EP2850169B1 - Low-water-content, liquid detergent comprising surfactants obtained from renewable raw materials - Google Patents
Low-water-content, liquid detergent comprising surfactants obtained from renewable raw materials Download PDFInfo
- Publication number
- EP2850169B1 EP2850169B1 EP13720952.4A EP13720952A EP2850169B1 EP 2850169 B1 EP2850169 B1 EP 2850169B1 EP 13720952 A EP13720952 A EP 13720952A EP 2850169 B1 EP2850169 B1 EP 2850169B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- cleaning agent
- soluble
- washing
- fatty
- 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 claims description 65
- 239000003599 detergent Substances 0.000 title description 50
- 239000004094 surface-active agent Substances 0.000 title description 16
- 239000002994 raw material Substances 0.000 title description 8
- 239000012459 cleaning agent Substances 0.000 claims description 80
- 238000005406 washing Methods 0.000 claims description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000009463 water soluble packaging Methods 0.000 claims description 30
- 150000002191 fatty alcohols Chemical class 0.000 claims description 21
- -1 fatty alcohol sulfates Chemical class 0.000 claims description 20
- 239000003945 anionic surfactant Substances 0.000 claims description 19
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 19
- 239000000194 fatty acid Substances 0.000 claims description 19
- 229930195729 fatty acid Natural products 0.000 claims description 19
- 150000004665 fatty acids Chemical class 0.000 claims description 19
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 17
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 17
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 14
- 239000000344 soap Substances 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 11
- 239000002736 nonionic surfactant Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 235000013772 propylene glycol Nutrition 0.000 claims description 10
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 150000002149 estolides Chemical class 0.000 claims description 4
- 150000004702 methyl esters Chemical class 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 22
- 238000000576 coating method Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 14
- 239000004615 ingredient Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 150000001298 alcohols Chemical class 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000003760 tallow Substances 0.000 description 4
- 244000060011 Cocos nucifera Species 0.000 description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002304 perfume Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000004006 olive oil Substances 0.000 description 2
- 235000008390 olive oil Nutrition 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000013042 solid detergent Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000003856 thermoforming Methods 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N 1-Tetradecanol Natural products CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 1
- FKKAGFLIPSSCHT-UHFFFAOYSA-N 1-dodecoxydodecane;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC FKKAGFLIPSSCHT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004382 Amylase Substances 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- 108010059892 Cellulase Proteins 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 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
- 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 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012753 anti-shrinkage agent Substances 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 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 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- 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 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N n-hexadecyl alcohol Natural products CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 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
- 230000003287 optical effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 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 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical class CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 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
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
- C11D17/043—Liquid or thixotropic (gel) 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
-
- 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
- C11D1/66—Non-ionic compounds
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
-
- 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
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with 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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
- C11D3/201—Monohydric alcohols linear
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2041—Dihydric alcohols
- C11D3/2044—Dihydric alcohols linear
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
-
- 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
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- 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
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
-
- 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
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- 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
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
-
- 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
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- 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
- C11D1/66—Non-ionic compounds
- C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
Definitions
- the invention relates to a water-soluble packaging comprising a water-soluble coating and a liquid washing or cleaning agent with anionic and nonionic surfactants.
- detergents or cleaners usually contain combinations of several surfactants in order to meet the requirements for the agent with regard to washing and cleaning performance.
- the surfactants are usually both those which are obtained from renewable raw materials, such as, for example, ethoxylated fatty alcohols, fatty alcohol sulfates, fatty alcohol ether sulfates or alkylpolyglycosides, and also petrochemically obtained surfactants, in particular alkylbenzenesulfonates.
- a detergent or cleaning agent that is as climate neutral as possible, which can be accomplished through the use of surfactants derived from renewable resources.
- Detergents or cleaners are now available to the consumer in a variety of forms.
- this offer includes, for example, liquids, gels or sachets (tablets or filled pouches).
- portion packs containing liquid detergents or cleaning agents are becoming increasingly popular, fulfilling, on the one hand, the consumer's desire for simplified dosing and, on the other hand, more and more consumers prefering liquid detergents or cleaners.
- WO2013 / 135512 A1 discloses a dusted water-soluble package containing an agent and a water-soluble wrapper.
- WO 2002/057398 A1 is, for example, a water-soluble container containing a liquid detergent composition comprising: a) an alkylbenzenesulfonic acid neutralized with an alkanolamine, b) an organic solvent and c) less than 3% by weight of water.
- Alkylbenzenesulfonates are preferably used not only because of their good washing and cleaning performance in low-water liquid detergents or cleaners, but also because they can be highly concentrated, that is in low-water form, can be used. This means that the use of alkylbenzenesulfonates as anionic surfactant little water enters the liquid detergents or cleaning agents.
- Other anionic surfactants such as fatty alcohol ether sulfates obtained from renewable raw materials, already contain large amounts (> 25%) of water in the raw material.
- the ionic strength I c of the washing or cleaning agent is preferably less than 250 mmol / l. It has been found that such an ionic strength prevents ingredients, in particular surfactants, of the liquid detergent or cleaning agent from being salted out and depositing on the inner surface of the water-soluble coating.
- the washing or cleaning agent has a particularly high cleaning performance and good foaming behavior, when the anionic surfactant is a mixture of fatty alcohol ether sulfate and fatty acid soap.
- the amount of fatty alcohol ether sulfate in the liquid detergent or cleaning agent is at least 5% by weight.
- the washing or cleaning agent has a water activity a w ⁇ 0.38.
- the amount of aerobically non-biodegradable organic ingredients (aNBO) in the detergent or cleaner is less than 0.55 g per kg wash load.
- the amount of anaerobically non-biodegradable organic ingredients (anNBO) in the detergent or cleaner is less than 0.70 g per kg wash load.
- the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
- Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.
- the application relates to a water-soluble packaging which contains a liquid washing or cleaning agent and a water-soluble coating.
- the water-soluble package contains a water-soluble envelope which forms a closed structure having in its interior one or more chambers for receiving one or more detergents or cleaning agents.
- the water-soluble packaging may be dimensionally stable or deformable.
- the water-soluble packaging may be formed as a dimensionally stable container, for example in the form of a capsule, box, box or container.
- the water-soluble packaging in principle it is also possible and preferred to mold the water-soluble packaging as a non-dimensionally stable container, for example as a bag.
- the shape of such a water-soluble packaging can be largely adapted to the conditions of use.
- various forms such as hoses, pillows, cylinders, bottles or discs in question.
- the water-soluble packaging contains a liquid washing or cleaning agent.
- the liquid washing or cleaning agent contains only surfactants, which are obtained from renewable raw materials.
- the liquid washing or cleaning agent contains nonionic surfactant selected from the group consisting of alkoxylated fatty alcohols, alkyl polyglycosides, ethoxylated methyl esters of natural fatty acids and mixtures thereof.
- the alkoxylated fatty alcohols used are preferably ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 4 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear.
- EO ethylene oxide
- alcohol ethoxylates having 12 to 18 C atoms for example coconut, palm, tallow or oleyl alcohol, and on average 5 to 8 EO per mole of alcohol are preferred.
- the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 4 EO or 7 EO, C 9-11 alcohols with 7 EO, C 12-18 alcohols with 5 EO or 7 EO and mixtures of these.
- the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- fatty alcohols containing more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- Alkoxylated fatty alcohols which contain EO and PO groups together in the molecule can also be used according to the invention.
- alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially methyl-branched in the 2-position aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
- nonionic surfactants are ethoxylated methyl esters of natural fatty acids, such as coconut, palm kernel or olive oil fatty acids, preferably having 8 to 18 EO units.
- the liquid washing or cleaning agent preferably contains exclusively alkoxylated fatty alcohols as nonionic surfactants.
- the total amount of nonionic surfactant in the liquid washing or cleaning agent is up to 45 wt .-%, preferably 15 to 40 wt .-% and particularly preferably 20 to 30 wt .-%, based on the total liquid detergent or cleaning agent.
- the liquid detergent or cleaning agent further contains anionic surfactant selected from the group consisting of fatty alcohol sulfates, fatty alcohol ether sulfates, fatty acid soaps, sulfonated estolides and mixtures thereof.
- the liquid washing or cleaning agent particularly preferably contains fatty alcohol ether sulfates and / or fatty acid soaps as anionic surfactant.
- the anionic surfactant most preferably contains a mixture of fatty alcohol ether sulfates and fatty acid soaps and is free of further anionic surfactants.
- fatty alcohol sulfates the salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut oil fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol are preferred.
- the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
- fatty alcohol ether sulfates are, for example, the sulfuric acid monoesters of ethoxylated with 1 to 6 moles of ethylene oxide straight or branched C 7-21 alcohols such as 2-methyl-branched C 9-11 alcohols having an average of 3.5 moles of ethylene oxide (EO) or C 12th -18 fatty alcohols with 1 to 4 EO used.
- EO ethylene oxide
- Suitable anionic surfactants are fatty acid soaps.
- Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
- the anionic surfactants may be in the form of their sodium, potassium or ammonium salts.
- the anionic surfactants are in the form of their sodium salts or ammonium salts.
- the ammonium salts may be the salts of organic bases.
- the amine used for the neutralization is preferably choline, triethylamine, monoethanolamine, diethanolamine, triethanolamine, methylethylamine or a mixture thereof, with monoethanolamine being preferred.
- Suitable sulfonated estolides include compounds of the following formula wherein n is an integer from 1 to 30, one of X or Y is SO 3 -Z and the other is hydrogen, wherein X and Y are present in each repeating unit, A 1 and A 2 are linear or branched, saturated or unsaturated, substituted or unsubstituted C 8 -C 22 alkylene units, a is independently 0, 1, or 2 in each repeat unit, R is a linear or branched, saturated or unsaturated, substituted or unsubstituted C 1 -C 24 alkyl moiety, W is a monovalent or divalent Metal cation, an ammonium cation, a substituted ammonium cation, hydrogen, an alkyl group or a substituted alkyl group and Z is hydrogen, a monovalent or divalent metal cation, an ammonium cation or a substituted ammonium cation.
