EP1126019A1 - Wässriges mehrphasiges Reinigungsmittel - Google Patents
Wässriges mehrphasiges Reinigungsmittel Download PDFInfo
- Publication number
- EP1126019A1 EP1126019A1 EP01103811A EP01103811A EP1126019A1 EP 1126019 A1 EP1126019 A1 EP 1126019A1 EP 01103811 A EP01103811 A EP 01103811A EP 01103811 A EP01103811 A EP 01103811A EP 1126019 A1 EP1126019 A1 EP 1126019A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phase
- agent
- alkyl
- agent according
- mixtures
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012459 cleaning agent Substances 0.000 title claims description 14
- 239000012071 phase Substances 0.000 claims abstract description 70
- 239000000839 emulsion Substances 0.000 claims abstract description 17
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 239000008346 aqueous phase Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 8
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims abstract description 6
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims abstract description 6
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 54
- 239000000203 mixture Substances 0.000 claims description 41
- -1 alkyl ether sulfates Chemical class 0.000 claims description 16
- 150000002170 ethers Chemical class 0.000 claims description 13
- 229920000151 polyglycol Polymers 0.000 claims description 12
- 239000010695 polyglycol Substances 0.000 claims description 12
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 11
- 230000002209 hydrophobic effect Effects 0.000 claims description 11
- 239000002736 nonionic surfactant Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000003945 anionic surfactant Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 150000001983 dialkylethers Chemical class 0.000 claims description 6
- 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 claims description 5
- 239000003093 cationic surfactant Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 239000000341 volatile oil Substances 0.000 claims description 5
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical class CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 4
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- 150000001860 citric acid derivatives Chemical class 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 3
- 235000015424 sodium Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 229940087305 limonene Drugs 0.000 claims description 2
- 235000001510 limonene Nutrition 0.000 claims description 2
- 239000010665 pine oil Substances 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 239000003599 detergent Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000005191 phase separation Methods 0.000 description 7
- 150000002191 fatty alcohols Chemical class 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002280 amphoteric surfactant Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000006384 oligomerization reaction Methods 0.000 description 3
- 239000002304 perfume Substances 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- WNWHHMBRJJOGFJ-UHFFFAOYSA-N 16-methylheptadecan-1-ol Chemical compound CC(C)CCCCCCCCCCCCCCCO WNWHHMBRJJOGFJ-UHFFFAOYSA-N 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 229930182470 glycoside Natural products 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000003752 hydrotrope Substances 0.000 description 2
- BTFJIXJJCSYFAL-UHFFFAOYSA-N icosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000000176 sodium gluconate Substances 0.000 description 2
- 235000012207 sodium gluconate Nutrition 0.000 description 2
- 229940005574 sodium gluconate Drugs 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 2
- CFOQKXQWGLAKSK-KTKRTIGZSA-N (13Z)-docosen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCCO CFOQKXQWGLAKSK-KTKRTIGZSA-N 0.000 description 1
- BZANQLIRVMZFOS-ZKZCYXTQSA-N (3r,4s,5s,6r)-2-butoxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound CCCCOC1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O BZANQLIRVMZFOS-ZKZCYXTQSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- DJYWKXYRGAMLRE-QXMHVHEDSA-N (z)-icos-9-en-1-ol Chemical compound CCCCCCCCCC\C=C/CCCCCCCCO DJYWKXYRGAMLRE-QXMHVHEDSA-N 0.000 description 1
- TVPWKOCQOFBNML-SEYXRHQNSA-N (z)-octadec-6-en-1-ol Chemical compound CCCCCCCCCCC\C=C/CCCCCO TVPWKOCQOFBNML-SEYXRHQNSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical class CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- CFOQKXQWGLAKSK-UHFFFAOYSA-N 13-docosen-1-ol Natural products CCCCCCCCC=CCCCCCCCCCCCCO CFOQKXQWGLAKSK-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- JBVOQKNLGSOPNZ-UHFFFAOYSA-N 2-propan-2-ylbenzenesulfonic acid Chemical compound CC(C)C1=CC=CC=C1S(O)(=O)=O JBVOQKNLGSOPNZ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 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
