to solvent is 6. Therefore, according to a preferred embodiment, a ratio of total surfactant content to solvent is described which is less than 10, in particular 4 and 5, as is the case in examples E1, E3, E4, and E5 is.
- example compositions with a higher total surfactant content were provided.
- the corresponding example compositions shown in Table 2 were provided using a basic recipe comprising 16% by weight anionic surfactant and 4% amine oxide surfactant. The total amount of surfactant is therefore 20% by weight.
- the recipe also contained smaller amounts of fragrances and dyes as well as protease and amylase enzymes.
- Table 2 Example Reference symbols EtOH C.S AM / LM total NaCl C2 110 1 1 10 1,875 E6 150 3.9 1 4 4.9
- compositions result from the values in Table 2 and the basic recipe.
- the solvent includes ethanol and cumene sulfonate, CS.
- the table also shows the ratio of the total amount of surfactant to the total amount of solvent.
- the viscosity curves are in Figure 2 shown.
- the comparison formulation C2 showed an even more pronounced viscosity peak than in the compositions with lower total surfactant amounts C1.
- the problem already presented applies particularly to higher total surfactant contents.
- composition E6 according to the invention is characterized by a particularly stable viscosity profile. Compared to the recipes E1 to E5 with a lower total surfactant content, even better stabilization of the viscosity is achieved.
- the advantageous stabilization of the viscosity curve occurs particularly at higher total surfactant amounts of at least 12% by weight.
- the ratio of total surfactant content to solvent is also preferably less than 10, in particular between 4 and 6, more preferably 4 or 5.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Description
Geschirrspülmittel, insbesondere flüssige Geschirrspülmittel für die manuelle Reinigung, von Geschirr sind bekannt. Allerdings werden niedrigviskose Handgeschirrspülzusammensetzungen vom Verbraucher als qualitativ geringwertiger wahrgenommen. Daher stellt die Viskosität ein wichtiges Qualitätskriterium für Handgeschirrspülzusammensetzungen dar. Gleichzeitig sollen moderne Handgeschirrspülmittel umweltschonend produziert werden und gleichzeitig eine möglichst gute Reinigungsleistung aufweisen. Eine weitere Besonderheit von Handgeschirrspülzusammensetzungen stellt die Anforderung dar, dass diese schonend zur Haut sein sollten.Dishwashing detergents, in particular liquid dishwashing detergents for manual cleaning, of dishes are known. However, low-viscosity hand dishwashing compositions are perceived by consumers as being of lower quality. Viscosity is therefore an important quality criterion for hand dishwashing compositions. At the same time, modern hand dishwashing detergents should be produced in an environmentally friendly manner and at the same time have the best possible cleaning performance. Another special feature of hand dishwashing compositions is the requirement that they should be gentle on the skin.
Die Anforderungen, die an moderne Handgeschirrspülzusammensetzungen gestellt werden, sind vor diesem Hintergrund also entsprechend hoch. Insbesondere die Einstellung der Viskosität im Herstellungsprozess stellt eine Herausforderung dar. So können Viskositätsspitzen der Zusammensetzungen die homogene Vermischung der Komponenten mittels Rührwerkzeugen erschweren, sodass die Prozesse energieaufwändiger und zeitaufwändiger oder sogar gänzlich unmöglich werden.Against this background, the demands placed on modern hand dishwashing compositions are correspondingly high. In particular, adjusting the viscosity in the manufacturing process represents a challenge. Viscosity peaks in the compositions can make it difficult to mix the components homogeneously using stirring tools, making the processes more energy-intensive and time-consuming or even completely impossible.
Insgesamt besteht also die ein Bedarf nach Handgeschirrspülmitteln, die den oben genannten Anforderungen genügen.Overall, there is a need for hand dishwashing detergents that meet the above requirements.
Die Aufgabe, die der vorliegenden Erfindung zu Grunde liegt, bestehts also darin, Zusammensetzungen bereitzustellen, die einerseits vom Verbraucher als qualitativ hochwertig wahrgenommen werden, als auch umweltfreundlich prozessierbar sind und gleichzeitig eine gute Hautverträglichkeit aufweisen.The object on which the present invention is based is therefore to provide compositions which, on the one hand, are perceived by the consumer as being of high quality and which can also be processed in an environmentally friendly manner and at the same time have good skin compatibility.
Gelöst wird diese Aufgabe durch ein Handgeschirrspülzusammensetzung umfassend:
- wenigstens ein Tensid,
- wobei die Zusammensetzung ferner umfasst
- wenigstens ein anorganisches Salz, wobei das Salz ein Alkalisalz und/oder ein Erdalkalisalz ist, sowie ein Lösungsmittel wobei das Lösungsmittel Ethanol und Cumolsulfonat umfasst, und wobei
- der pH Wert der Zusammensetzung wenigstens 7,5 beträgt und weniger als 8,5 und die Viskosität der
Zusammensetzung 1000 cps bis 4000 cps beträgt.
- at least one surfactant,
- wherein the composition further comprises
- at least one inorganic salt, the salt being an alkali metal salt and/or an alkaline earth metal salt, and a solvent, the solvent comprising ethanol and cumene sulfonate, and wherein
- the pH of the composition is at least 7.5 and less than 8.5 and the viscosity of the composition is 1000 cps to 4000 cps.
Es wurde überraschend festgestellt, dass die erfindungsgemäßen Zusammensetzungen insbesondere ein gutes Viskositätsprofil im hautfreundlichen pH Bereich von wenigstens 7,5 bis weniger als 8,5 aufzeigen. Unter einem "gutem Viskositätsprofil" ist in diesem Zusammenhang gemeint, dass die Viskosität der Zusammensetzungen zum einen derart ist, dass die Zusammensetzungen vom Verbraucher als qualitativ hochwertig wahrgenommen werden und die Viskosität innerhalb des betreffenden pH Bereichs eine verhältnismäßig geringe Veränderung in Abhängigkeit vom pH-Wert aufweist. Hierbei wurde identifiziert, dass der Viskositätsbereich zwischen 1000 cps bis 4000 cps eine besonders vorteilhafter Bereich im Sinne eine Balance Findung von guter Prozessierbarkeit einerseits und hochwertigen Produkteigenschaften andererseits darstellt.It was surprisingly found that the compositions according to the invention in particular have a good viscosity profile in the skin-friendly pH range of at least 7.5 to less than 8.5. In this context, a “good viscosity profile” means that the viscosity of the compositions is such that the consumer perceives the compositions as being of high quality and the viscosity is within the range The relevant pH range has a relatively small change depending on the pH value. It was identified that the viscosity range between 1000 cps and 4000 cps represents a particularly advantageous range in terms of finding a balance between good processability on the one hand and high-quality product properties on the other.
Gemäß einer weiter bevorzugten Ausführungsform beträgt die Viskosität der Zusammensetzung wenigstens 1500 cps bis 2500 cps.According to a further preferred embodiment, the viscosity of the composition is at least 1500 cps to 2500 cps.
Gemäß einer noch weiter bevorzugten Ausführungsform beträgt die Viskosität der Zusammensetzung wenigstens 1800 cps bis 2200 cps.According to a still further preferred embodiment, the viscosity of the composition is at least 1800 cps to 2200 cps.
Die Viskosität wird mittels eines Brookfield LVDV II+, Spindel 31 bei einer Temperatur von 20°C, mit 12 Upm bestimmt.The viscosity is determined using a Brookfield LVDV II+, spindle 31 at a temperature of 20 ° C, at 12 rpm.
Gemäß einer bevorzugten Ausführungsform wird die Handgeschirrspülzusammensetzung beschrieben, wobei das Salz ein Alkalihalogenid und/oder ein Erdalkalihalogenid ist, bevorzugt Natriumchlorid.According to a preferred embodiment, the hand dishwashing composition is described, wherein the salt is an alkali metal halide and/or an alkaline earth metal halide, preferably sodium chloride.
Gemäß einer bevorzugten Ausführungsform wird die Handgeschirrspülzusammensetzung beschrieben, wobei die Menge an anorganischem Salz wenigstens 2 Gew.-% beträgt, bevorzugt wenigstens 4 Gew.-%.According to a preferred embodiment, the hand dishwashing composition is described, wherein the amount of inorganic salt is at least 2% by weight, preferably at least 4% by weight.
Gemäß einer bevorzugten Ausführungsform wird die Handgeschirrspülzusammensetzung beschrieben, wobei das Verhältnis von Gesamttensidgehalt zu Lösungsmittel weniger als 10 beträgt, bevorzugt zwischen 4 und 6 liegt, weiter bevorzugt 4 oder 5 beträgt.According to a preferred embodiment, the hand dishwashing composition is described, wherein the ratio of total surfactant content to solvent is less than 10, preferably between 4 and 6, more preferably 4 or 5.
Gemäß einer bevorzugten Ausführungsform wird die Handgeschirrspülzusammensetzung beschrieben, wobei die Handgeschirrspülzusammensetzung wenigstens ein Enzym umfasst.According to a preferred embodiment, the hand dishwashing composition is described, wherein the hand dishwashing composition comprises at least one enzyme.
Gemäß einer bevorzugten Ausführungsform wird die Handgeschirrspülzusammensetzung beschrieben, wobei die Handgeschirrspülzusammensetzung ein anionisches Tensid umfasst.According to a preferred embodiment, the hand dishwashing composition is described, wherein the hand dishwashing composition comprises an anionic surfactant.
Gemäß einer bevorzugten Ausführungsform wird die Handgeschirrspülzusammensetzung beschrieben, wobei die Handgeschirrspülzusammensetzung ein Aminoxid und/oder ein Betain Tensid umfasst.According to a preferred embodiment, the hand dishwashing composition is described, wherein the hand dishwashing composition comprises an amine oxide and/or a betaine surfactant.