- the liquid washing or cleaning agent contains the sodium salt of a fatty alcohol ether sulfate and a fatty acid neutralized with monoethanolamine. It is also preferred that the amount of fatty alcohol ether sulfate in the total liquid detergent or cleaning agent is at least 5% by weight.
- the total amount of anionic surfactant in the liquid washing or cleaning agent is up to 35% by weight and preferably 15 to 30% by weight, based on the total liquid detergent or cleaning agent.
- the total amount of nonionic and anionic surfactant in the liquid washing or cleaning agent is up to 75% by weight and preferably 50 to 60% by weight, based on the total liquid detergent or cleaning agent.
- the liquid detergent or cleaning agent further contains organic solvent comprising a mixture of 1,2-propanediol and ethanol.
- the amount of ethanol is up to 5 wt .-%, and preferably between 1 and 3 wt .-%, each based on the total washing or cleaning agent.
- the amount of 1,2-propanediol is up to 50 wt .-%, preferably between 10 and 40 wt .-%, and most preferably between 20 and 35 wt .-%, each based on the total washing or cleaning agent.
- liquid washing or cleaning agents which have other organic solvent systems, for example a mixture of 1,2-propanediol and isopropanol, are unstable.
- liquid washing or cleaning agent is free of isopropanol and in a most preferred embodiment free of further organic solvents. Accordingly, a particularly preferred liquid washing or cleaning agent contains an organic solvent which is a mixture of 1,2-propanediol and ethanol.
- the liquid washing or cleaning agent contains water, wherein the content of water is less than 15 wt .-%, and more preferably less than 13 wt .-%, each based on the total liquid detergent or cleaning agent. Particularly preferably, the entire liquid washing or cleaning agent contains 7 to 12 wt .-% water.
- the liquid washing or cleaning agent has a water activity a w of more than 0.38, and more preferably more than 0.42.
- the determination of the water activity is carried out at 25 ° C with an "AquaLab Lite" device from IUL Instruments GmbH.
- the water activity a w is a measure of freely available water in a material and indicates the availability of the water for chemical, biochemical and microbial reactions.
- the washing or cleaning agent may contain other ingredients containing the improve the performance and / or aesthetic properties of the detergent or cleaning agent, but not destroy the structural integrity of the water-soluble envelope.
- the washing or cleaning agent preferably additionally contains one or more substances from the group of builders, bleaches, enzymes, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils, antiredeposition agents, grayness inhibitors, anti-shrinkage agents Anti-crease agents, color transfer inhibitors, antimicrobial agents, non-aqueous solvents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, skin-care agents, swelling and anti-slip agents, plasticizing components and UV absorbers ,
- liquid washing or cleaning agent is free from added inorganic salts.
- the amount of aerobic non-biodegradable organic ingredients (aNBO) in the detergent or cleaning agent is less than 0.55 g per kg wash load.
- anaerobically nonbiodegradable organic ingredients (anNBO) in the detergent or cleaner be less than 0.70 g per kg wash load.
- a wash load corresponds to a dosage of 35 g washing or cleaning agent to 4.5 kg of laundry.
- the liquid washing or cleaning agent is in a water-soluble coating.
- a water-soluble packaging contains, in addition to the liquid washing or cleaning agent, a water-soluble coating.
- the water-soluble coating is preferably formed by a water-soluble film material.
- Such water-soluble packages can be made by either vertical fill-seal (VFFS) or thermoforming techniques.
- VFFS vertical fill-seal
- the thermoforming process generally includes forming a first layer of water-soluble sheet material to form protrusions for receiving a composition therein, filling the composition into the protrusions, covering the composition-filled protrusions with a second layer of water-soluble sheet material, and sealing the first and second layers at least around the bulges.
- the water-soluble coating is preferably formed from a water-soluble film material selected from the group comprising polymers and polymer blends.
- the wrapper may be formed of one or two or more layers of the water-soluble film material.
- the water-soluble film material of the first layer and the further layers, if present, may be the same or different.
- the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
- Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 10,000 to 1,000,000 gmol -1 , preferably 20,000 to 500,000 gmol -1 , more preferably 30,000 to 100,000 gmol -1 and especially from 40,000 to 80,000 gmol -1 .
- polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible.
- polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
- a polymer selected from the group consisting of (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acids or mixtures of the above may additionally be selected from a polyvinyl alcohol-containing film material suitable for producing the water-soluble coating Be added polymers.
- a preferred additional polymer is polylactic acids.
- Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers.
- Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
- polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters.
- Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.
- the film material contains further additives.
- the film material may contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof.
- Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-sticking agents or mixtures thereof.
- Suitable water-soluble films for use in the water-soluble casings of the water-soluble packaging according to the invention are films sold by MonoSol LLC, for example under the designation M8630, M8310, C8400 or M8900.
- Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
- the water-soluble packaging has a chamber for receiving the liquid detergent or cleaning agent.
- the water-soluble packaging has two chambers.
- the first chamber contains the above-described liquid detergent or cleaning agent and the second chamber may contain a solid or a liquid detergent or cleaning agent.
- the water-soluble packaging has three chambers, these chambers can each contain a liquid washing or cleaning agent. But it is also possible that a chamber containing a solid detergent or detergent and two chambers containing a liquid detergent or cleaning agent. It is also possible that a solid detergent or cleaning agent is contained in two chambers and a liquid detergent or cleaning agent in a chamber.
- At least one chamber contains the above-described liquid detergent or cleaning agent according to the invention with exclusively surfactants which are obtained from renewable raw materials.
- the liquid detergents or cleaning agents contained in the other chambers of a water-soluble packaging may have the same composition.
- the liquid detergents or cleaners in a water-soluble packaging with at least two chambers preferably have compositions which differ at least in the content of an ingredient.
- the amount of detergent or cleaning agent, which is in total in the water-soluble packaging, preferably corresponds to the full or half dose required for a wash.
- Liquid detergents or cleaners were prepared by conventional and known methods and procedures. Table 1 below shows the compositions of two detergents or cleaners E1 and E2 according to the invention and four detergents or cleaners V1 to V4 not according to the invention. Table 1: Liquid washing or cleaning agents E1 and E2 and also V1 to V4 [all amounts are given in% by weight of active ingredient based on the composition] ingredients E1 E2 V1 V2 V3 V4 Na lauryl ether sulfate (2 EO) 12 12 12 12 12 12 12 C 12-18 fatty alcohol with 7 EO 25 25 25 25 25 25 25 C 12-18 fatty acid 15 15 15 15 15 15 15 15 15 15 15 15 15 15 ethanol 1.4 1.4 - - - - isopropanol - - 1.4 1.4 1.4 1.4 phosphonate 1 1 1 1 1 1 Monoethanolamine 3.86 3.86 3.94 3.67 3.71 3.91 Citric acid, sodium salt - - - 1.4 2.25 - MgCl 2 ⁇ 6
- the ionic strength I c of the liquid washing or cleaning agents E1 and E2 was in each case less than 150 mmol / l.
- the amount of aerobic non-biodegradable organic ingredients (aNBO) in detergents E1 and E2 was 0.13 g per kg wash load, respectively.
- the amount of aerobic non-biodegradable organic ingredients (ANNBO) in detergents E1 and E2 was 0.14 g per kg wash load, respectively.
- the water activity a w of the liquid washing or cleaning agents E1 and E2 was 0.45 in each case.
- a film of the type M 8630 Ex Monosol
- a thickness of 76 ⁇ m was pulled into a depression by means of a vacuum to form a bulge.
- the bulge was mixed with 30 ml of one of the liquid detergents or cleaners E1, E2 or V1 to V4 filled.
- the first and second layers were sealed together.
- the sealing temperature was 150 ° C and the sealing time 1.1 seconds.
- a liquid detergent or cleaning agent which acts as a surfactant system C 12-18 fatty acid soap, C 12-18 fatty alcohol containing 7 EO and a C 9-13 alkylbenzenesulfonate, an equally good cleaning performance.
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)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Dispersion Chemistry (AREA)
- Detergent Compositions (AREA)
Description
Die Erfindung betrifft eine wasserlösliche Verpackung, umfassend eine wasserlösliche Umhüllung und ein flüssiges Wasch- oder Reinigungsmittel mit anionischen und nichtionischen Tensiden.The invention relates to a water-soluble packaging comprising a water-soluble coating and a liquid washing or cleaning agent with anionic and nonionic surfactants.
Handelsübliche Wasch- oder Reinigungsmittel enthalten meist Kombinationen aus mehreren Tensiden, um die Anforderungen an das Mittel bezüglich Wasch- und Reinigungsleistung zu erfüllen. Bei den Tensiden handelt es sich dabei üblicherweise sowohl um solche, die aus nachwachsenden Rohstoffen gewonnen werden, wie beispielsweise ethoxylierte Fettalkohole, Fettalkoholsulfate, Fettalkoholethersulfate oder Alkylpolyglycoside, als auch um petrochemisch gewonnene Tenside, wie insbesondere Alkylbenzolsulfonate. Im Zuge des steigenden Umweltbewusstseins bei Industrie und Verbrauchern ist es jedoch wünschenswert, ein Wasch- oder Reinigungsmittel zu formulieren, welches so klimaneutral wie möglich ist, was durch den Einsatz von aus nachwachsenden Rohstoffen gewonnenen Tensiden bewirkt werden kann.Commercially available detergents or cleaners usually contain combinations of several surfactants in order to meet the requirements for the agent with regard to washing and cleaning performance. The surfactants are usually both those which are obtained from renewable raw materials, such as, for example, ethoxylated fatty alcohols, fatty alcohol sulfates, fatty alcohol ether sulfates or alkylpolyglycosides, and also petrochemically obtained surfactants, in particular alkylbenzenesulfonates. However, in the context of increasing environmental awareness among industry and consumers, it is desirable to formulate a detergent or cleaning agent that is as climate neutral as possible, which can be accomplished through the use of surfactants derived from renewable resources.