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229940027983 antiseptic and disinfectant quaternary ammonium compound Drugs 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical class O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229940071118 cumenesulfonate Drugs 0.000 description 1
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 229960004670 didecyldimethylammonium chloride Drugs 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229960000735 docosanol Drugs 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229940043348 myristyl alcohol Drugs 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
- UZZYXUGECOQHPU-UHFFFAOYSA-M n-octyl sulfate Chemical compound CCCCCCCCOS([O-])(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-M 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229940067739 octyl sulfate Drugs 0.000 description 1
- ALSTYHKOOCGGFT-MDZDMXLPSA-N oleyl alcohol Chemical compound CCCCCCCC\C=C\CCCCCCCCO ALSTYHKOOCGGFT-MDZDMXLPSA-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
- 239000003605 opacifier Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000010850 salt effect Methods 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007785 strong electrolyte Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- UZZYXUGECOQHPU-UHFFFAOYSA-N sulfuric acid monooctyl ester Natural products CCCCCCCCOS(O)(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-N 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 229940057402 undecyl alcohol Drugs 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000004711 α-olefin 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
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0017—Multi-phase liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
-
- 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
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-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
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
- 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
Definitions
- the invention relates to aqueous multiphase liquid surfactant-containing cleaning agents Allow to emulsify temporarily by shaking and can be used to clean hard surfaces are and a process for their preparation.
- all-purpose cleaners represent predominantly neutral to weakly alkaline aqueous liquid products, the 1 to 30% by weight surfactants, 0 to 5% by weight builder (e.g. citrates, gluconates, soda, polycarboxylates) 0 to 10% by weight of hydrotropes (e.g. alcohols, urea), 0 to 10% by weight of water-soluble Solvents (e.g. alcohols, glycol ethers) and optionally, among others Skin protection, coloring and Contain fragrances. It is usually used as an approx. 1% solution in water local stain removal also undiluted. There are also ready-to-use all-purpose cleaners as a so-called spray cleaner in the trade.
- Such aqueous liquid cleaners are usually homogeneous or stable solutions Dispersions.
- the use of certain, especially hydrophobic, components in such cleaning agents can, however, result in this homogeneity being lost and inhomogeneous agents are obtained, their acceptance by the consumer as low is to be assessed.
- the alternative formulation of funds is required despite its inhomogeneity, it is a defined exterior that is acceptable to the consumer Show appearance and application form.
- European patent application 116 422 describes a liquid hair or body shampoo with two aqueous phases which can be temporarily dispersed into one another by shaking, and both phases being miscible with water in any ratio.
- the upper phase contains 8 to 25% by weight, based on the total composition, of at least one surfactant and the lower phase contains at least 6% by weight, based on the total composition, of dissolved sodium hexametaphosphate of the formula I, in which n stands for an average of approximately 12.
- Additional builder salts can optionally be contained in the lower phase.
- Anionic, cationic, amphoteric and / or nonionic surfactants can be contained as surfactants, preferably at least one anionic surfactant being contained.
- the object of the present invention was to provide powerful and storage-stable agents Cleaning of hard surfaces in defined inhomogeneous, easy to handle and for the Provide consumers with acceptable form.
- the invention relates to an aqueous liquid multiphase detergent containing surfactant with at least two continuous phases, the at least one lower aqueous phase I and an upper immiscible with this phase has aqueous phase II and temporarily convert to an emulsion by shaking lets, and contains 0 to 5 wt .-% sodium hexametaphosphate.
- sodium hexametaphosphate is to be understood as a mixture of condensed orthophosphates of the formula I, where n is an average of about 12.
- an agent according to the invention consists of a lower continuous one Phase consisting of the entire phase I and an upper continuous phase consisting of of the entire phase II.