Gemäß einer bevorzugten Ausführungsform wird die Handgeschirrspülzusammensetzung beschrieben, wobei die Gesamtmenge an Tensid wenigstens 8 Gew.-% beträgt, weiter bevorzugt wenigstens 12 Gew.-% beträgt, weiter bevorzugt wenigstens 20 Gew.-%.According to a preferred embodiment, the hand dishwashing composition is described, wherein the total amount of surfactant is at least 8% by weight, more preferably at least 12% by weight, more preferably at least 20% by weight.
Gemäß einer bevorzugten Ausführungsform wird die Handgeschirrspülzusammensetzung beschrieben, wobei die Handgeschirrspülzusammensetzung wenigstens ein Enzym umfasst. Gemäß einer bevorzugten Ausführungsform wird die Handgeschirrspülzusammensetzung beschrieben, wobei die Handgeschirrspülzusammensetzung ein anionisches Tensid umfasst. Gemäß einer bevorzugten Ausführungsform beträgt die Gesamtmenge an Lösungsmittel wenigstens 1 Gew.-%, weiter bevorzugt wenigstens 2 Gew.-% und weiter bevorzugt wenigstens 2, 5 Gew..-%.According to a preferred embodiment, the hand dishwashing composition is described, wherein the hand dishwashing composition comprises at least one enzyme. According to a preferred embodiment, the hand dishwashing composition is described, wherein the hand dishwashing composition comprises an anionic surfactant. According to a preferred embodiment, the total amount of solvent is at least 1% by weight, more preferably at least 2% by weight and more preferably at least 2.5% by weight.
Gemäß einem weiteren Aspekt wird die Verwendung der Zusammensetzung zur manuellen Reinigung von Geschirr verwendet.According to a further aspect, the use of the composition is for manual cleaning of dishes.
Gemäß einem weiteren Aspekt wird die Herstellung der Zusammensetzung zur manuellen Reinigung von Geschirr beschreiben, umfassend die Schritte:
- Bereitstellen wenigstens eines Tensid,
- Bereitstellen wenigstens eines anorganischen Salzes, wobei das Salz ein Alkalisalz und/oder ein Erdalkalisalz ist,
- Bereitstellen von Lösungsmittel, und
- Einstellen des pH Wertes der Zusammensetzung in einem Bereich von wenigstens 7.
- providing at least one surfactant,
- Providing at least one inorganic salt, the salt being an alkali metal salt and/or an alkaline earth metal salt,
- Providing solvent, and
- Adjusting the pH of the composition to a range of at least 7.
Bevorzugt ist die Menge an Gesamttensid wenigstens 5% Gew.-% ,10 Gew.-% bezogen auf das Gesamtgewicht der Zusammensetzung.Preferably, the amount of total surfactant is at least 5% by weight, 10% by weight based on the total weight of the composition.
Gemäß einer bevorzugten Ausführungsform wird eine Handgeschirrspülzusammensetzung beschrieben, wobei der Anteil an Aminoxiden, die einen C16 oder längeren Rest aufweisen, weniger als 20 %, weiter bevorzugt weniger als 10 %, bezogen auf das Gesamtgewicht der Aminoxide in der Zusammensetzung ist.According to a preferred embodiment, a hand dishwashing composition is described, wherein the proportion of amine oxides having a C16 or longer residue is less than 20%, more preferably less than 10%, based on the total weight of the amine oxides in the composition.
Gemäß einer bevorzugten Ausführungsform wird eine Handgeschirrspülzusammensetzung beschrieben, wobei das anionische Tensid in einer Menge von wenigstens 4 Gew.-%, bevorzugt wenigstens 10 Gew.-% bezogen auf das Gesamtgewicht der Zusammensetzung vorliegt. Gemäß einer bevorzugten Ausführungsform wird eine Handgeschirrspülzusammensetzung beschrieben, wobei Aminxoid in einer Menge von wenigstens 4 Gew.-% bezogen auf das Gesamtgewicht der Zusammensetzung vorliegt.According to a preferred embodiment, a hand dishwashing composition is described, wherein the anionic surfactant is present in an amount of at least 4% by weight, preferably at least 10% by weight, based on the total weight of the composition. According to a preferred embodiment, a hand dishwashing composition is described, wherein aminexoid is present in an amount of at least 4% by weight based on the total weight of the composition.
Gemäß einer bevorzugten Ausführungsform wird eine Handgeschirrspülzusammensetzung beschrieben, wobei Betain in einer Menge von wenigstens 4 Gew.-% bezogen auf das Gesamtgewicht der Zusammensetzung vorliegt.According to a preferred embodiment, a hand dishwashing composition is described, wherein betaine is present in an amount of at least 4% by weight based on the total weight of the composition.
Gemäß einer bevorzugten Ausführungsform wird eine Handgeschirrspülzusammensetzung beschrieben, wobei die Zusammensetzung ein organisches Lösungsmittel umfasst, welches wenigstens in einer Menge von 2 Gew.-% vorliegt Gemäß einer bevorzugten Ausführungsform wird eine Handgeschirrspülzusammensetzung beschrieben, wobei der Anteil an Aminoxiden, die einen C12 Rest aufweisen zwischen 50 und 85 % bezogen auf die Gesamtmenge an Aminoxid beträgt, bevorzugt zwischen 60 und 85 %. Gemäß einer bevorzugten Ausführungsform wird eine Handgeschirrspülzusammensetzung beschrieben, wobei der Anteil an Aminoxiden, die einen C14 Rest aufweisen, zwischen 20 und 35 % bezogen auf die Gesamtmenge an Aminoxid beträgt.According to a preferred embodiment, a hand dishwashing composition is described, wherein the composition comprises an organic solvent which is present in at least an amount of 2% by weight. According to a preferred embodiment, a hand dishwashing composition is described, wherein the proportion of amine oxides that have a C12 residue is between 50 and 85% based on the total amount of amine oxide, preferably between 60 and 85%. According to a preferred embodiment, a hand dishwashing composition is described, wherein the proportion of amine oxides which have a C14 residue is between 20 and 35% based on the total amount of amine oxide.
Gemäß einer bevorzugten Ausführungsform wird eine Handgeschirrspülzusammensetzung beschrieben, wobei der Anteil an Aminoxiden, die nur C10 oder kleinere Reste aufweisen, weniger als 5 % bezogen auf die Gesamtmenge an Aminoxid beträgt.According to a preferred embodiment, a hand dishwashing composition is described, wherein the proportion of amine oxides which only have C10 or smaller residues is less than 5% based on the total amount of amine oxide.
Gemäß einer bevorzugten Ausführungsform wird eine Handgeschirrspülzusammensetzung beschrieben, wobei das Tensidsystem mindestens ein anionisches Tensid, ausgewählt aus Ethersulfaten, Alkylsulfaten und Mischungen davon enthält.According to a preferred embodiment, a hand dishwashing composition is described, wherein the surfactant system contains at least one anionic surfactant selected from ether sulfates, alkyl sulfates and mixtures thereof.
Handgeschirrspülzusammensetzung wobei das Geschirrspülzusammensetzung mindestens einen zusätzlichen Inhaltsstoff ausgewählt aus der Gruppe bestehend aus Wasser, Enzymen, organischen Lösungsmitteln, Enzymen, Additiven zur Verbesserung des Ablauf- und Trocknungsverhaltens, zur Einstellung der Viskosität und/oder zur Stabilisierung, UV-Stabilisatoren, Parfüm, Perlglanzmitteln, Farbstoffen, Korrosionsinhibitoren, Bitterstoffen, organischen Salzen, Desinfektionsmitteln, strukturgebenden Polymeren, Entschäumern, verkapselten Inhaltsstoffen, pH-Stellmitteln sowie Hautgefühl-verbessernden oder pflegenden Additiven enthält.Hand dishwashing composition, wherein the dishwashing composition contains at least one additional ingredient selected from the group consisting of water, enzymes, organic solvents, enzymes, additives to improve drainage and drying behavior, to adjust the viscosity and / or for stabilization, UV stabilizers, perfume, pearlescent agents, Dyes, corrosion inhibitors, bitter substances, organic salts, disinfectants, structuring polymers, defoamers, encapsulated ingredients, pH adjusters and additives that improve or care for skin feel.
In einem weiteren Aspekt richtet sich die vorliegende Erfindung ferner auf die Verwendung des erfindungsgemäßen Geschirrspülmittels zur manuellen Reinigung von Geschirr.In a further aspect, the present invention is further directed to the use of the dishwashing detergent according to the invention for manually cleaning dishes.
"Mindestens ein", wie hierin verwendet, bezieht sich auf 1 oder mehr, beispielsweise 2, 3, 4, 5, 6, 7, 8, 9 oder mehr. Im Zusammenhang mit Bestandteilen der hierin beschriebenen Verbindungen bezieht sich diese Angabe nicht auf die absolute Menge an Molekülen, sondern auf die Art des Bestandteils. "Mindestens ein Tensid" bedeutet daher beispielsweise, dass nur eine Art von Tensidverbindung oder mehrere verschiedene Arten von Tensidverbindungen, ohne Angaben über die Menge der einzelnen Verbindungen zu machen, enthalten sein können."At least one" as used herein refers to 1 or more, for example 2, 3, 4, 5, 6, 7, 8, 9 or more. In connection with components of the compounds described herein, this information does not refer to the absolute amount of molecules, but rather to the type of component. “At least one surfactant” therefore means, for example, that only one type of surfactant compound or several different types of surfactant compounds can be included, without providing information about the amount of the individual compounds.
Alle im Zusammenhang mit den hierin beschriebenen Geschirrspülmitteln angegeben Mengenangaben beziehen sich, sofern nichts anderes angegeben ist, auf Gew.-% jeweils bezogen auf das Gesamtgewicht des Geschirrspülmittels. Des Weiteren beziehen sich derartige Mengenangaben, die sich auf mindestens einen Bestandteil beziehen, immer auf die Gesamtmenge dieser Art von Bestandteil, die in dem Geschirrspülmittel enthalten ist, sofern nicht explizit etwas anderes angegeben ist. Das heißt, dass sich derartige Mengenangaben, beispielsweise im Zusammenhang mit "mindestens einem Tensid", auf die Gesamtmenge von Tensiden, welche in dem Geschirrspülmittel enthalten sind, bezieht, wenn nicht explizit etwas anderes angegeben ist.Unless otherwise stated, all quantities given in connection with the dishwashing detergents described herein refer to % by weight based on the total weight of the dishwashing detergent. Furthermore, such quantities that relate to at least one component always refer to the total amount of this type of component contained in the dishwashing detergent, unless explicitly stated otherwise. This means that such quantities, for example in connection with “at least one surfactant”, refer to the total amount of surfactants contained in the dishwashing detergent, unless explicitly stated otherwise.