Wasch- oder Reinigungsmittel sind heute für den Verbraucher in vielfältigen Angebotsformen erhältlich. Neben Pulvern und Granulaten umfasst dieses Angebot beispielsweise auch Flüssigkeiten, Gele oder Portionspackungen (Tabletten oder gefüllte Beutel).Detergents or cleaners are now available to the consumer in a variety of forms. In addition to powders and granules, this offer includes, for example, liquids, gels or sachets (tablets or filled pouches).
Insbesondere Portionspackungen mit flüssigen Wasch- oder Reinigungsmitteln werden immer beliebter, erfüllen sie einerseits den Wunsch des Verbrauchers nach vereinfachter Dosierung und andererseits bevorzugen immer mehr Verbraucher flüssige Wasch- oder Reinigungsmittel.In particular, portion packs containing liquid detergents or cleaning agents are becoming increasingly popular, fulfilling, on the one hand, the consumer's desire for simplified dosing and, on the other hand, more and more consumers prefering liquid detergents or cleaners.
Bei der Formulierung von flüssigen Wasch- oder Reinigungsmitteln zur Verpackung in wasserlöslichen Beuteln muss insbesondere darauf geachtet werden, dass die Inhaltsstoffe des Wasch- oder Reinigungsmittels die wasserlösliche Umhüllung des Beutels nicht schon vor ihrem Einsatz auf- oder anlösen und so zu unerwünschten Leckagen führen.When formulating liquid detergents or cleaners for packaging in water-soluble bags, particular care must be taken to ensure that the ingredients of the washing or cleaning agent do not dissolve or dissolve the water-soluble envelope of the bag before they are used and thus lead to undesirable leaks.
Ein Inhaltsstoff, der die strukturelle Integrität der wasserlöslichen Umhüllung eines Beutels zerstören kann, ist Wasser. Aus diesem Grund enthalten flüssige Wasch- oder Reinigungsmittel zur Verpackung in wasserlöslichen Beuteln einen möglichst geringen Gehalt an Wasser
Aus der
Alkylbenzolsulfonate werden nicht nur wegen ihrer guten Wasch- und Reinigungsleistung bevorzugt in wasserarmen flüssigen Wasch- oder Reinigungsmitteln eingesetzt, sondern auch weil sie hochkonzentriert, dass heißt in wasserarmer Form, eingesetzt werden können. Dies bedeutet, dass über den Einsatz von Alkylbenzolsulfonaten als anionisches Tensid wenig Wasser in die flüssigen Wasch- oder Reinigungsmitteln gelangt. Andere anionische Tenside, wie beispielsweise aus nachwachsenden Rohstoffen gewonnene Fettalkoholethersulfate, enthalten bereits im Rohstoff hohe Mengen (> 25 %) Wasser.Alkylbenzenesulfonates are preferably used not only because of their good washing and cleaning performance in low-water liquid detergents or cleaners, but also because they can be highly concentrated, that is in low-water form, can be used. This means that the use of alkylbenzenesulfonates as anionic surfactant little water enters the liquid detergents or cleaning agents. Other anionic surfactants, such as fatty alcohol ether sulfates obtained from renewable raw materials, already contain large amounts (> 25%) of water in the raw material.
Es besteht somit Bedarf, in wasserlöslichen Umhüllungen verpackte Wasch- oder Reinigungsmitteln bereitzustellen, die ausschließlich Tenside enthalten, die aus nachwachsenden Rohstoffen gewonnenen werden.There is thus a need to provide detergents or cleaners packaged in water-soluble wraps, which contain only surfactants which are obtained from renewable raw materials.
Entsprechend war es eine Aufgabe der vorliegenden Erfindung, stabile, in wasserlöslichen Umhüllungen verpackte Wasch- oder Reinigungsmittel bereitzustellen, die ausschließlich Tenside enthalten, die aus nachwachsenden Rohstoffen gewonnenen werden.Accordingly, it has been an object of the present invention to provide stable detergents or cleaners packaged in water-soluble coatings which contain only surfactants derived from renewable resources.
Diese Aufgabe wird gelöst durch eine wasserlösliche Verpackung, die ein flüssiges Wasch- oder Reinigungsmittel und eine wasserlösliche Umhüllung enthält, wobei das flüssige Wasch- oder Reinigungsmittel
- a) nichtionisches Tensid ausgewählt aus der Gruppe bestehend aus alkoxylierten Fettalkoholen, Alkylpolyglycosiden, ethoxylierten Methylestern von natürlichen Fettsäuren und Mischungen daraus,
- b) anionisches Tensid ausgewählt aus der Gruppe bestehend aus Fettalkoholsulfaten, Fettalkoholethersulfaten, Fettsäureseifen, sulfonierten Estoliden und Mischungen daraus,
- c) organisches Lösungsmittel, welches eine Mischung aus 1,2-Propandiol und Ethanol umfasst,
- d) bis zu 15 Gew.-%, bezogen auf das gesamte Wasch- oder Reinigungsmittel, Wasser,
- e) bis zu 50 Gew.-%, bezogen auf das gesamte Wasch- oder Reinigungsmittel, 1,2-Propandiol,
- f) bis zu 5 Gew.-%, bezogen auf das gesamte Wasch- oder Reinigungsmittel, Ethanol enthält, und g) frei von Isopropanol, vorzugsweise frei von weiteren organischen Lösungsmittel, ist,
- a) nonionic surfactant selected from the group consisting of alkoxylated fatty alcohols, alkyl polyglycosides, ethoxylated methyl esters of natural fatty acids and mixtures thereof,
- b) anionic surfactant selected from the group consisting of fatty alcohol sulfates, fatty alcohol ether sulfates, fatty acid soaps, sulfonated estolides and mixtures thereof,
- c) organic solvent comprising a mixture of 1,2-propanediol and ethanol,
- d) up to 15% by weight, based on the total washing or cleaning agent, of water,
- e) up to 50% by weight, based on the total washing or cleaning agent, 1,2-propanediol,
- f) up to 5% by weight, based on the total washing or cleaning agent, of ethanol, and g) free of isopropanol, preferably free of further organic solvents,
Es hat sich überraschenderweise gezeigt, dass mit Hilfe des ausgewählten Tensidsystems und des ausgewählten Lösungsmittelsystems eine stabile wasserlösliche Verpackung mit einem flüssigen Wasch- oder Reinigungsmittel, umfassend ausschließlich aus nachwachsenden Rohstoffen gewonnene Tenside, erhalten werden kann. Andere Lösungsmittelsysteme führen zu Sedimentationen und/oder Synärese.It has surprisingly been found that with the aid of the selected surfactant system and the selected solvent system, a stable water-soluble packaging can be obtained with a liquid detergent or cleaning agent comprising exclusively surfactants obtained from renewable raw materials. Other solvent systems lead to sedimentation and / or syneresis.
Bevorzugt beträgt die Ionenstärke Ic des Wasch- oder Reinigungsmittels kleiner 250 mmol/l. Es hat sich gezeigt, dass eine solche lonenstärke verhindert, dass Inhaltsstoffe, insbesondere Tenside, des flüssigen Wasch- oder Reinigungsmittels ausgesalzt werden und sich an der inneren Oberfläche der wasserlöslichen Umhüllung ablagern.The ionic strength I c of the washing or cleaning agent is preferably less than 250 mmol / l. It has been found that such an ionic strength prevents ingredients, in particular surfactants, of the liquid detergent or cleaning agent from being salted out and depositing on the inner surface of the water-soluble coating.
Das Wasch- oder Reinigungsmittel weist eine besonders hohe Reinigungsleistung und gutes Schaumverhalten auf, wenn das anionische Tensid eine Mischung aus Fettalkoholethersulfat und Fettsäureseife ist.The washing or cleaning agent has a particularly high cleaning performance and good foaming behavior, when the anionic surfactant is a mixture of fatty alcohol ether sulfate and fatty acid soap.
Es ist ferner bevorzugt, dass die Menge an Fettalkoholethersulfat in dem flüssigen Wasch- oder Reinigungsmittel mindestens 5 Gew.-% beträgt.It is further preferred that the amount of fatty alcohol ether sulfate in the liquid detergent or cleaning agent is at least 5% by weight.
Außerdem ist es bevorzugt, dass das Wasch- oder Reinigungsmittel eine Wasseraktivität aw ≥ 0,38 aufweist.In addition, it is preferred that the washing or cleaning agent has a water activity a w ≥ 0.38.
In einer bevorzugten Ausführungsform der Erfindung beträgt die Menge an aerob nicht biologisch abbaubaren organischen Inhaltsstoffen (aNBO) in dem Wasch- oder Reinigungsmittel weniger als 0,55 g pro kg Waschladung.In a preferred embodiment of the invention, the amount of aerobically non-biodegradable organic ingredients (aNBO) in the detergent or cleaner is less than 0.55 g per kg wash load.
In einer weiteren Ausführungsform der Erfindung beträgt die Menge an anaerob nicht biologisch abbaubaren organischen Inhaltsstoffen (anNBO) in dem Wasch- oder Reinigungsmittel weniger als 0,70 g pro kg Waschladung.In another embodiment of the invention, the amount of anaerobically non-biodegradable organic ingredients (anNBO) in the detergent or cleaner is less than 0.70 g per kg wash load.
Es ist bevorzugt, dass die wasserlösliche Umhüllung Polyvinylalkohol oder ein Polyvinylalkoholcopolymer enthält. Wasserlösliche Umhüllungen, die Polyvinylalkohol oder ein Polyvinylalkoholcopolymer enthalten, weisen eine gute Stabilität bei einer ausreichend hohen Wasserlöslichkeit, insbesondere Kaltwasserlöslichkeit, auf.It is preferable that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.
Im Folgenden soll die Erfindung, unter anderem anhand von Beispielen, eingehender erläutert werden.In the following, the invention will be explained in more detail, inter alia, by way of examples.