Zahlenwerte, die hierin ohne Dezimalstellen angegeben sind, beziehen sich jeweils auf den vollen angegebenen Wert mit einer Dezimalstelle. So steht beispielsweise "99%" für "99,0%".Numerical values stated herein without decimal places refer to the full stated value with one decimal place. For example, "99%" stands for "99.0%".
Der Ausdrücke "ungefähr" "ca." oder "etwa", in Zusammenhang mit einem Zahlenwert, bezieht sich auf eine Varianz von ±10% bezogen auf den angegebenen Zahlenwert, bevorzugt ±5%, besonders bevorzugt ±1 %.The expressions “approximately” “approx.” or "about", in connection with a numerical value, refers to a variance of ±10% based on the specified numerical value, preferably ±5%, particularly preferably ±1%.
Der Ausdruck "im Wesentlichen frei von" bedeutet, dass die jeweilige Verbindung grundsätzlich enthalten sein kann, dann allerdings in einer Menge vorliegt, die eine Funktion der anderen Komponenten nicht beeinträchtigt. Im Rahmen der vorliegenden Erfindung wird daher unter der Eigenschaft "im Wesentlichen frei von" einer bestimmten Verbindung bevorzugt ein Gesamtgewicht von unter 0,1 Gew.-%, stärker bevorzugt unter 0,001 Gew.-%, insbesondere frei von dieser, bezogen auf das Gesamtgewicht des Geschirrspülmittels, angesehen.The expression “essentially free of” means that the respective compound can in principle be included, but is then present in an amount that does not impair the function of the other components. In the context of the present invention, the property “substantially free of” a particular compound is therefore preferably a total weight of less than 0.1% by weight, more preferably less than 0.001% by weight, in particular free of this, based on the total weight of dishwashing detergent.
Numerische Bereiche, die in dem Format "in/von x bis y" angegeben sind, schließen die genannten Werte ein. Wenn mehrere bevorzugte numerische Bereiche in diesem Format angegeben sind, ist es selbstverständlich, dass alle Bereiche, die durch die Kombination der verschiedenen Endpunkte entstehen, ebenfalls erfasst werden.Numerical ranges specified in the format "in/from x to y" include the stated values. When multiple preferred numerical ranges are specified in this format, it is understood that any ranges resulting from the combination of the various endpoints will also be captured.
Angaben über das Molekulargewicht beziehen sich auf das gewichtsmittlere Molekulargewicht in g/mol, falls nicht explizit das zahlenmittlere Molekulargewicht genannt ist. Molekulargewichte werden bevorzugt mittels GPC unter Verwendung von Polystyrol-Standards ermittelt.Information about the molecular weight refers to the weight-average molecular weight in g/mol, unless the number-average molecular weight is explicitly stated. Molecular weights are preferably determined by GPC using polystyrene standards.
Im Rahmen der vorliegenden Erfindung stehen Fettsäuren bzw. Fettalkohole bzw. deren Derivate - soweit nicht anders angegeben - stellvertretend für verzweigte oder unverzweigte Carbonsäuren bzw. Alkohole bzw. deren Derivate mit vorzugsweise 6 bis 22 Kohlenstoffatomen. Insbesondere sind auch die beispielsweise nach der ROELENschen Oxo-Synthese erhältlichen Oxo-Alkohole bzw. deren Derivate entsprechend einsetzbar.In the context of the present invention, fatty acids or fatty alcohols or their derivatives - unless otherwise stated - represent branched or unbranched carboxylic acids or alcohols or their derivatives with preferably 6 to 22 carbon atoms. In particular, the oxo alcohols or their derivatives obtainable, for example, by ROELEN's oxo synthesis can also be used accordingly.
Sind Bestandteile der vorliegenden Mittel Salze, so handelt es sich dabei bevorzugt um Alkalimetall- oder Erdalkalimetallsalze der jeweiligen Verbindungen, stärker bevorzugt um die Alkalimetallsalze, insbesondere um die Natrium- oder Kaliumsalze, am stärksten bevorzugt Natriumsalze, davon. Wann immer im Folgenden Erdalkalimetalle als Gegenionen für einwertige Anionen genannt sind, so bedeutet das, dass das Erdalkalimetall natürlich nur in der halben - zum Ladungsausgleich ausreichenden - Stoffmenge wie das Anion vorliegt.If components of the present agents are salts, they are preferably alkali metal or alkaline earth metal salts of the respective compounds, more preferably the alkali metal salts, in particular the sodium or potassium salts, most preferably sodium salts thereof. Whenever alkaline earth metals are mentioned below as counterions for monovalent anions, this means that the alkaline earth metal is of course only present in half the amount of substance as the anion - which is sufficient to balance the charge.
In der vorliegenden Erfindung sind substituierte Reste bevorzugt solche Reste, in welchen der Substituent ausgewählt ist aus -F, -Cl, -Br, -OH, -OC1-4Alkyl, =O, -NH2, oder-N(C1-4Alkyl)2, bevorzugt ersetzt dabei der Substituent ein oder mehrere H Atome.In the present invention, substituted radicals are preferably those radicals in which the substituent is selected from -F, -Cl, -Br, -OH, -OC1-4Alkyl, =O, -NH2, or -N(C1-4Alkyl)2 , the substituent preferably replaces one or more H atoms.
Diese und weitere Aspekte, Merkmale und Vorteile der Erfindung werden für den Fachmann aus dem Studium der folgenden detaillierten Beschreibung und Ansprüche ersichtlich. Dabei kann jedes Merkmal oder jede Ausführungsform aus einem Aspekt der Erfindung in jedem anderen Aspekt der Erfindung eingesetzt werden. Beispielweise können beschriebene Merkmale oder Ausführungsformen der Geschirrspülmittel auch auf die beanspruchten Verwendungen angewendet werden, und umgekehrt. Ferner ist es selbstverständlich, dass die hierin enthaltenen Beispiele die Erfindung beschreiben und veranschaulichen sollen, diese aber nicht einschränken und insbesondere die Erfindung nicht auf diese Beispiele beschränkt ist.These and other aspects, features and advantages of the invention will become apparent to those skilled in the art from reading the following detailed description and claims. Any feature or embodiment from one aspect of the invention can be used in any other aspect of the invention. For example, described features or embodiments of the dishwashing detergents can also be applied to the claimed uses, and vice versa. Furthermore, it is to be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it and in particular the invention is not limited to these examples.
Das erfindungsgemäße Geschirrspülmittel ist bevorzugt im Wesentlichen frei von kationischen Tensiden.The dishwashing detergent according to the invention is preferably essentially free of cationic surfactants.
Gemäß einer Ausführungsform weist die Zusammensetzung mindestens eine Alkylbenzolsulfonat auf, welches dabei bevorzugt einen C2-18 Alkylrest aufweisen. Besonders bevorzugt ist es Cumolsulfonat. Erfindungsgemäß verstehen sich unter dem Merkmal Alkylbenzolsulfonat lediglich ein mit einem Alkylrest substituierte Benzolring, der ferner einen Sulfonatrest trägt.According to one embodiment, the composition has at least one alkyl benzene sulfonate, which preferably has a C2-18 alkyl radical. Cumenesulfonate is particularly preferred. According to the invention, the term alkylbenzenesulfonate refers only to a benzene ring substituted with an alkyl radical and which also carries a sulfonate radical.
In bevorzugten Ausführungsformen ist das mindestens eine Alkylbenzolsulfonat in 0,5 bis 50 Gew.%, bevorzugt 0,5 bis 30 Gew.-%, insbesondere bevorzugt in 0,5 bis 5 Gew.-%, basierend auf dem Gesamtgewicht des Geschirrspülmittels enthalten.In preferred embodiments, the at least one alkylbenzene sulfonate is contained in 0.5 to 50% by weight, preferably 0.5 to 30% by weight, particularly preferably in 0.5 to 5% by weight, based on the total weight of the dishwashing detergent.
Das mindestens eine Fettalkoholsulfat ist bevorzugt ausgewählt aus C8-18 Fettalkoholsulfaten, Besonders bevorzugte Fettalkoholsulfate sind abgeleitet von C12-18-Fettalkoholen, beispielsweise von Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol. Insbesondere ist Natriumlaurylsulfat bevorzugt.The at least one fatty alcohol sulfate is preferably selected from C8-18 fatty alcohol sulfates. Particularly preferred fatty alcohol sulfates are derived from C12-18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol. Sodium lauryl sulfate is particularly preferred.
In bevorzugten Ausführungsformen ist das mindestens eine Fettalkoholsulfat in 0,5 bis 45 Gew.-%, bevorzugt 0,5 bis 40 Gew.-%, stärker bevorzugt in 3 bis 15 Gew.-%, basierend auf dem Gesamtgewicht des Geschirrspülmittels enthalten.In preferred embodiments, the at least one fatty alcohol sulfate is contained in 0.5 to 45% by weight, preferably 0.5 to 40% by weight, more preferably in 3 to 15% by weight, based on the total weight of the dishwashing detergent.