Die Anmeldung betrifft eine wasserlösliche Verpackung, die ein flüssiges Wasch- oder Reinigungsmittel und eine wasserlösliche Umhüllung enthält.The application relates to a water-soluble packaging which contains a liquid washing or cleaning agent and a water-soluble coating.
Die wasserlösliche Verpackung enthält eine wasserlösliche Umhüllung, welche eine geschlossene Struktur ausbildet, die in ihrem Inneren eine oder mehrere Kammern zur Aufnahme eines oder mehrerer Wasch- oder Reinigungsmittel aufweist.The water-soluble package contains a water-soluble envelope which forms a closed structure having in its interior one or more chambers for receiving one or more detergents or cleaning agents.
Die wasserlösliche Verpackung kann formstabil oder verformbar ausgebildet sein.The water-soluble packaging may be dimensionally stable or deformable.
Die wasserlösliche Verpackung kann als formstabiler Behälter, beispielsweise in Form einer Kapsel, Box, Dose oder eines Containers ausgebildet sein.The water-soluble packaging may be formed as a dimensionally stable container, for example in the form of a capsule, box, box or container.
Es ist grundsätzlich jedoch auch möglich und bevorzugt, die wasserlösliche Verpackung als einen nicht formstabilen Behälter, beispielsweise als Beutel auszuformen. Die Form einer derartigen wasserlöslichen Verpackung kann den Gebrauchsgegebenheiten weitgehend angepasst werden. Es kommen beispielsweise verschiedenste Formen wie beispielsweise Schläuche, Kissen, Zylinder, Flaschen oder Scheiben in Frage.However, in principle it is also possible and preferred to mold the water-soluble packaging as a non-dimensionally stable container, for example as a bag. The shape of such a water-soluble packaging can be largely adapted to the conditions of use. There are, for example, various forms such as hoses, pillows, cylinders, bottles or discs in question.
Die wasserlösliche Verpackung enthält ein flüssiges Wasch- oder Reinigungsmittel. Das flüssige Wasch- oder Reinigungsmittel enthält ausschließlich Tenside, die aus nachwachsenden Rohstoffen gewonnenen werden.The water-soluble packaging contains a liquid washing or cleaning agent. The liquid washing or cleaning agent contains only surfactants, which are obtained from renewable raw materials.
Das flüssige Wasch- oder Reinigungsmittel enthält nichtionisches Tensid ausgewählt aus der Gruppe bestehend aus alkoxylierten Fettalkoholen, Alkylpolyglycosiden, ethoxylierten Methylestern von natürlichen Fettsäuren und Mischungen daraus.The liquid washing or cleaning agent contains nonionic surfactant selected from the group consisting of alkoxylated fatty alcohols, alkyl polyglycosides, ethoxylated methyl esters of natural fatty acids and mixtures thereof.
Als alkoxylierte Fettalkohole werden vorzugsweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 4 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear ist. Insbesondere sind Alkoholethoxylate mit 12 bis 18 C-Atomen, zum Beispiel aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 5 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-14-Alkohole mit 4 EO oder 7 EO, C9-11-Alkohol mit 7 EO, C12-18-Alkohole mit 5 EO oder 7 EO und Mischungen aus diesen. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE). Zusätzlich zu diesen alkoxylierte Fettalkoholen oder alternativ können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind Talgfettalkohol mit 14 EO, 25 EO, 30 EO oder 40 EO. Auch alkoxylierte Fettalkohole, die EO- und PO-Gruppen zusammen im Molekül enthalten, sind erfindungsgemäß einsetzbar.The alkoxylated fatty alcohols used are preferably ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 4 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear. In particular, alcohol ethoxylates having 12 to 18 C atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 5 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 4 EO or 7 EO, C 9-11 alcohols with 7 EO, C 12-18 alcohols with 5 EO or 7 EO and mixtures of these. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these alkoxylated fatty alcohols, or alternatively, fatty alcohols containing more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Alkoxylated fatty alcohols which contain EO and PO groups together in the molecule can also be used according to the invention.
Außerdem können als nichtionische Tenside Alkylglykoside der allgemeinen Formel RO(G)x eingesetzt werden, in der R einen primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet 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.In addition, as nonionic surfactants alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially methyl-branched in the 2-position aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
Weitere geeignete nichtionische Tenside sind ethoxylierte Methylester von natürlichen Fettsäuren, wie beispielsweise Kokos-, Palmkern- oder Olivenölfettsäuren, mit vorzugsweise 8 bis 18 EO-Einheiten.Further suitable nonionic surfactants are ethoxylated methyl esters of natural fatty acids, such as coconut, palm kernel or olive oil fatty acids, preferably having 8 to 18 EO units.
Vorzugsweise enthält das flüssige Wasch- oder Reinigungsmittel ausschließlich alkoxylierte Fettalkohole als nichtionische Tenside.The liquid washing or cleaning agent preferably contains exclusively alkoxylated fatty alcohols as nonionic surfactants.
Die Gesamtmenge an nichtionischem Tensid in dem flüssigen Wasch- oder Reinigungsmittel beträgt bis zu 45 Gew.-%, vorzugsweise 15 bis 40 Gew.-% und besonders bevorzugt 20 bis 30 Gew.-%, bezogen auf das gesamte flüssige Wasch- oder Reinigungsmittel.The total amount of nonionic surfactant in the liquid washing or cleaning agent is up to 45 wt .-%, preferably 15 to 40 wt .-% and particularly preferably 20 to 30 wt .-%, based on the total liquid detergent or cleaning agent.
Das flüssige Wasch- oder Reinigungsmittel enthält ferner anionisches Tensid ausgewählt aus der Gruppe bestehend aus Fettalkoholsulfaten, Fettalkoholethersulfaten, Fettsäureseifen, sulfonierten Estoliden und Mischungen daraus. Insbesondere bevorzugt enthält das flüssige Wasch- oder Reinigungsmittel als anionisches Tensid Fettalkoholethersulfate und/oder Fettsäureseifen. Ganz besonders bevorzugt enthält das anionische Tensid eine Mischung aus Fettalkoholethersulfaten und Fettsäureseifen und ist frei von weiteren anionischen Tensiden.The liquid detergent or cleaning agent further contains anionic surfactant selected from the group consisting of fatty alcohol sulfates, fatty alcohol ether sulfates, fatty acid soaps, sulfonated estolides and mixtures thereof. The liquid washing or cleaning agent particularly preferably contains fatty alcohol ether sulfates and / or fatty acid soaps as anionic surfactant. The anionic surfactant most preferably contains a mixture of fatty alcohol ether sulfates and fatty acid soaps and is free of further anionic surfactants.
Als Fettalkoholsulfate werden die Salze der Schwefelsäurehalbester der C12-C18-Fettalkohole, beispielsweise aus Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol bevorzugt. Aus waschtechnischem Interesse sind die C12-C16-Alkylsulfate und C12-C15-Alkylsulfate sowie C14-C15-Alkylsulfate bevorzugt.As fatty alcohol sulfates, the salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut oil fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol are preferred. Of washing technology interest, the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
Als Fettalkoholethersulfate werden beispielsweise die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7-21-Alkohole, wie 2-Methyl-verzweigte C9-11-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder C12-18-Fettalkohole mit 1 bis 4 EO, eingesetzt.As fatty alcohol ether sulfates are, for example, the sulfuric acid monoesters of ethoxylated with 1 to 6 moles of ethylene oxide straight or branched C 7-21 alcohols such as 2-methyl-branched C 9-11 alcohols having an average of 3.5 moles of ethylene oxide (EO) or C 12th -18 fatty alcohols with 1 to 4 EO used.
Weitere geeignete anionische Tenside sind Fettsäureseifen. Geeignet sind gesättigte und ungesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, (hydrierten) Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, zum Beispiel Kokos-, Palmkern-, Olivenöl- oder Talgfettsäuren, abgeleitete Seifengemische.Further suitable anionic surfactants are fatty acid soaps. Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
Die anionischen Tenside, einschließlich der Fettsäureseifen, können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natriumsalze oder Ammoniumsalze vor. Die Ammoniumsalze können die Salze organischer Basen sein. Das zur Neutralisation eingesetzte Amin ist vorzugsweise Cholin, Triethylamin, Monoethanolamin, Diethanolamin, Triethanolamin, Methylethylamin oder eine Mischung daraus, wobei Monoethanolamin bevorzugt ist.The anionic surfactants, including the fatty acid soaps, may be in the form of their sodium, potassium or ammonium salts. Preferably, the anionic surfactants are in the form of their sodium salts or ammonium salts. The ammonium salts may be the salts of organic bases. The amine used for the neutralization is preferably choline, triethylamine, monoethanolamine, diethanolamine, triethanolamine, methylethylamine or a mixture thereof, with monoethanolamine being preferred.
Geeignete sulfonierte Estolide umfassen Verbindungen der folgenden Formel
In einer ganz besonders bevorzugten Ausführungsform enthält das flüssige Wasch- oder Reinigungsmittel das Natriumsalz eines Fettalkoholethersulfats und eine mit Monoethanolamin neutralisierte Fettsäure. Es ist auch bevorzugt, dass die Menge an Fettalkoholethersulfat in dem gesamten flüssigen Wasch- oder Reinigungsmittel mindestens 5 Gew.-% beträgt.In a very particularly preferred embodiment, the liquid washing or cleaning agent contains the sodium salt of a fatty alcohol ether sulfate and a fatty acid neutralized with monoethanolamine. It is also preferred that the amount of fatty alcohol ether sulfate in the total liquid detergent or cleaning agent is at least 5% by weight.
Die Gesamtmenge an anionischem Tensid in dem flüssigen Wasch- oder Reinigungsmittel beträgt bis zu 35 Gew.-% und vorzugsweise 15 bis 30 Gew.-%, bezogen auf das gesamte flüssige Wasch- oder Reinigungsmittel.The total amount of anionic surfactant in the liquid washing or cleaning agent is up to 35% by weight and preferably 15 to 30% by weight, based on the total liquid detergent or cleaning agent.
Die Gesamtmenge an nichtionischem und anionischem Tensid in dem flüssigen Wasch- oder Reinigungsmittel beträgt bis zu 75 Gew.-% und vorzugsweise 50 bis 60 Gew.-%, bezogen auf das gesamte flüssige Wasch- oder Reinigungsmittel.The total amount of nonionic and anionic surfactant in the liquid washing or cleaning agent is up to 75% by weight and preferably 50 to 60% by weight, based on the total liquid detergent or cleaning agent.
Das flüssige Wasch- oder Reinigungsmittel enthält ferner organisches Lösungsmittel, welches eine Mischung aus 1,2-Propandiol und Ethanol umfasst.The liquid detergent or cleaning agent further contains organic solvent comprising a mixture of 1,2-propanediol and ethanol.
Die Menge an Ethanol beträgt dabei bis zu 5 Gew.-% und vorzugsweise zwischen 1 und 3 Gew.-%, jeweils bezogen auf das gesamte Wasch- oder Reinigungsmittel.The amount of ethanol is up to 5 wt .-%, and preferably between 1 and 3 wt .-%, each based on the total washing or cleaning agent.
Die Menge an 1,2-Propandiol beträgt bis zu 50 Gew.-%, vorzugsweise zwischen 10 und 40 Gew.-%, und ganz besonders bevorzugt zwischen 20 und 35 Gew.-%, jeweils bezogen auf das gesamte Wasch- oder Reinigungsmittel.The amount of 1,2-propanediol is up to 50 wt .-%, preferably between 10 and 40 wt .-%, and most preferably between 20 and 35 wt .-%, each based on the total washing or cleaning agent.
Es hat sich insbesondere gezeigt, dass flüssige Wasch- oder Reinigungsmittel, die andere organische Lösungsmittelsysteme besitzen, beispielsweise eine Mischung aus 1,2-Propandiol und Isopropanol, instabil sind.It has been found, in particular, that liquid washing or cleaning agents which have other organic solvent systems, for example a mixture of 1,2-propanediol and isopropanol, are unstable.
Deshalb ist das flüssige Wasch- oder Reinigungsmittel frei von Isopropanol und in einer ganz besonders bevorzugten Ausführungsform frei von weiteren organischen Lösungsmitteln. Entsprechend enthält ein besonders bevorzugtes flüssiges Wasch- oder Reinigungsmittel ein organisches Lösungsmittel, welches eine Mischung aus 1,2-Propandiol und Ethanol ist.Therefore, the liquid washing or cleaning agent is free of isopropanol and in a most preferred embodiment free of further organic solvents. Accordingly, a particularly preferred liquid washing or cleaning agent contains an organic solvent which is a mixture of 1,2-propanediol and ethanol.
Das flüssige Wasch- oder Reinigungsmittel enthält Wasser, wobei der Gehalt an Wasser weniger als 15 Gew.-% und mehr bevorzugt weniger als 13 Gew.-%, jeweils bezogen auf das gesamte flüssige Wasch- oder Reinigungsmittel, beträgt. Insbesondere bevorzugt enthält das gesamte flüssige Wasch- oder Reinigungsmittel 7 bis 12 Gew.-% Wasser.The liquid washing or cleaning agent contains water, wherein the content of water is less than 15 wt .-%, and more preferably less than 13 wt .-%, each based on the total liquid detergent or cleaning agent. Particularly preferably, the entire liquid washing or cleaning agent contains 7 to 12 wt .-% water.
Vorzugsweise weist das flüssige Wasch- oder Reinigungsmittel eine Wasseraktivität aw von mehr als 0,38 und mehr bevorzugt von mehr als 0,42 auf. Die Bestimmung der Wasseraktivität erfolgt bei 25 °C mit einem "AquaLab Lite"-Gerät der Firma IUL Instruments GmbH.Preferably, the liquid washing or cleaning agent has a water activity a w of more than 0.38, and more preferably more than 0.42. The determination of the water activity is carried out at 25 ° C with an "AquaLab Lite" device from IUL Instruments GmbH.
Die Wasseraktivität aw ist ein Maß für frei verfügbares Wasser in einem Material und gibt die Verfügbarkeit des Wassers für chemische, biochemische und mikrobielle Reaktionen an. Die Wasseraktivität wird als aw-Wert angegeben und ist definiert als der Quotient aus der Konzentration an Wasser in der Dampfphase im Luftraum über dem Material und der Wasserkonzentration im Luftraum über reinem Wasser bei einer bestimmten Temperatur:
Zusätzlich zu dem nichtionischen Tensid, dem anionischen Tensid und dem organischen Lösungsmittel kann das Wasch- oder Reinigungsmittel weitere Inhaltsstoffe enthalten, die die anwendungstechnischen und/oder ästhetischen Eigenschaften des Wasch- oder Reinigungsmittels weiter verbessern, aber die die strukturelle Integrität der wasserlöslichen Umhüllung nicht zerstören. Im Rahmen der vorliegenden Erfindung enthält das Wasch- oder Reinigungsmittel vorzugsweise zusätzlich einen oder mehrere Stoffe aus der Gruppe der Gerüststoffe, Bleichmittel, Enzyme, pH-Stellmittel, Parfüme, Parfümträger, Fluoreszenzmittel, Farbstoffe, Hydrotope, Schauminhibitoren, Silikonöle, Antiredepositionsmittel, Vergrauungsinhibitoren, Einlaufverhinderer, Knitterschutzmittel, Farbübertragungsinhibitoren, antimikrobiellen Wirkstoffe, nicht-wässrigen Lösungsmittel, Germizide, Fungizide, Antioxidantien, Konservierungsmittel, Korrosionsinhibitoren, Antistatika, Bittermittel, Bügelhilfsmittel, Phobier- und Imprägniermittel, Haut-pflegende Wirkstoffe, Quell- und Schiebefestmittel, weichmachenden Komponenten sowie UV-Absorber.In addition to the nonionic surfactant, the anionic surfactant and the organic solvent, the washing or cleaning agent may contain other ingredients containing the improve the performance and / or aesthetic properties of the detergent or cleaning agent, but not destroy the structural integrity of the water-soluble envelope. In the context of the present invention, the washing or cleaning agent preferably additionally contains one or more substances from the group of builders, bleaches, enzymes, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils, antiredeposition agents, grayness inhibitors, anti-shrinkage agents Anti-crease agents, color transfer inhibitors, antimicrobial agents, non-aqueous solvents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, skin-care agents, swelling and anti-slip agents, plasticizing components and UV absorbers ,
Das flüssige Wasch- oder Reinigungsmittel weist vorzugsweise eine Ionenstärke Ic von kleiner 250 mmol/l, mehr bevorzugt kleiner 200 mmol/l und ganz besonders bevorzugt kleiner 150 mmol/l auf. Die Ionenstärke I einer Lösung ist ein Maß für die elektrische Feldstärke aufgrund gelöster Ionen. Die Ionenstärke I kann sowohl über die Molarität c, als auch die Molalität b der gelösten Ionen wie folgt definiert werden:
- ci = Molarität der Ionensorte i (in mol/l)
- bi = Molalität der Ionensorte i (in mol/kg)
- zi = Ladungszahl der Ionensorte i
- Ic bzw. Ib: Ionenstärke der Lösung bezogen auf die Molarität bzw. die Molalität
- c i = molarity of the ion type i (in mol / l)
- b i = molarity of the ion type i (in mol / kg)
- z i = charge number of the ion type i
- I c or I b : ionic strength of the solution based on the molarity or molality
Es hat sich gezeigt, dass eine Erhöhung der Ionenstärke Ic auf 250 mol/l und mehr, beispielsweise durch Zusatz von anorganischen Salzen, um freies Wasser zu binden, zu einem Aussalzen von Inhaltsstoffen des Wasch- oder Reinigungsmittels und/oder zu Ablagerungen an der wasserlöslichen Umhüllung führen kann.It has been found that an increase in the ionic strength I c to 250 mol / l and more, for example by addition of inorganic salts to bind free water, to a salting out of ingredients of the detergent or / and deposits on the water-soluble envelope may result.
Aus diesem Grund kann es bevorzugt sein, dass das flüssige Wasch- oder Reinigungsmittel frei von zugesetzten anorganischen Salzen ist.For this reason, it may be preferred that the liquid washing or cleaning agent is free from added inorganic salts.
Es ist ferner bevorzugt, dass die Menge an aerob nicht biologisch abbaubaren organischen Inhaltsstoffen (aNBO) in dem Wasch- oder Reinigungsmittel weniger als 0,55 g pro kg Waschladung beträgt.It is further preferred that the amount of aerobic non-biodegradable organic ingredients (aNBO) in the detergent or cleaning agent is less than 0.55 g per kg wash load.
Ebenso ist bevorzugt, dass die Menge an anaerob nicht biologisch abbaubaren organischen Inhaltsstoffen (anNBO) in dem Wasch- oder Reinigungsmittel weniger als 0,70 g pro kg Waschladung beträgt.It is also preferred that the amount of anaerobically nonbiodegradable organic ingredients (anNBO) in the detergent or cleaner be less than 0.70 g per kg wash load.
Eine Waschladung entspricht einer Dosierung von 35 g Wasch- oder Reinigungsmittel auf 4,5 kg Wäsche.A wash load corresponds to a dosage of 35 g washing or cleaning agent to 4.5 kg of laundry.
Das flüssige Wasch- oder Reinigungsmittel befindet sich in einer wasserlöslichen Umhüllung.The liquid washing or cleaning agent is in a water-soluble coating.
Eine wasserlösliche Verpackung enthält neben dem flüssigen Wasch- oder Reinigungsmittel eine wasserlösliche Umhüllung. Die wasserlösliche Umhüllung wird vorzugsweise durch ein wasserlösliches Folienmaterial gebildet.A water-soluble packaging contains, in addition to the liquid washing or cleaning agent, a water-soluble coating. The water-soluble coating is preferably formed by a water-soluble film material.