In einer bevorzugten Ausführungsform ist das mindestens eine Aminoxid eine Verbindungen, die die Formel R1R2R3NO aufweist, wobei jedes R1, R2 und R3 unabhängig von den anderen eine gegebenenfalls substituierte, beispielsweise Hydroxy-substituierte, C1-C30 Kohlenwasserstoffkette ist. Besonders bevorzugt eingesetzte Aminoxide sind solche in denen R1 C10-C16 Alkyl und R2 und R3 jeweils unabhängig C1-C4 Alkyl sind, insbesondere C10-C16 Alkyldimethylaminoxide. Beispielhafte Vertreter geeigneter Aminoxide sind N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid. Das mindestens eine Aminoxid ist bevorzugt ausgewählt aus C12-16 Aminoxiden, insbesondere bevorzugt aus niederkettigen C12-14 Alkyldimethylaminoxiden.In a preferred embodiment, the at least one amine oxide is a compound having the formula R1R2R3NO, where each R1, R2 and R3, independently of the others, is an optionally substituted, for example hydroxy-substituted, C1-C30 hydrocarbon chain. Particularly preferred amine oxides used are those in which R1 is C10-C16 alkyl and R2 and R3 are each independently C1-C4 alkyl, in particular C10-C16 alkyldimethylamine oxides. Examples of suitable amine oxides are N-cocoalkyl-N,N-dimethylamine oxide and N-tallow alkyl-N,N-dihydroxyethylamine oxide. The at least one amine oxide is preferably selected from C12-16 amine oxides, particularly preferably from low-chain C12-14 alkyldimethylamine oxides.
In bevorzugten Ausführungsformen ist das mindestens eine Aminoxid in 0,1 bis 20 Gew.-%, bevorzugt 0,3 bis 10 Gew.-%, stärker bevorzugt in 0,5 bis 3 Gew.-%, basierend auf dem Gesamtgewicht des Geschirrspülmittels enthalten.In preferred embodiments, the at least one amine oxide is contained in 0.1 to 20 wt.%, preferably 0.3 to 10 wt.%, more preferably 0.5 to 3 wt.%, based on the total weight of the dishwashing detergent .
Falls vorhanden, so ist das mindestens eine weitere anionische, nichtionische oder zwitterionische Tensid, bevorzugt in 0,1 bis 45 Gew.-%, bevorzugt 0,5 bis 40 Gew.-%, stärker bevorzugt in 1 bis 25 Gew.-%, basierend auf dem Gesamtgewicht des Geschirrspülmittels enthalten.If present, this is at least one further anionic, nonionic or zwitterionic surfactant, preferably in 0.1 to 45% by weight, preferably 0.5 to 40% by weight, more preferably in 1 to 25% by weight, based on the total weight of the dishwashing detergent included.
Als weitere anionische Tenside sind alle für Geschirrspülmittel bekannten anionischen Tenside geeignet.All anionic surfactants known for dishwashing detergents are suitable as further anionic surfactants.
Geeignete weitere Tenside sind beispielsweise alpha-Olefinsulfonate. Bevorzugte alpha-Olefinsulfonate sind ausgewählt aus C10-20 alpha-Olefinsulfonaten, stärker bevorzugt aus linearen C10-20 alpha-Olefinsulfonaten. Insbesondere ist es ausgewählt aus C12-14 alpha-Olefinsulfonaten; am stärksten bevorzugt ist es ein lineares C12-14 alpha-Olefinsulfonat.Other suitable surfactants are, for example, alpha-olefin sulfonates. Preferred alpha-olefin sulfonates are selected from C10-20 alpha-olefin sulfonates, more preferably linear C10-20 alpha-olefin sulfonates. In particular it is selected from C12-14 alpha-olefin sulfonates; most preferably it is a linear C12-14 alpha-olefin sulfonate.
Das mindestens eine alpha-Olefinsulfonat ist dabei bevorzugt in 2,5 bis 45 Gew.-%, stärker bevorzugt 3 bis 30 Gew.-%, insbesondere bevorzugt in 5 bis 25 Gew.-%, basierend auf dem Gesamtgewicht des Geschirrspülmittels enthalten.The at least one alpha-olefin sulfonate is preferably contained in 2.5 to 45% by weight, more preferably 3 to 30% by weight, particularly preferably in 5 to 25% by weight, based on the total weight of the dishwashing detergent.
Ein geeignetes alpha-Olefinsulfonat ist beispielsweise unter dem Handelsnahmen Bio-Terge® AS-40 der Firma Stephan kommerziell erhältlich.A suitable alpha-olefin sulfonate is commercially available, for example, under the trade name Bio- Terge® AS-40 from Stephan.
In einer Ausführungsform ist das mindestens eine weitere anionische Tensid ausgewählt aus Ethersulfaten, Alkylsulfaten und Mischungen davon.In one embodiment, the at least one further anionic surfactant is selected from ether sulfates, alkyl sulfates and mixtures thereof.
Bevorzugte Ethersulfate sind solche der Formel (I)
R1-O-(AO)n-SO3- X+ (I).
Preferred ether sulfates are those of the formula (I)
R1-O-(AO)n-SO3- X+ (I).
In dieser Formel (I) steht R1 für einen linearen oder verzweigten, substituierten oder unsubstituierten Alkylrest, vorzugsweise für einen linearen, unsubstituierten Alkylrest, besonders bevorzugt für einen Fettalkoholrest. Bevorzugte Reste R1 sind ausgewählt aus Decyl-, Undecyl-, Dodecyl-, Tridecyl-, Tetradecyl, Pentadecyl-, Hexadecyl-, Heptadecyl-, Octadecyl-, Nonadecyl-, Eicosylresten und deren Mischungen, wobei die Vertreter mit gerader Anzahl an C-Atomen bevorzugt sind. Besonders bevorzugte Reste R1 sind abgeleitet von C12-C18-Fettalkoholen, beispielsweise von Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder von C10-C20-Oxoalkoholen.In this formula (I), R1 represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R1 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives having an even number of carbon atoms are preferred. Particularly preferred radicals R1 are derived from C12-C18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C10-C20 oxo alcohols.
X steht für ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations, bevorzugt sind dabei die Alkalimetallionen und darunter Na+ oder K+, wobei Na+ äußerst bevorzugt ist. Weitere Kationen X+ können ausgewählt sein aus NH4+, ½ Zn2+, ½ Mg2+,½ Ca2+,½ Mn2+, und deren Mischungen.X stands for a single-quality cation or the n-ten part of an N-quality cation, preferably the alkali metal ions and below Na+ or K+, where Na+ is extremely preferred. Further cations
AO steht für eine Ethylenoxid- (EO) oder Propylenoxid- (PO) Gruppierung, vorzugsweise für eine Ethylenoxidgruppierung. Der Index n steht für eine ganze Zahl von 1 bis 50, vorzugsweise von 1 bis 20 und insbesondere von 2 bis 10. Ganz besonders bevorzugt steht n für die Zahlen 2, 3, 4, 5, 6, 7 oder 8.AO represents an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group. The index n represents an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. Very particularly preferably n represents the numbers 2, 3, 4, 5, 6, 7 or 8.
Weitere geeignete anionischen Tenside sind die Alkylsulfate, welche sich nicht von Fettalkoholen ableiten, der Formel
R2-O-SO3- X+ (II).
Other suitable anionic surfactants are the alkyl sulfates, which are not derived from fatty alcohols, of the formula
R2-O-SO3-X+ (II).
In dieser Formel (II) steht R2 für einen linearen oder verzweigten, substituierten oder unsubstituierten Alkylrest, vorzugsweise für einen linearen, unsubstituierten Alkylrest, besonders bevorzugt für einen Fettalkoholrest. Bevorzugte Reste R2 sind ausgewählt aus Decyl-, Undecyl-, Dodecyl-, Tridecyl-, Tetradecyl, Pentadecyl-, Hexadecyl-, Heptadecyl-, Octadecyl-, Nonadecyl-, Eicosylresten und deren Mischungen, wobei die Vertreter mit gerader Anzahl an C-Atomen bevorzugt sind. Besonders bevorzugt sind sie von C10-20-Oxoalkoholen abgeleitet.In this formula (II), R2 represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R2 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives having an even number of carbon atoms are preferred. They are particularly preferably derived from C10-20 oxo alcohols.
X steht für ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations, bevorzugt sind dabei die Alkalimetallionen und darunter Na+ oder K+, wobei Na+ äußerst bevorzugt ist. Weitere Kationen X+ können ausgewählt sein aus NH4+, ½ Zn2+, ½ Mg2+,½ Ca2+,½ Mn2+, und deren Mischungen.X stands for a single-quality cation or the n-ten part of an N-quality cation, preferably the alkali metal ions and below Na+ or K+, where Na+ is extremely preferred. Further cations
Falls vorhanden, so ist das mindestens eine weitere nichtionische Tensid in 0,1 bis 20 Gew.-%, bevorzugt 0,5 bis 10 Gew.-%, stärker bevorzugt in 1 bis 8 Gew.-%, basierend auf dem Gesamtgewicht des Geschirrspülmittels enthalten.If present, the at least one further nonionic surfactant is 0.1 to 20 wt.%, preferably 0.5 to 10 wt.%, more preferably 1 to 8 wt.%, based on the total weight of the dishwashing detergent contain.
Als weitere nichtionische Tenside sind alle für Geschirrspülmittel bekannten nichtionischen Tenside geeignet.All nonionic surfactants known for dishwashing detergents are suitable as further nonionic surfactants.
In einer Ausführungsform ist das mindestens eine weitere nichtionische Tensid ausgewählt aus alkoxylierten Fettsäurealkylestern, Polyhydroxyfettsäureamiden, Alkylglykosiden und alkoxylierten Alkoholen und Mischungen davon.In one embodiment, the at least one further nonionic surfactant is selected from alkoxylated fatty acid alkyl esters, polyhydroxy fatty acid amides, alkyl glycosides and alkoxylated alcohols and mixtures thereof.
Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette.Another class of preferably used nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
Weitere geeignete Tenside sind die als PHFA bekannten Polyhydroxyfettsäureamide.Other suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.
Ebenfalls geeignet sind Alkylglykoside der allgemeinen Formel RO(G)x in der R einem primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen entspricht und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl zwischen 1 und 10; vorzugsweise liegt x bei 1 ,2 bis 1 ,4.Also suitable are alkyl glycosides of the general formula RO (G) a glycose unit with 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
In einer Ausführungsform sind die weiteren nichtionische Tenside aus der Gruppe der alkoxylierten Alkohole ausgewählt. Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) oder Propylenoxid (PO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann beziehungsweise lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, zum Beispielaus Kokos-, Palm-, Talgfett oder Oleylalkohol, und durchschnittlich 2 bis 8 Mol EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-14-Alkohole mit 3 EO oder 4 EO, C8-11-Alkohol mit 7 EO, C13-15-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12-14-Alkohol mit 3 EO und C12-18-Alkohol mit 5 EO.In one embodiment, the further nonionic surfactants are selected from the group of alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) or propylene oxide (PO) per mole of alcohol, in which the alcohol residue is linear or preferably in 2 position can be methyl-branched or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C12-14 alcohols with 3 EO or 4 EO, C8-11 alcohol with 7 EO, C13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12-18 Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-14 alcohol with 3 EO and C12-18 alcohol with 5 EO.
In verschiedenen Ausführungsformen beträgt die Gesamtmenge der Tenside, d.h. des Tensidsystems, bezogen auf das Gewicht des Mittels 2,5 bis 70 Gew.-%, vorzugsweise 5 bis 60 Gew.-%, noch bevorzugter 6 bis 50 Gew.-%.In various embodiments, the total amount of surfactants, i.e. the surfactant system, based on the weight of the agent, is 2.5 to 70% by weight, preferably 5 to 60% by weight, more preferably 6 to 50% by weight.
Das Geschirrspülmittel gemäß der vorliegenden Erfindung kann ferner mindestens einen zusätzlichen Inhaltsstoff ausgewählt aus der Gruppe bestehend aus Wasser, Enzymen, Additiven zur Verbesserung des Ablauf- und Trocknungsverhaltens, zur Einstellung der Viskosität und/oder zur Stabilisierung, UV-Stabilisatoren, Parfüm, Perlglanzmitteln, Farbstoffen, Korrosionsinhibitoren, Konservierungsmitteln, Bitterstoffen, organischen Salzen, Desinfektionsmitteln, strukturgebenden Polymeren, Entschäumern, verkapselten Inhaltsstoffen, pH-Stellmitteln sowie Hautgefühl-verbessernden oder pflegenden Additiven enthalten.The dishwashing detergent according to the present invention can also contain at least one additional ingredient selected from the group consisting of water, enzymes, additives to improve drainage and drying behavior, to adjust the viscosity and / or for stabilization, UV stabilizers, perfume, pearlescent agents, dyes , corrosion inhibitors, preservatives, bitter substances, organic salts, disinfectants, structuring polymers, defoamers, encapsulated ingredients, pH adjusters and additives that improve or care for skin feel.
In einer Ausführungsform sind die Geschirrspülmittel gemäß der vorliegenden Erfindung flüssig und enthalten Wasser als Hauptlösungsmittel, d.h. es handelt sich um wässrige Geschirrspülmittelmittel. Der Wassergehalt des erfindungsgemäßen wässrigen Mittels beträgt üblicherweise 15 bis 90 Gew.-%, vorzugsweise 20 bis 60 Gew.-%.In one embodiment, the dishwashing detergents according to the present invention are liquid and contain water as the main solvent, i.e. they are aqueous dishwashing detergents. The water content of the aqueous agent according to the invention is usually 15 to 90% by weight, preferably 20 to 60% by weight.
Daneben können dem Geschirrspülmittel weitere organische Lösungsmittel zugesetzt werden. Geeignete organische Lösungsmittel umfassen Cumolsulfonat, ein- oder mehrwertige Alkohole, Alkanolamine oder Glykolether, sofern sie im angegebenen Konzentrationsbereich mit Wasser mischbar sind. Vorzugsweise werden die Lösungsmittel ausgewählt aus Ethanol, n-Propanol, i-Propanol, Butanolen, Glykol, Propandiol, Butandiol, Methylpropandiol, Glycerin, Diglykol, Propyldiglycol, Butyldiglykol, Hexylenglycol, Ethylenglykolmethylether, Ethylenglykolethylether, Ethylenglykolpropylether, Ethylenglykolmono-n-butylether, Diethylenglykolmethylether, Diethylenglykolethylether, Propylenglykolmethylether, Propylenglykolethylether, Propylenglykolpropylether, Dipropylenglykolmonomethylether, Dipropylenglykolmonoethylether, Methoxytriglykol, Ethoxytriglykol, Butoxytriglykol, 1-Butoxyethoxy-2-propanol, 3-Methyl-3-methoxybutanol, Propylen-glykol-t-butylether, Di-n-octylether sowie Mischungen dieser Lösungsmittel. Insbesondere ist Ethanol bevorzugt. Bevorzugt ist das organische Lösungsmittel in 0,1 bis 10 Gew.-%, basierend auf dem Gesamtgewicht des Geschirrspülmittels enthalten.In addition, other organic solvents can be added to the dishwashing detergent. Suitable organic solvents include cumene sulfonate, mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the specified concentration range. The solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerin, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, Ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3 -methoxybutanol, propylene glycol-t- butyl ether, di-n-octyl ether and mixtures of these solvents. Ethanol is particularly preferred. The organic solvent is preferably contained in 0.1 to 10% by weight, based on the total weight of the dishwashing detergent.
Erfindungsgemäss umfasst das Lösungsmittel Cumolsulfonat und Ethanol.According to the invention, the solvent comprises cumene sulfonate and ethanol.
Die hierin beschriebenen Geschirrspülmittel können in verschiedenen Ausführungsformen ferner mindestens ein Enzym, vorzugsweise eine Protease enthalten. Die eingesetzten Proteasen sind vorzugsweise alkalische Serin-Proteasen. Sie wirken als unspezifische Endopeptidasen, das heißt, sie hydrolysieren beliebige Säureamidbindungen, die im Inneren von Peptiden oder Proteinen liegen und bewirken dadurch den Abbau proteinhaltiger Anschmutzungen auf dem Reinigungsgut. Ihr pH-Optimum liegt meist im deutlich alkalischen Bereich.In various embodiments, the dishwashing detergents described herein may further contain at least one enzyme, preferably a protease. The proteases used are preferably alkaline serine proteases. They act as non-specific endopeptidases, that is, they hydrolyze any acid amide bonds that are inside peptides or proteins and thereby cause the breakdown of protein-containing soils on the items to be cleaned. Their pH optimum is usually in the significantly alkaline range.
Bei den erfindungsgemäß bevorzugt eingesetzten Proteasen handelt es sich vorzugsweise um eine Serin-Protease, insbesondere um eine Subtilase, besonders bevorzugt um ein Subtilisin. Das Subtilisin kann dabei ein Wildtypenzym oder eine Subtilisin-Variante sein, wobei das Wildtypenzym bzw. das Ausgangsenzym der Variante vorzugsweise aus einer der folgenden ausgewählt ist:
- der Alkalischen Protease aus Bacillus amyloliquefaciens (BPN'),
- der Alkalischen Protease aus Bacillus licheniformis (Subtilisin Carlsberg),
- der Alkalischen Protease PB92,
- Subtilisin 147 und/oder 309 (Savinase)
- der Alkalischen Protease aus Bacillus lentus, vorzugsweise aus Bacillus lentus (DSM 5483),
- der Alkalischen Protease aus Bacillus alcalophilus (DSM 11233),
- der Alkalischen Protease aus Bacillus gibsonii (DSM 14391) oder einer hierzu mindestens zu 70% identischen Alkalischen Protease,
- der Alkalischen Protease aus Bacillus sp. (DSM 14390) oder einer hierzu mindestens zu 98,5% identischen Alkalischen Protease, und
- der Alkalischen Protease aus Bacillus sp. (DSM 14392) oder einer hierzu mindestens zu 98,1 % identischen Alkalischen Protease.
- the alkaline protease from Bacillus amyloliquefaciens (BPN'),
- the alkaline protease from Bacillus licheniformis (Subtilisin Carlsberg),
- the alkaline protease PB92,
- Subtilisin 147 and/or 309 (Savinase)
- the alkaline protease from Bacillus lentus, preferably from Bacillus lentus (DSM 5483),
- the alkaline protease from Bacillus alcalophilus (DSM 11233),
- the alkaline protease from Bacillus gibsonii (DSM 14391) or an alkaline protease that is at least 70% identical,
- the alkaline protease from Bacillus sp. (DSM 14390) or an alkaline protease that is at least 98.5% identical, and
- the alkaline protease from Bacillus sp. (DSM 14392) or an alkaline protease that is at least 98.1% identical.
Beispiele für die in den hierin beschriebenen Mitteln einsetzbaren Proteasen sind Subtilisin 309 oder funktionale Fragmente/Varianten davon und Varianten der Alkalischen Protease aus Bacillus lentus oder Varianten davon. Subtilisin 309 wird unter dem Handelsnamen Savinase® von der Firma Novozymes A/S, Bagsvaerd, Dänemark vertrieben. Von dem Subtilisin 309 aus Bacillus lentus sind unter den Handelsnamen Blaze® und Ovozyme® von der Firma Novozymes optimierte Enzymvarianten erhältlich, die eine bevorzugte Ausführungsform der Erfindung darstellen. Von der Alkalischen Protease aus Bacillus lentus DSM 5483 leiten sich beispielsweise die unter der Bezeichnung BLAP® geführten Protease-Varianten ab. Bevorzugt sind hier insbesondere solche Protease-Varianten, die gegenüber dem BLAP wt (Wildtyp) Enzym, in der Zählung gemäß BLAP wt, mindestens eine Mutation an R99 aufweisen, insbesondere R99E oder R99D, insbesondere bevorzugt ist R99E, sowie optional zusätzlich mindestens eine oder zwei, vorzugsweise alle drei der Aminosäuresubstitutionen S3T, V4I und V199I aufweist, insbesondere bevorzugt sind die BLAP-Varianten, wie sie in SeqlD No 4 oder 5 der
In den hierin beschriebenen Geschirrspülmitteln können die einzusetzenden Enzyme ferner zusammen mit Begleitstoffen, etwa aus der Fermentation, konfektioniert sein. In flüssigen Mitteln werden die Enzyme bevorzugt als Enzymflüssigformulierung(en) eingesetzt.In the dishwashing detergents described here, the enzymes to be used can also be formulated together with accompanying substances, for example from fermentation. In liquid agents, the enzymes are preferably used as enzyme liquid formulation(s).