Solche wasserlöslichen Verpackungen können entweder durch Verfahren des vertikalen Formfüllversiegelns (VFFS) oder Warmformverfahren hergestellt werden.Such water-soluble packages can be made by either vertical fill-seal (VFFS) or thermoforming techniques.
Das Warmformverfahren schließt im Allgemeinen das Formen einer ersten Lage aus einem wasserlöslichen Folienmaterial zum Bilden von Ausbuchtungen zum Aufnehmen einer Zusammensetzung darin, Einfüllen der Zusammensetzung in die Ausbuchtungen, Bedecken der mit der Zusammensetzung gefüllten Ausbuchtungen mit einer zweiten Lage aus einem wasserlöslichen Folienmaterial und Versiegeln der ersten und zweiten Lagen miteinander zumindest um die Ausbuchtungen herum ein.The thermoforming process generally includes forming a first layer of water-soluble sheet material to form protrusions for receiving a composition therein, filling the composition into the protrusions, covering the composition-filled protrusions with a second layer of water-soluble sheet material, and sealing the first and second layers at least around the bulges.
Die wasserlösliche Umhüllung wird vorzugsweise aus einem wasserlöslichen Folienmaterial ausgewählt aus der Gruppe umfassend Polymeren und Polymergemischen gebildet. Die Umhüllung kann aus einer oder aus zwei oder mehr Lagen aus dem wasserlöslichen Folienmaterial gebildet werden. Das wasserlösliche Folienmaterial der ersten Lage und der weiteren Lagen, falls vorhanden, kann gleich oder unterschiedlich sein.The water-soluble coating is preferably formed from a water-soluble film material selected from the group comprising polymers and polymer blends. The wrapper may be formed of one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if present, may be the same or different.
Es ist bevorzugt, dass die wasserlösliche Umhüllung Polyvinylalkohol oder ein Polyvinylalkoholcopolymer enthält.It is preferable that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
Geeignete wasserlösliche Folien zur Herstellung der wasserlöslichen Umhüllung basieren bevorzugt auf einem Polyvinylalkohol oder einem Polyvinylalkoholcopolymer, dessen Molekulargewicht im Bereich von 10.000 bis 1.000.000 gmol-1, vorzugsweise von 20.000 bis 500.000 gmol-1, besonders bevorzugt von 30.000 bis 100.000 gmol-1 und insbesondere von 40.000 bis 80.000 gmol-1 liegt.Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 10,000 to 1,000,000 gmol -1 , preferably 20,000 to 500,000 gmol -1 , more preferably 30,000 to 100,000 gmol -1 and especially from 40,000 to 80,000 gmol -1 .
Die Herstellung von Polyvinylalkohol geschieht üblicherweise durch Hydrolyse von Polyvinylacetat, da der direkte Syntheseweg nicht möglich ist. Ähnliches gilt für Polyvinylalkoholcopolymere, die aus entsprechend aus Polyvinylacetatcopolymeren hergestellt werden. Bevorzugt ist, wenn wenigstens eine Lage der wasserlöslichen Umhüllung einen Polyvinylalkohol umfasst, dessen Hydrolysegrad 70 bis 100 Mol-%, vorzugsweise 80 bis 90 Mol-%, besonders bevorzugt 81 bis 89 Mol-% und insbesondere 82 bis 88 Mol-% ausmacht.The production of polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
Einem zur Herstellung der wasserlöslichen Umhüllung geeignetem Polyvinylalkohol-enthaltendem Folienmaterial kann zusätzlich ein Polymer ausgewählt aus der Gruppe umfassend (Meth)Acrylsäure-haltige (Co)Polymere, Polyacrylamide, Oxazolin-Polymere, Polystyrolsulfonate, Polyurethane, Polyester, Polyether, Polymilchsäuren oder Mischungen der vorstehenden Polymere zugesetzt sein. Ein bevorzugtes zusätzliches Polymer sind Polymilchsäuren.In addition, a polymer selected from the group consisting of (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acids or mixtures of the above may additionally be selected from a polyvinyl alcohol-containing film material suitable for producing the water-soluble coating Be added polymers. A preferred additional polymer is polylactic acids.
Bevorzugte Polyvinylalkoholcopolymere umfassen neben Vinylalkohol Dicarbonsäuren als weitere Monomere. Geeignete Dicarbonsäure sind Itaconsäure, Malonsäure, Bernsteinsäure und Mischungen daraus, wobei Itaconsäure bevorzugt ist.Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
Ebenfalls bevorzugte Polyvinylalkoholcopolymere umfassen neben Vinylalkohol eine ethylenisch ungesättige Carbonsäure, deren Salz oder deren Ester. Besonders bevorzugt enthalten solche Polyvinylalkoholcopolymere neben Vinylalkohol Acrylsäure, Methacrylsäure, Acrylsäureester, Methacrylsäureester oder Mischungen daraus.Likewise preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.
Es kann bevorzugt sein, dass das Folienmaterial weitere Zusatzstoffe enthält. Das Folienmaterial kann beispielsweise Weichmacher wie Dipropylenglycol, Ethylenglycol, Diethylenglycol, Propylenglycol, Glycerin, Sorbitol, Mannitol oder Mischungen daraus enthalten. Weitere Zusatzstoffe umfassen beispielsweise Freisetzungshilfen, Füllmittel, Vernetzungsmittel, Tenside, Antioxidationsmittel, UV-Absorber, Antiblockmittel, Antiklebemittel oder Mischungen daraus.It may be preferred that the film material contains further additives. The film material may contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof. Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-sticking agents or mixtures thereof.
Geeignete wasserlösliche Folien zum Einsatz in den wasserlöslichen Umhüllungen der wasserlöslichen Verpackungen gemäß der Erfindung sind Folien, die von der Firma MonoSol LLC beispielsweise unter der Bezeichnung M8630, M8310, C8400 oder M8900 vertrieben werden. Andere geeignete Folien umfassen Folien mit der Bezeichnung Solublon® PT, Solublon® GA, Solublon® KC oder Solublon® KL von der Aicello Chemical Europe GmbH oder die Folien VF-HP von Kuraray.Suitable water-soluble films for use in the water-soluble casings of the water-soluble packaging according to the invention are films sold by MonoSol LLC, for example under the designation M8630, M8310, C8400 or M8900. Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
In einer bevorzugten Ausführungsform weist die wasserlösliche Verpackung eine Kammer zur Aufnahme des flüssigen Wasch- oder Reinigungsmittels auf.In a preferred embodiment, the water-soluble packaging has a chamber for receiving the liquid detergent or cleaning agent.
In einer weiteren, ebenfalls bevorzugten Ausführungsform weist die wasserlösliche Verpackung zwei Kammern auf. In dieser Ausführungsform enthält die erste Kammer das oben beschriebene flüssige Wasch- oder Reinigungsmittel und die zweite Kammer kann ein festes oder ein flüssiges Wasch- oder Reinigungsmittel enthalten.In a further, likewise preferred embodiment, the water-soluble packaging has two chambers. In this embodiment, the first chamber contains the above-described liquid detergent or cleaning agent and the second chamber may contain a solid or a liquid detergent or cleaning agent.
Weist die wasserlösliche Verpackung drei Kammern auf, können diese Kammern alle jeweils ein flüssiges Wasch- oder Reinigungsmittel enthalten. Möglich ist aber auch, dass eine Kammer ein festes Wasch- oder Reinigungsmittel und zwei Kammern ein flüssiges Wasch- oder Reinigungsmittel enthalten. Außerdem ist es möglich, dass in zwei Kammern ein festes Wasch- oder Reinigungsmittel und in einer Kammer ein flüssiges Wasch- oder Reinigungsmittel enthalten ist.If the water-soluble packaging has three chambers, these chambers can each contain a liquid washing or cleaning agent. But it is also possible that a chamber containing a solid detergent or detergent and two chambers containing a liquid detergent or cleaning agent. It is also possible that a solid detergent or cleaning agent is contained in two chambers and a liquid detergent or cleaning agent in a chamber.
Bei wasserlöslichen Verpackungen mit vier oder mehr Kammern bestehen entsprechend noch mehr Kombinationsmöglichkeiten im Hinblick auf die Zahl der Kammern mit einem festen oder einem flüssigen Wasch- oder Reinigungsmittel.In the case of water-soluble packaging with four or more chambers, there are correspondingly even more possible combinations with regard to the number of chambers with a solid or a liquid washing or cleaning agent.
Bei wasserlöslichen Verpackungen mit zwei oder mehr Kammern enthält mindestens eine Kammer das oben beschriebene, erfindungsgemäße flüssige Wasch- oder Reinigungsmittel mit ausschließlich Tensiden, die aus nachwachsenden Rohstoffen gewonnenen werden. Die flüssigen Wasch- oder Reinigungsmittel, die in den anderen Kammern einer wasserlöslichen Verpackung enthalten sind, können dieselbe Zusammensetzung aufweisen. Vorzugsweise weisen die flüssigen Wasch- oder Reinigungsmittels in einer wasserlöslichen Verpackung mit mindestens zwei Kammern Zusammensetzungen auf, die sich mindestens im Gehalt eines Inhaltsstoffs unterscheiden.In the case of water-soluble packaging with two or more chambers, at least one chamber contains the above-described liquid detergent or cleaning agent according to the invention with exclusively surfactants which are obtained from renewable raw materials. The liquid detergents or cleaning agents contained in the other chambers of a water-soluble packaging may have the same composition. The liquid detergents or cleaners in a water-soluble packaging with at least two chambers preferably have compositions which differ at least in the content of an ingredient.
Die Menge an Wasch- oder Reinigungsmittel, welche sich insgesamt in der wasserlöslichen Verpackung befindet, entspricht vorzugsweise der vollen oder halben Dosis, die für einen Waschgang benötigt wird.The amount of detergent or cleaning agent, which is in total in the water-soluble packaging, preferably corresponds to the full or half dose required for a wash.