Die Proteasen werden in der Regel nicht in Form des reinen Proteins sondern vielmehr in Form stabilisierter, lager- und transportfähiger Zubereitungen bereitgestellt. Zu diesen vorkonfektionierten Zubereitungen zählen beispielsweise die durch Granulation, Extrusion oder Lyophilisierung erhaltenen festen Präparationen oder, insbesondere bei flüssigen oder gelförmigen Mitteln, Lösungen der Enzyme, vorteilhafterweise möglichst konzentriert, wasserarm und/oder mit Stabilisatoren oder weiteren Hilfsmitteln versetzt.The proteases are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations. These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and/or mixed with stabilizers or other auxiliaries.
Alternativ können die Enzyme sowohl für die feste als auch für die flüssige Darreichungsform verkapselt werden, beispielsweise durch Sprühtrocknung oder Extrusion der Enzymlösung zusammen mit einem vorzugsweise natürlichen Polymer oder in Form von Kapseln, beispielsweise solchen, bei denen die Enzyme wie in einem erstarrten Gel eingeschlossen sind oder in solchen vom Kern-Schale-Typ, bei dem ein enzymhaltiger Kern mit einer Wasser-, Luft- und/oder Chemikalien-undurchlässigen Schutzschicht überzogen ist. In aufgelagerten Schichten können zusätzlich weitere Wirkstoffe, beispielsweise Stabilisatoren, Emulgatoren, Pigmente, Bleich- oder Farbstoffe aufgebracht werden. Derartige Kapseln werden nach an sich bekannten Methoden, beispielsweise durch Schüttel- oder Rollgranulation oder in Fluid-bed-Prozessen aufgebracht. Vorteilhafterweise sind derartige Granulate, beispielsweise durch Aufbringen polymerer Filmbildner, staub-arm und aufgrund der Beschichtung lagerstabil.Alternatively, the enzymes can be encapsulated for both the solid and liquid dosage forms, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is covered with a water-, air- and/or chemical-impermeable protective layer. Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers. Such capsules are applied using methods known per se, for example by shaking or rolling granulation or in fluid bed processes. Such granules are advantageously low-dust, for example by applying polymeric film formers, and are storage-stable due to the coating.
Weiterhin ist es möglich, zwei oder mehrere Enzyme zusammen zu konfektionieren, so dass ein einzelnes Granulat mehrere Enzymaktivitäten aufweist.Furthermore, it is possible to assemble two or more enzymes together so that a single granulate has several enzyme activities.
Erfindungsgemäße Geschirrspülmittel können alternativ oder neben der mindestens einen Protease ein oder mehrere weitere Enzyme enthalten, insbesondere aus folgender Gruppe: Amylasen, Hemicellulasen, Cellulasen, Lipasen und Oxidoreduktasen.Dishwashing detergents according to the invention can alternatively or in addition to the at least one protease contain one or more further enzymes, in particular from the following group: amylases, hemicellulases, cellulases, lipases and oxidoreductases.
Das erfindungsgemäße Geschirrspülmittel enthält besonders bevorzugt ferner mindestens eine Amylase.The dishwashing detergent according to the invention particularly preferably also contains at least one amylase.
Bei der/den Amylase(n) handelt es sich vorzugsweise um eine α-Amylase. Bei der Hemicellulase handelt es sich vorzugsweise um eine β- Glucanase, eine Pektinase, eine Pullulanase und/oder eine Mannanase. Bei der Cellulase handelt es sich vorzugsweise um ein Cellulase-Gemisch oder eine Einkomponenten-Cellulase, vorzugsweise bzw. überwiegend um eine Endoglucanase und/oder eine Cellobiohydrolase. Bei der Oxidoreduktase handelt es sich vorzugsweise um eine Oxidase, insbesondere eine Cholin-Oxidase, oder um eine Perhydrolase. Die genannten Enzyme können alle wie oben für die Proteasen beschrieben konfektioniert sein.The amylase(s) is preferably an α-amylase. The hemicellulase is preferably a β-glucanase, a pectinase, a pullulanase and/or a mannanase. The cellulase is preferably a cellulase mixture or a single-component cellulase, preferably or predominantly an endoglucanase and/or a cellobiohydrolase. The oxidoreductase is preferably an oxidase, in particular a choline oxidase, or a perhydrolase. The enzymes mentioned can all be formulated as described above for the proteases.
In erfindungsgemäßen Geschirrspülmitteln, ist das mindestens eine Enzym, vorzugsweise die mindestens eine Protease und/oder mindestens eine Amylase in einer Menge von 0,01 - 1,6 Gew.-%, vorzugsweise 0,05 - 1,2 Gew.-% bezogen auf das Gesamtgewicht des Geschirrspülmittels, in diesem enthalten.In dishwashing detergents according to the invention, the at least one enzyme, preferably the at least one protease and/or at least one amylase, is present in an amount of 0.01 - 1.6% by weight, preferably 0.05 - 1.2% by weight on the total weight of the dishwashing detergent contained in it.
In verschiedenen Ausführungsformen können das Enzym/die Enzyme mit Enzymstabilisatoren in einer Enzymzusammensetzung vorformuliert vorliegen. Das Enzym-Protein bildet dabei üblicherweise nur einen Bruchteil des Gesamtgewichts der Enzym-Zubereitung. Bevorzugt eingesetzte Enzymzubereitungen enthalten zwischen 0,1 und 40 Gew.-%, bevorzugt zwischen 0,2 und 30 Gew.-%, besonders bevorzugt zwischen 0,4 und 20 Gew.-% und insbesondere zwischen 0,8 und 10 Gew.-% des Enzymproteins. In solchen Zusammensetzungen kann ein Enzymstabilisator in einer Menge von 0,05-35 Gew.-%, vorzugsweise 0,05-10 Gew.-%, bezogen auf das Gesamtgewicht, in der Enzymzusammensetzung enthalten sein. Diese Enzymzusammensetzung kann dann in erfindungsgemäßen Geschirrspülmitteln eingesetzt werden und zwar in Mengen, die zu den oben angegeben Endkonzentrationen im Geschirrspülmittel führen. Geeignete Enzymstabilisatoren sind im Stand der Technik bekannt. In verschiedenen Ausführungsformen kann das erfindungsgemäße Mittel dementsprechend zusätzlich einen oder mehrere Enzymstabilisatoren aufweisen.In various embodiments, the enzyme(s) may be preformulated with enzyme stabilizers in an enzyme composition. The enzyme protein usually only forms a fraction of the total weight of the enzyme preparation. Enzyme preparations used with preference contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0.8 and 10% by weight. % of enzyme protein. In such compositions, an enzyme stabilizer may be included in an amount of 0.05-35% by weight, preferably 0.05-10% by weight, based on the total weight, in the enzyme composition. This enzyme composition can then be used in dishwashing detergents according to the invention in amounts which lead to the final concentrations in the dishwashing detergent specified above. Suitable enzyme stabilizers are known in the art. In various embodiments, the agent according to the invention can accordingly additionally have one or more enzyme stabilizers.
Die Proteinkonzentration kann mit Hilfe bekannter Methoden, zum Beispiel dem BCA-Verfahren (Bicinchoninsäure; 2,2'-Bichinolyl-4,4'-dicarbonsäure) oder dem Biuret-Verfahren bestimmt werden. Die Bestimmung der Aktivproteinkonzentration erfolgt diesbezüglich über eine Titration der aktiven Zentren unter Verwendung eines geeigneten irreversiblen Inhibitors (für Proteasen beispielsweise Phenylmethylsulfonylfluorid (PMSF)) und Bestimmung der Restaktivität (vgl.
Zur weiteren Verbesserung des Ablauf- und/oder Trocknungsverhaltens kann das erfindungsgemäße Mittel ein oder mehrere Additive aus der Gruppe der Polymere und der Buildersubstanzen (Builder) enthalten, üblicherweise in einer Menge von 0,001 bis 5 Gew.-%, vorzugsweise 0,01 bis 4 Gew.-%, insbesondere 0,1 bis 3 Gew.-%, besonders bevorzugt 0,2 bis 2 Gew.-%, äußerst bevorzugt 0,5 bis 1,5 Gew.-%, beispielsweise 1 Gew.-%.To further improve the drainage and/or drying behavior, the agent according to the invention can contain one or more additives from the group of polymers and builders, usually in an amount of 0.001 to 5% by weight, preferably 0.01 to 4 % by weight, in particular 0.1 to 3% by weight, particularly preferably 0.2 to 2% by weight, most preferably 0.5 to 1.5% by weight, for example 1% by weight.
Polymere Verdickungsmittel im Sinne der vorliegenden Erfindung sind die als Polyelektrolyte verdickend wirkenden Polycarboxylate, vorzugsweise Homo und Copolymerisate der Acrylsäure, insbesondere Acrylsäure-Copolymere wie Acrylsäure-Methacrylsäure-Copolymere, und die Polysaccharide, insbesondere Heteropolysaccharide, sowie andere übliche verdickende Polymere.Polymeric thickeners in the context of the present invention are the polycarboxylates, which act as polyelectrolytes and have a thickening effect, preferably homo and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, in particular heteropolysaccharides, as well as other common thickening polymers.