Es wurden flüssige Wasch- oder Reinigungsmittel mittels üblicher und bekannter Methoden und Verfahren hergestellt. In der folgenden Tabelle 1 sind die Zusammensetzungen von zwei erfindungsgemäßen Wasch- oder Reinigungsmitteln E1 und E2 sowie vier nicht erfindungsgemäßen Wasch- oder Reinigungsmitteln V1 bis V4 gezeigt.
Die Ionenstärke Ic der flüssigen Wasch- oder Reinigungsmittel E1 und E2 betrug jeweils kleiner 150 mmol/l. Die Menge an aerob nicht biologisch abbaubaren organischen Inhaltsstoffen (aNBO) betrug in den Wasch- oder Reinigungsmitteln E1 und E2 jeweils 0,13 g pro kg Waschladung. Die Menge an aerob nicht biologisch abbaubaren organischen Inhaltsstoffen (anNBO) betrug in den Wasch- oder Reinigungsmitteln E1 und E2 jeweils 0,14 g pro kg Waschladung. Die Wasseraktivität aw der flüssigen Wasch- oder Reinigungsmittel E1 und E2 betrug jeweils 0,45.The ionic strength I c of the liquid washing or cleaning agents E1 and E2 was in each case less than 150 mmol / l. The amount of aerobic non-biodegradable organic ingredients (aNBO) in detergents E1 and E2 was 0.13 g per kg wash load, respectively. The amount of aerobic non-biodegradable organic ingredients (ANNBO) in detergents E1 and E2 was 0.14 g per kg wash load, respectively. The water activity a w of the liquid washing or cleaning agents E1 and E2 was 0.45 in each case.
Zur Herstellung von wasserlöslichen Verpackungen mit den Wasch- oder Reinigungsmitteln E1 und E2 sowie V1 bis V4 wurde eine Folie vom Typ M 8630 (ex Monosol) mit einer Dicke von 76 µm zum Ausbilden einer Ausbuchtung mittels Vakuum in eine Mulde gezogen. Anschließend wurde die Ausbuchtung mit 30 ml eines der flüssigen Wasch- oder Reinigungsmittel E1, E2 oder V1 bis V4 befüllt. Nach Bedecken der mit dem Mittel befüllten Ausbuchtungen mit einer zweiten Lage einer Folie vom Typ M 8630 wurden die erste und zweite Lage miteinander versiegelt. Die Siegelungstemperatur betrug 150 °C und die Siegelungsdauer 1,1 Sekunden.To prepare water-soluble packages with the detergents E1 and E2 and V1 to V4, a film of the type M 8630 (ex Monosol) with a thickness of 76 μm was pulled into a depression by means of a vacuum to form a bulge. Subsequently, the bulge was mixed with 30 ml of one of the liquid detergents or cleaners E1, E2 or V1 to V4 filled. After covering the agent filled bulges with a second layer of M 8630 film, the first and second layers were sealed together. The sealing temperature was 150 ° C and the sealing time 1.1 seconds.
Nach 4, 8 und 12 Wochen Lagerzeit der wasserlöslichen Verpackungen mit den Wasch- oder Reinigungsmitteln E1 und E2 unter verschiedenen klimatischen Bedingungen konnte keinerlei An- oder Auflösung der wasserlöslichen Umhüllung beobachtet werden. Zudem konnten keine Poren oder Löcher, die ebenfalls zum Produktaustritt oder Leckagen führen würden, festgestellt werden.After 4, 8 and 12 weeks storage time of the water-soluble packaging with the detergents or cleaning agents E1 and E2 under different climatic conditions, no contact or dissolution of the water-soluble coating could be observed. In addition, no pores or holes, which would also lead to product leakage or leaks, were found.
Wasserlösliche Verpackungen mit den flüssigen Wasch- oder Reinigungsmitteln E1 und E2 lösten sich in Waschgängen bei Temperaturen, die im Bereich von 20 bis 95 °C lagen, rückstandslos auf und zeigten verglichen mit einer wasserlöslichen Verpackung mit einem flüssigen Wasch- oder Reinigungsmittel, welches als Tensidsystem C12-18-Fettsäureseife, C12-18-Fettalkohol mit 7 EO und ein C9-13-Alkylbenzolsulfonat enthielt, eine gleich gute Reinigungsleistung auf.Water-soluble packaging with the liquid washing or cleaning agents E1 and E2 dissolved in washes at temperatures ranging from 20 to 95 ° C, without residue and showed compared with a water-soluble packaging with a liquid detergent or cleaning agent which acts as a surfactant system C 12-18 fatty acid soap, C 12-18 fatty alcohol containing 7 EO and a C 9-13 alkylbenzenesulfonate, an equally good cleaning performance.
Bei wasserlöslichen Verpackungen mit den flüssigen Wasch- oder Reinigungsmitteln V2 bis V4 zeigten sich bereits nach einem Tag starke Sedimentationen. Das flüssige Wasch- oder Reinigungsmittel V1 gelierte während der Lagerung in der wasserlöslichen Verpackung. Außerdem trat Flüssigkeit durch die wasserlösliche Umhüllung auf die Oberfläche der wasserlöslichen Verpackung aus.In the case of water-soluble packaging containing liquid washing or cleaning agents V2 to V4, sedimentation already occurred after one day. The liquid washing or cleaning agent V1 gelled during storage in the water-soluble packaging. In addition, liquid leaked out through the water-soluble envelope onto the surface of the water-soluble package.
Claims (6)
- A water-soluble packaging which contains a liquid washing or cleaning agent and a water soluble wrapping, characterized in that the liquid washing or cleaning agent containsa) non-ionic surfactant selected from the group consisting of alkoxylated fatty alcohols, alkyl polyglycosides, ethoxylated methyl esters of natural fatty acids and mixtures thereof,b) anionic surfactant selected from the group consisting of fatty alcohol sulfates, fatty alcohol ether sulfates, fatty acid soaps, sulfonated estolides and mixtures thereof,c) organic solvent which comprises a mixture of 1,2-propanediol and ethanol,d) up to 15 wt.%, based on the entire washing or cleaning agent, water,e) up to 50 wt.%, based on the entire washing or cleaning agent, 1,2-propanediol,f) up to 5 wt.%, based on the entire washing or cleaning agent, ethanol, and isg) free of isopropanol, preferably free of additional organic solvents, the total amount of anionic surfactant being up to 35 wt.% based on the entire washing or cleaning agent.
- The water-soluble packaging according to claim 1, characterized in that the ionic strength Ic of the washing or cleaning agent is less than 250 mmol/l.
- The water-soluble packaging according to one of claims 1 to 2, characterized in that the anionic surfactant is a mixture of fatty alcohol ether sulfates and fatty acid soaps.
- The water-soluble packaging according to one of claims 1 to 3, characterized in that the liquid washing or cleaning agent contains at least 5 wt.% fatty alcohol ether sulfate.
- The water-soluble packaging according to one of claims 1 to 4, characterized in that the washing or cleaning agent has a water activity aw ≥ 0.38.