Geeignete Polysaccharide bzw. Heteropolysaccharide sind die Polysaccharidgummen, beispielsweise Gummi arabicum, Agar, Alginate, Carrageene und ihre Salze, Guar, Guaran, Tragacant, Gellan, Ramsan, Dextran oder Xanthan und ihre Derivate, z.B. propoxyliertes Guar, sowie ihre Mischungen. Andere Polysaccharidverdicker, wie Stärken oder Cellulosederivate, können alternativ, vorzugsweise aber zusätzlich zu einem Polysaccharidgummi eingesetzt werden, beispielsweise Stärken verschiedensten Ursprungs und Stärkederivate, z.B. Hydroxyethylstärke, Stärkephosphatester oder Stärkeacetate, oder Carboxymethylcellulose bzw. ihr Natriumsalz, Methyl-, Ethyl-, Hydroxyethyl-, Hydroxypropyl-, Hydroxypropyl-methyl- oder Hydroxyethyl-methylcellulose oder Celluloseacetat.Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacantum, gellan, ramsan, dextran or xanthan gum and their derivatives, for example propoxylated guar, as well as their mixtures. Other polysaccharide thickeners, such as starches or cellulose derivatives, can be used alternatively, but preferably in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, e.g. hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.
Als polymere Verdickungsmittel geeignete Acrylsäure-Polymere sind beispielsweise hochmolekulare mit einem Polyalkenylpolyether, insbesondere einem Allylether von Saccharose, Pentaerythrit oder Propylen, vernetzte Homopolymere der Acrylsäure (INCI Carbomer), die auch als Carboxyvinylpolymere bezeichnet werden.Acrylic acid polymers suitable as polymeric thickeners are, for example, high molecular weight homopolymers of acrylic acid (INCI carbomer) crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyvinyl polymers.
Besonders geeignete polymere Verdickungsmittel sind aber folgende Acrylsäure-Copolymere: (i) Copolymere von zwei oder mehr Monomeren aus der Gruppe der Acrylsäure, Methacrylsäure und ihrer einfachen, vorzugsweise mit C1 4 Alkanolen gebildeten, Ester (INCI Acrylates Copolymer), zu denen etwa die Copolymere von Methacrylsäure, Butylacrylat und Methylmethacrylat (
Der Gehalt an polymerem Verdickungsmittel beträgt üblicherweise nicht mehr als 8 Gew.-%, vorzugsweise zwischen 0,1 und 7 Gew.-%, besonders bevorzugt zwischen 0,5 und 6 Gew.-%, insbesondere zwischen 1 und 5 Gew.-% und äußerst bevorzugt zwischen 1,5 und 4 Gew.-%, beispielsweise zwischen 2 und 2,5 Gew.-%, bezogen auf das Gesamtgewicht des Geschirrspülmittels.The content of polymeric thickener is usually not more than 8% by weight, preferably between 0.1 and 7% by weight, particularly preferably between 0.5 and 6% by weight, in particular between 1 and 5% by weight. and most preferably between 1.5 and 4% by weight, for example between 2 and 2.5% by weight, based on the total weight of the dishwashing detergent.
Zur Stabilisierung des erfindungsgemäßen Mittels, insbesondere bei hohem Tensidgehalt, können ein oder mehrere Dicarbonsäuren und/oder deren Salze zugesetzt werden, insbesondere eine Zusammensetzung aus Na-Salzen der Adipin-, Bernstein- und Glutarsäure, wie sie z.B. unter dem Handelsnamen Sokalan® DSC erhältlich ist. Der Einsatz erfolgt hierbei vorteilhafterweise in Mengen von 0,1 bis 8 Gew.-%, vorzugsweise 0,5 bis 7 Gew.-%, insbesondere 1,3 bis 6 Gew.-% und besonders bevorzugt 2 bis 4 Gew.-%, bezogen auf das Gesamtgewicht des Geschirrspülmittels.To stabilize the agent according to the invention, especially when there is a high surfactant content, one or more dicarboxylic acids and/or their salts can be added, in particular a composition of Na salts of adipic, succinic and glutaric acid, such as those available under the trade name Sokalan® DSC is. It is advantageously used in amounts of 0.1 to 8% by weight, preferably 0.5 to 7% by weight, in particular 1.3 to 6% by weight and particularly preferably 2 to 4% by weight, based on the total weight of the dishwashing detergent.
Kann jedoch auf deren Einsatz verzichtet werden, so ist das erfindungsgemäße Mittel vorzugsweise frei von Dicarbonsäure(salze)n.However, if their use can be dispensed with, the agent according to the invention is preferably free of dicarboxylic acid (salts).
Daneben können noch ein oder mehrere weitere - insbesondere in Handgeschirrspülmitteln - übliche Hilfs- und Zusatzstoffe, insbesondere UV-Stabilisatoren, Parfüm, Perlglanzmittel (INCI Opacifying Agents; beispielsweise Glykoldistearat, z.B. Cutina®AGS der Fa. Cognis, bzw. dieses enthaltende Mischungen, z.B. die Euperlane® der Fa. Cognis), Farbstoffe, Korrosionsinhibitoren, Konservierungsmittel (z.B. das technische auch als Bronopol bezeichnete 2-Brom-2-nitropropan-1,3-diol (
Na-Xylolsulfonat kann als Additiv verwendet werden.Na-xylenesulfonate can be used as an additive.
Der pH-Wert des erfindungsgemäßen Mittels kann mittels üblicher pH-Regulatoren, beispielsweise Säuren wie Mineralsäuren oder Citronensäure und/oder Alkalien wie Natrium- oder Kaliumhydroxid, eingestellt werden, wobei - insbesondere bei gewünschter Handverträglichkeit - ein Bereich von 4 bis 9.The pH value of the agent according to the invention can be adjusted using conventional pH regulators, for example acids such as mineral acids or citric acid and/or alkalis such as sodium or potassium hydroxide, with a range of 4 to 9 - particularly if hand tolerance is desired.
Zur Einstellung und/oder Stabilisierung des pH-Werts kann das erfindungsgemäße Mittel ein oder mehrere Puffer-Substanzen (INCI Buffering Agents) enthalten, üblicherweise in Mengen von 0,001 bis 5 Gew.-%, vorzugsweise 0,005 bis 3 Gew.-%, insbesondere 0,01 bis 2 Gew.-%, besonders bevorzugt 0,05 bis 1 Gew.-%, äußerst bevorzugt 0,1 bis 0,5 Gew.-%, beispielsweise 0,2 Gew.-%. Bevorzugt sind Puffer-Substanzen, die zugleich Komplexbildner oder sogar Chelatbildner (Chelatoren, INCI Chelating Agents) sind. Besonders bevorzugte Puffer-Substanzen sind die Citronensäure bzw. die Citrate, insbesondere die Natrium- und Kaliumcitrate, beispielsweise Trinatriumcitrat·2 H2O und Trikaliumcitrat·H2O.To adjust and/or stabilize the pH value, the agent according to the invention can contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5% by weight, preferably 0.005 to 3% by weight, in particular 0 .01 to 2% by weight, particularly preferably 0.05 to 1% by weight, most preferably 0.1 to 0.5% by weight, for example 0.2% by weight. Buffer substances that are also complexing agents or even chelating agents (chelators, INCI chelating agents) are preferred. Particularly preferred buffer substances are citric acid or citrates, in particular sodium and potassium citrates, for example trisodium citrate 2 H2O and tripotassium citrate H2O.
Die Beispielzusammensetzungen, die in Tabelle 1 gezeigt sind, wurden anhand einer Grundrezeptur umfassend 6,4 Gew.-% anionisches Tensid und 1,6 % Aminoxidtensid bereitgestellt. Die Gesamtmenge an Tensid beträgt also 8 Gew.-%. Dier Rezeptur enthielt ferner noch geringere Mengen Duftstoffe und Farbstoffe sowie Protease und Amylase Enzyme.
Alle Angaben sind als Gew.-% in Bezug auf die Gesamtzusammensetzung gemacht. Die Zusammensetzungen ergeben sich additiv aus den Werten von Tabelle 1 und der Grundrezeptur. Gemäß Tabelle 1 umfasst das Lösungsmittel Ethanol und Cumolsulfonat, CS. In der Tabelle ist ferner das Verhältnis der Gesamttensidmenge zur Gesamtmenge Lösungsmittel angegeben. Die Viskositätskurven sind in
Die erfindungsgemäßen Beispielrezepturen E1 bis E5 zeigen, dass die erfindungsgemäßen Zusammensetzungen insbesondere ein gutes Viskositätsprofil im hautfreundlichen pH Bereich von wenigstens 7 aufzeigen. Dabei sind die Viskositäten der Zusammensetzungen derart, dass die Zusammensetzungen vom Verbraucher als qualitativ hochwertig wahrgenommen werden und die Viskosität innerhalb des betreffenden pH Bereichs eine verhältnismäßig geringe/stabile Veränderung in Abhängigkeit vom pH-Wert aufweisen. Die homogene Vermischung der Komponenten mittels Rührwerkzeugen war ausreichend gut möglich.The example recipes E1 to E5 according to the invention show that the compositions according to the invention in particular have a good viscosity profile in the skin-friendly pH range of at least 7. The viscosities of the compositions are such that the consumer perceives the compositions to be of high quality and the viscosity within the relevant pH range has a relatively small/stable change depending on the pH value. The homogeneous mixing of the components using stirring tools was possible sufficiently well.
Die Vergleichsrezeptur C1 zeigte hingegen ein ungeeignetes Viskositätsprofil. Zwar konnten hohe Viskositätswerte erreicht werden. Im Gegensatz zu den erfindungsgemäßen Beispielrezepturen waren diese allerdings nicht ausreichend konstant/stabil in Abhängigkeit vom pH Wert. Der Herstellungsprozess einer solchen Zusammensetzung wird wegen der Viskositätsspitzen erheblich erschwert bis gänzlich unmöglich gemacht, da eine ausreichende Vermischung der Zusammensetzung mittels Rührwerkzeugen verhindert wird.The comparison formulation C1, however, showed an unsuitable viscosity profile. High viscosity values could be achieved. In contrast to the example recipes according to the invention, however, these were not sufficiently constant/stable depending on the pH value. The manufacturing process of such a composition is made considerably more difficult or even impossible due to the viscosity peaks, since sufficient mixing of the composition using stirring tools is prevented.