- The water-soluble packaging according to one of claims 1 to 5, characterized in that the water-soluble wrapping contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102012208286A DE102012208286A1 (en) | 2012-05-16 | 2012-05-16 | Low-water, liquid detergent with surfactants derived from renewable raw materials |
PCT/EP2013/059469 WO2013171095A1 (en) | 2012-05-16 | 2013-05-07 | Low-water-content, liquid detergent comprising surfactants obtained from renewable raw materials |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2850169A1 EP2850169A1 (en) | 2015-03-25 |
EP2850169B1 true EP2850169B1 (en) | 2018-11-14 |
Family
ID=48325722
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP13720952.4A Active EP2850169B1 (en) | 2012-05-16 | 2013-05-07 | Low-water-content, liquid detergent comprising surfactants obtained from renewable raw materials |
Country Status (4)
Country | Link |
---|---|
US (1) | US10160939B2 (en) |
EP (1) | EP2850169B1 (en) |
DE (1) | DE102012208286A1 (en) |
WO (1) | WO2013171095A1 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102014202221A1 (en) * | 2014-02-06 | 2015-08-06 | Henkel Ag & Co. Kgaa | Multi-phase pre-portioned detergent |
DE102014225478A1 (en) * | 2014-12-10 | 2016-06-16 | Henkel Ag & Co. Kgaa | Washing or cleaning agent with special a-amylase and defined water activity aw |
US9796948B2 (en) | 2016-01-13 | 2017-10-24 | The Procter & Gamble Company | Laundry detergent compositions comprising renewable components |
US9896648B2 (en) | 2016-03-02 | 2018-02-20 | The Procter & Gamble Company | Ethoxylated diols and compositions containing ethoxylated diols |
EP3363889A1 (en) * | 2017-02-21 | 2018-08-22 | The Procter & Gamble Company | Use of liquid laundry detergent composition to minimize adverse effects upon accidental exposure to contents of water-soluble unit dose articles |
EP3372664A3 (en) * | 2017-02-21 | 2018-11-28 | The Procter & Gamble Company | Use of liquid laundry detergent composition to minimize adverse effects upon accidental exposure to contents of water-soluble unit dose articles |
US20190048296A1 (en) * | 2017-08-10 | 2019-02-14 | Henkel IP & Holding GmbH | Unit dose detergent products with improved pac rigidity |
CN114231362B (en) * | 2021-12-29 | 2023-10-31 | 赞宇科技集团股份有限公司 | Antibacterial laundry gel bead and preparation method thereof |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998000491A1 (en) | 1996-06-28 | 1998-01-08 | The Procter & Gamble Company | Detergent composition |
US7012053B1 (en) | 1999-10-22 | 2006-03-14 | The Procter & Gamble Company | Fabric care composition and method comprising a fabric care polysaccharide and wrinkle control agent |
US20100093595A1 (en) | 2008-10-15 | 2010-04-15 | Holzhauer Frederick W | Liquid cleaning compositions |
US20110065625A1 (en) | 2009-09-14 | 2011-03-17 | Jean-Pol Boutique | External structuring system for liquid laundry detergent composition |
WO2011075551A1 (en) | 2009-12-18 | 2011-06-23 | The Procter & Gamble Company | Perfumes and perfume encapsulates |
US8097579B2 (en) | 2007-11-09 | 2012-01-17 | The Procter & Gamble Company | Cleaning compositions with amphiphilic water-soluble polyalkylenimines having an inner polyethylene oxide block and an outer polypropylene oxide block |
WO2012166768A1 (en) | 2011-06-03 | 2012-12-06 | The Procter & Gamble Company | Laundry care compositions containing dyes |
WO2013135512A1 (en) * | 2012-03-14 | 2013-09-19 | Henkel Ag & Co. Kgaa | Dusted, water-soluble packaging |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4341050A1 (en) * | 1993-12-02 | 1995-06-08 | Huels Chemische Werke Ag | Surfactant concentrates as a base side for concentrated liquid formulations |
US6995126B2 (en) * | 2000-04-28 | 2006-02-07 | The Procter & Gamble Company | Pouched compositions |
MXPA03006455A (en) | 2001-01-19 | 2004-02-12 | Reckitt Benckiser Nv | Improvements in or relating to liquid detergent compositions. |
EP1354939A1 (en) * | 2002-04-19 | 2003-10-22 | The Procter & Gamble Company | Pouched cleaning compositions |
US7666828B2 (en) * | 2008-01-22 | 2010-02-23 | Stepan Company | Sulfonated estolides and other derivatives of fatty acids, methods of making them, and compositions and processes employing them |
US7879790B2 (en) * | 2008-01-22 | 2011-02-01 | Stepan Company | Mixed salts of sulfonated estolides and other derivatives of fatty acids, and methods of making them |
EP2133410B1 (en) * | 2008-06-13 | 2011-12-28 | The Procter & Gamble Company | Multi-compartment pouch |
US7939487B2 (en) * | 2008-08-26 | 2011-05-10 | The Clorox Company | Natural cleaners |
US8119588B2 (en) * | 2009-01-21 | 2012-02-21 | Stepan Company | Hard surface cleaner compositions of sulfonated estolides and other derivatives of fatty acids and uses thereof |
EP2258820B1 (en) * | 2009-06-02 | 2019-12-18 | The Procter and Gamble Company | Water-soluble pouch |
RU2546651C2 (en) * | 2010-01-29 | 2015-04-10 | МОНОСОЛ, ЭлЭлСи | Water-soluble film with improved solubility and improved mechanical properties, as well as packets, produced from it |
CN105647715B (en) * | 2010-07-02 | 2019-10-25 | 宝洁公司 | Detergent product |
EP2441824A1 (en) * | 2010-10-15 | 2012-04-18 | Cognis IP Management GmbH | Laundry liquid suitable for packaging in polyvinyl alcohol pouches |
-
2012
- 2012-05-16 DE DE102012208286A patent/DE102012208286A1/en not_active Withdrawn
-
2013
- 2013-05-07 WO PCT/EP2013/059469 patent/WO2013171095A1/en unknown
- 2013-05-07 EP EP13720952.4A patent/EP2850169B1/en active Active
-
2014
- 2014-11-06 US US14/534,902 patent/US10160939B2/en not_active Expired - Fee Related
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998000491A1 (en) | 1996-06-28 | 1998-01-08 | The Procter & Gamble Company | Detergent composition |
US7012053B1 (en) | 1999-10-22 | 2006-03-14 | The Procter & Gamble Company | Fabric care composition and method comprising a fabric care polysaccharide and wrinkle control agent |
US8097579B2 (en) | 2007-11-09 | 2012-01-17 | The Procter & Gamble Company | Cleaning compositions with amphiphilic water-soluble polyalkylenimines having an inner polyethylene oxide block and an outer polypropylene oxide block |
US20100093595A1 (en) | 2008-10-15 | 2010-04-15 | Holzhauer Frederick W | Liquid cleaning compositions |
WO2010044835A1 (en) | 2008-10-15 | 2010-04-22 | Method Products, Inc. | Liquid cleaning compositions |
US20110065625A1 (en) | 2009-09-14 | 2011-03-17 | Jean-Pol Boutique | External structuring system for liquid laundry detergent composition |
WO2011075551A1 (en) | 2009-12-18 | 2011-06-23 | The Procter & Gamble Company | Perfumes and perfume encapsulates |
WO2012166768A1 (en) | 2011-06-03 | 2012-12-06 | The Procter & Gamble Company | Laundry care compositions containing dyes |
WO2013135512A1 (en) * | 2012-03-14 | 2013-09-19 | Henkel Ag & Co. Kgaa | Dusted, water-soluble packaging |
Also Published As
Publication number | Publication date |
---|---|
US20150065410A1 (en) | 2015-03-05 |
EP2850169A1 (en) | 2015-03-25 |
US10160939B2 (en) | 2018-12-25 |
DE102012208286A1 (en) | 2013-11-21 |
WO2013171095A1 (en) | 2013-11-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2850169B1 (en) | Low-water-content, liquid detergent comprising surfactants obtained from renewable raw materials | |
EP2867352B1 (en) | Highly concentrated liquid washing or cleaning composition | |
EP2773735B1 (en) | Structured detergent composition having a flow limit | |
DE60106631T2 (en) | WATER-SOLUBLE, HOT-MOLDED, AQUEOUS CONTAINERS CONTAINING CONTAINERS | |
EP2802643B1 (en) | Fragrant, water-soluble packaging | |
DE60216256T2 (en) | WATER-SOLUBLE CONTAINER WITH AT LEAST TWO OPENINGS | |
WO2016055346A1 (en) | Film-packaged agent portion | |
EP3354592A1 (en) | Coloured, water soluble package | |
EP2828368B1 (en) | Liquid detergent composition with increased cleaning performance | |
DE602004007791T2 (en) | WATER-SOLUBLE CONTAINER | |
WO2015150231A1 (en) | Water-soluble singe-use packet having a dimensionally stable lid | |
WO2014040865A1 (en) | Structured, low-water, liquid detergent having particles | |
EP2809759B1 (en) | Low-water, liquid detergent having increased fat-dissolving power | |
EP2875107B1 (en) | Stable, liquid detergent with anti-redeposition action | |
DE102013226426A1 (en) | Preservative system for detergents | |
DE602004000316T2 (en) | Water-soluble packaging with liquid contents | |
DE102011085639A1 (en) | Liquid detergent or cleaning agent useful e.g. for washing textile sheet material or hard surface, comprises anionic surfactant including sulfonate- or sulfate surfactants, nonionic surfactant including e.g. amine oxides and inorganic salt | |
DE102014014767A1 (en) | Foil wrapped medium portion | |
EP2875106B1 (en) | Stable liquid detergent composition showing anti redepositon effect | |
DE102016206647A1 (en) | liquid detergent | |
DE102019219881A1 (en) | Rinse aid for automatic dishwashers | |
WO2015091109A1 (en) | Hpmc-containing liquid laundry detergent |
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 |
|
17P | Request for examination filed |
Effective date: 20140306 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: KOELLING, LEYLA Inventor name: SCHUEMANN, SABINE Inventor name: MEIER, FRANK Inventor name: BELLOMI, LUCA Inventor name: SUNDER, MATTHIAS |
|
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20170104 |
|
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: 20180627 |
|
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: CH Ref legal event code: EP Ref country code: AT Ref legal event code: REF Ref document number: 1064828 Country of ref document: AT Kind code of ref document: T Effective date: 20181115 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502013011608 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20181114 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: 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: 20181114 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: 20190314 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: 20190214 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: 20181114 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: 20190214 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181114 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: 20181114 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181114 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181114 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: 20181114 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181114 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: 20190215 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: 20181114 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: 20190314 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181114 Ref country code: PL 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: 20181114 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181114 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: 20181114 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R026 Ref document number: 502013011608 Country of ref document: DE |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
PLAX | Notice of opposition and request to file observation + time limit sent |
Free format text: ORIGINAL CODE: EPIDOSNOBS2 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181114 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181114 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181114 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181114 |
|
26 | Opposition filed |
Opponent name: THE PROCTER & GAMBLE COMPANY Effective date: 20190814 Opponent name: DALLI-WERKE GMBH & CO. KG Effective date: 20190809 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181114 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PLBB | Reply of patent proprietor to notice(s) of opposition received |
Free format text: ORIGINAL CODE: EPIDOSNOBS3 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190531 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190531 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181114 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20190531 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190507 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181114 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190507 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190531 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 1064828 Country of ref document: AT Kind code of ref document: T Effective date: 20190507 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190507 |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
PLCK | Communication despatched that opposition was rejected |
Free format text: ORIGINAL CODE: EPIDOSNREJ1 |
|
R26 | Opposition filed (corrected) |
Opponent name: DALLI-WERKE GMBH & CO. KG Effective date: 20190809 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181114 |
|
APAH | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOSCREFNO |
|
APBM | Appeal reference recorded |
Free format text: ORIGINAL CODE: EPIDOSNREFNO |
|
APBP | Date of receipt of notice of appeal recorded |
Free format text: ORIGINAL CODE: EPIDOSNNOA2O |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181114 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20130507 |
|
APBQ | Date of receipt of statement of grounds of appeal recorded |
Free format text: ORIGINAL CODE: EPIDOSNNOA3O |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181114 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230530 |
|
APBU | Appeal procedure closed |
Free format text: ORIGINAL CODE: EPIDOSNNOA9O |
|
PLAY | Examination report in opposition despatched + time limit |
Free format text: ORIGINAL CODE: EPIDOSNORE2 |
|
PLBC | Reply to examination report in opposition received |
Free format text: ORIGINAL CODE: EPIDOSNORE3 |
|
PLAY | Examination report in opposition despatched + time limit |
Free format text: ORIGINAL CODE: EPIDOSNORE2 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20240521 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240521 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20240528 Year of fee payment: 12 |