Die Zusammensetzung E2 weist insgesamt einen leichten Peak in der Viskosität auf. Das Verhältnis von Gesamttensidgehalt zu Lösungsmittel beträgt 6. Daher wird gemäß einer bevorzugten Ausführungsform ein Verhältnis von Gesamttensidgehalt zu Lösungsmittel beschrieben, welches kleiner ist als 10, insbesondere 4 und 5 beträgt, wie dies in den Beispielen E1, E3, E4, und E5 der Fall ist.Overall, the composition E2 has a slight peak in viscosity. The ratio of total surfactant content to solvent is 6. Therefore, according to a preferred embodiment, a ratio of total surfactant content to solvent is described which is less than 10, in particular 4 and 5, as is the case in examples E1, E3, E4, and E5 is.
Ferner wurden Beispielzusammensetzungen bei höherem Gesamttensidgehalt bereitgestellt. Die entsprechenden Beispielzusammensetzungen, die in Tabelle 2 gezeigt sind, wurden anhand einer Grundrezeptur umfassend 16 Gew.-% anionisches Tensid und 4 % Aminoxidtensid bereitgestellt. Die Gesamtmenge an Tensid beträgt also 20 Gew.-%. Dier Rezeptur enthielt ferner noch geringere Mengen Duftstoffe und Farbstoffe sowie Protease und Amylase Enzyme.
Alle Angaben sind als Gew.-% in Bezug auf die Gesamtzusammensetzung gemacht. Die Zusammensetzungen ergeben sich additiv aus den Werten von Tabelle 2 und der Grundrezeptur. Gemäß Tabelle 2 umfasst das Lösungsmittel Ethanol und Cumolsulfonat, CS. In der Tabelle ist ferner das Verhältnis der Gesamttensidmenge zur Gesamtmenge Lösungsmittel angegeben. Die Viskositätskurven sind in
Die Vergleichsrezeptur C2 zeigte einen noch stärker ausgeprägten Viskositätspeak als in den Zusammensetzungen mit geringeren Gesamttensidmengen C1. Die bereits dargestellte Problematik gilt also für höhere Gesamttensidgehalte ganz besonders.The comparison formulation C2 showed an even more pronounced viscosity peak than in the compositions with lower total surfactant amounts C1. The problem already presented applies particularly to higher total surfactant contents.
Die erfindungsgemäße Zusammensetzung E6 zeichnet sich durch ein besonders stabiles Viskositätsprofil aus. Im Vergleich zu den Rezepturen E1 bis E5 mit geringerem Gesamttensidgehalt wird eine noch bessere Stabilisierung der Viskosität erreicht.The composition E6 according to the invention is characterized by a particularly stable viscosity profile. Compared to the recipes E1 to E5 with a lower total surfactant content, even better stabilization of the viscosity is achieved.
Abschließend ist also festzustellen, dass die vorteilhafte Stabilisierung der Viskositätskurve insbesondere bei höheren Gesamttensidmengen von wenigstens 12 Gew-% stattfindet. Hier ist das Verhältnis von Gesamttensidgehalt zu Lösungsmittel also ebenfalls bevorzugt kleiner als 10, insbesondere zwischen 4 und 6, weiter bevorzugt 4 oder 5.In conclusion, it should be noted that the advantageous stabilization of the viscosity curve occurs particularly at higher total surfactant amounts of at least 12% by weight. Here the ratio of total surfactant content to solvent is also preferably less than 10, in particular between 4 and 6, more preferably 4 or 5.
Claims (10)
- Hand dishwashing composition comprising:at least one surfactant,characterized in that the composition further comprisesat least one inorganic salt, wherein the salt is an alkali metal salt and/or an alkaline earth metal salt, solvent, and wherein the viscosity of the composition is 1000 cps to 4000 cps, andwherein the pH of the composition is at least 7.5 and less than 8.5, and wherein the solvent comprises ethanol and cumene sulfonate.
- Hand dishwashing composition according to claim 1, wherein the viscosity of the composition is 1500 cps to 3500 cps, preferably 1500 to 3000 cps.
- Hand dishwashing composition according to any one of the preceding claims, wherein the salt is an alkali metal halide and/or an alkaline earth metal halide, preferably potassium chloride and/or sodium chloride.
- Hand dishwashing composition according to any one of the preceding claims, wherein the amount of inorganic salt is at least 2% by weight, preferably at least 4% by weight.
- Hand dishwashing composition according to any one of the preceding claims, wherein the ratio of total surfactant content to solvent is less than 10, preferably between 4 and 6, more preferably 4 or 5.
- A hand dishwashing composition according to any one of the preceding claims, wherein the hand dishwashing composition comprises at least one enzyme.
- A hand dishwashing composition according to any one of the preceding claims, wherein the hand dishwashing composition comprises an anionic surfactant.
- Hand dishwashing composition according to any one of the preceding claims, wherein
the hand dishwashing composition comprises an amine oxide and/or a betaine surfactant. - Hand dishwashing composition according to any one of the preceding claims, wherein the total amount of surfactant is at least 12% by weight, preferably at least 20% by weight.
- Use of a composition according to any one of the preceding claims for the manual cleaning of dishes.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL21177322.1T PL4098727T3 (en) | 2021-06-02 | 2021-06-02 | Viscosity-modified washing up liquid |
EP21177322.1A EP4098727B1 (en) | 2021-06-02 | 2021-06-02 | Viscosity-modified washing up liquid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP21177322.1A EP4098727B1 (en) | 2021-06-02 | 2021-06-02 | Viscosity-modified washing up liquid |
Publications (2)
Publication Number | Publication Date |
---|---|
EP4098727A1 EP4098727A1 (en) | 2022-12-07 |
EP4098727B1 true EP4098727B1 (en) | 2024-01-03 |
Family
ID=76250164
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP21177322.1A Active EP4098727B1 (en) | 2021-06-02 | 2021-06-02 | Viscosity-modified washing up liquid |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP4098727B1 (en) |
PL (1) | PL4098727T3 (en) |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2059728T3 (en) * | 1988-03-21 | 1994-11-16 | Unilever Nv | LIQUID DETERGENT COMPOSITION. |
US5500151A (en) * | 1988-10-07 | 1996-03-19 | Colgate-Palmolive Co. | Heavy duty fabric softening laundry detergent composition |
WO1999000470A1 (en) * | 1997-06-30 | 1999-01-07 | The Procter & Gamble Company | LIGHT-DUTY LIQUID OR GEL DISHWASHING DETERGENT COMPOSITIONS HAVING CONTROLLED pH AND DESIRABLE FOOD SOIL REMOVAL, RHEOLOGICAL AND SUDSING CHARACTERISTICS |
DE19817833A1 (en) * | 1997-11-26 | 1999-10-28 | Henkel Kgaa | Dishwashing liquid with a specific viscosity profile |
CA2751171A1 (en) * | 2009-02-02 | 2010-08-05 | The Procter & Gamble Company | Liquid hand dishwashing detergent composition |
DE102013207933A1 (en) | 2013-04-30 | 2014-10-30 | Henkel Ag & Co. Kgaa | Detergent containing proteases |
EP3572494A1 (en) * | 2017-06-29 | 2019-11-27 | The Procter & Gamble Company | Cleaning composition |
EP3670637A1 (en) * | 2018-12-18 | 2020-06-24 | Henkel AG & Co. KGaA | Viscosity regulation in handwash agents |
-
2021
- 2021-06-02 EP EP21177322.1A patent/EP4098727B1/en active Active
- 2021-06-02 PL PL21177322.1T patent/PL4098727T3/en unknown
Also Published As
Publication number | Publication date |
---|---|
PL4098727T3 (en) | 2024-04-29 |
EP4098727A1 (en) | 2022-12-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3670637A1 (en) | Viscosity regulation in handwash agents | |
EP3433351A1 (en) | Cleaning agent containing protease and amylase | |
DE102019207891A1 (en) | Foam stabilization through a specific surfactant mixture | |
DE102019207890A1 (en) | Foam stabilization through a specific surfactant mixture | |
EP4098727B1 (en) | Viscosity-modified washing up liquid | |
EP4047077A1 (en) | Stable manual dishwashing compositions with catalase | |
WO2017153565A1 (en) | Stabilization of enzymes in cleaning agents containing surfactants | |
DE102019203801A1 (en) | Hand dishwashing detergents comprising glutamic acid complexing agents | |
EP3839026B1 (en) | Method for increasing the stability of cleaning agents | |
EP4098728A1 (en) | Method for the preparation of viscosity modified dishwashing agents | |
WO2017153564A1 (en) | Cleaning agents containing amine oxide | |
WO2020169680A1 (en) | Alpha-olefin sulfonate-containing dishwashing detergents | |
DE102021203331A1 (en) | Use of viscosity-controlled hand dishwashing detergents at low temperatures | |
DE102021206648A1 (en) | Hand dishwashing detergent with catalase and additional enzyme | |
DE102021201250A1 (en) | Germicidal hand dishwashing detergents | |
DE102020215131A1 (en) | Use of a dishwashing detergent to increase dosing accuracy | |
EP3786270A1 (en) | Stable dishwashing liquid with bleach | |
EP3786273A1 (en) | Washing up liquid with bleach | |
EP3858963A1 (en) | Manual dishwashing compositions with short-chain amine oxide distribution | |
EP3712236A1 (en) | Improvement to the solubility of different surfactant systems by use of phosphonates | |
EP4047078A1 (en) | Preservative dishwashing composition with catalase | |
WO2020239543A1 (en) | Improved solubility by means of a specific surfactant mixture | |
WO2017144677A1 (en) | Stabilized cleaning compositions | |
DE102019107448A1 (en) | Foam stabilization through a specific surfactant mixture | |
EP3819360A1 (en) | Improved solubility of surfactant systems through adaptation of the addition of raw materials |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20210602 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230531 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20230928 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502021002328 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG9D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240103 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240103 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20240103 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240103 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240103 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240503 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240103 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240619 Year of fee payment: 4 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240404 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240403 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240103 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240103 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240403 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240403 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240103 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240503 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240103 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240404 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240103 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240103 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20240628 Year of fee payment: 4 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240503 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PL Payment date: 20240524 Year of fee payment: 4 |