- One or more continuous phases of one According to the invention, however, parts of another phase can also be emulsified Contain form, so that in such an agent, for example, phase I in part as continuous phase I is present, which is the lower continuous phase of the agent, and to a different extent than discontinuous phase I in the upper continuous phase II is emulsified.
- phase II and other continuous phases are examples of phase II and other continuous phases.
- temporary is understood to mean that 90% of the demixing of the emulsion formed by shaking into the separate phases takes place at temperatures of about 20 ° C. to about 40 ° C. within 2 minutes to 10 hours and the last 2 % of the separation into the phase state before shaking within a further 15 minutes to 50 hours.
- the invention relates to the use of a in a second embodiment aqueous liquid multi-phase surfactant-containing cleaning agent with at least two continuous phases, the at least one lower aqueous phase I and one with this Has phase immiscible upper aqueous phase II and temporarily shaking in can transfer an emulsion for cleaning hard surfaces.
- aqueous liquid multi-phase surfactant-containing cleaning agent with at least two continuous phases, the at least one lower aqueous phase I and one with this Has phase immiscible upper aqueous phase II and temporarily shaking in can transfer an emulsion for cleaning hard surfaces.
- the agents according to the invention are characterized by an unusually good cleaning performance of stubborn grease dirt when used undiluted. Furthermore the agents show a favorable residue behavior.
- the individual phases are on average stable for a long time without e.g. Deposits formed, and the transfer into one temporary emulsion remains reversible even after frequent shaking.
- the Separation of ingredients in separate phases promote the chemical stability of the agent.
- the invention also relates to a method for producing an inventive one By mixing directly from its raw materials, then mixing and finally standing the means for separating the temporary emulsion.
- the continuous phases I and II delimited from each other by a sharp interface.
- one or both of the continuous phases I and II parts preferably 0.1 to 25 vol .-%, in particular 0.2 to 15 vol .-%, based on the volume of the respective continuous phase, each phase other than dispersant.
- the continuous phase I or II is then around Volume part reduced, which is distributed as dispersant in the other phase.
- Especially agents in which phase I in amounts of 0.1 to 25% by volume are preferred 0.2 to 15 vol .-%, based on the volume of phase II, is emulsified in phase II.
- a further preferred embodiment of the invention lies next to the continuous Phases I and II part of the two phases as an emulsion of one of the two phases in the other phase, this emulsion being characterized by two sharp interfaces, an upper one and a lower part compared to the parts of phases I and II not involved in the emulsion is delimited.
- the agents according to the invention contain phase I and phase II in a volume ratio from 90:10 to 10:90, preferably 75:25 to 25:75, in particular 65:35 to 35:65.
- the agents contain one or more hydrophobic components.
- Suitable hydrophobic components are, for example dialkyl ethers having identical or different C 4 to C 14 alkyl radicals, in particular dioctyl ethers; Hydrocarbons with a boiling range from 100 to 300 ° C, in particular 140 to 280 ° C, for example aliphatic hydrocarbons with a boiling range from 145 to 200 ° C, isoparaffins with a boiling range from 200 to 260 ° C; essential oils, in particular limonene and pine oil extracted from pine roots and stumps; and also mixtures of these hydrophobic components, in particular mixtures of two or three of the hydrophobic components mentioned.
- Preferred mixtures of hydrophobic components are mixtures of various dialkyl ethers, of dialkyl ethers and hydrocarbons, of dialkyl ethers and essential oils, of hydrocarbons and essential oils, of dialkyl ethers and hydrocarbons and essential oils and of these mixtures.
- the agents contain hydrophobic components in amounts, based on the composition, of 0 to 20% by weight, preferably 0.1 to 14% by weight, in particular 0.5 to 10% by weight, most preferably 0.8 to 7 % By weight.
- the agents according to the invention can contain phase separation aids.
- Suitable Phase separation aids are, for example, the alkali metal and alkaline earth metal chlorides and sulfates, especially sodium and potassium chloride and sulfate, and ammonium chloride and sulfate or mixtures thereof.
- the salts mentioned support the as strong electrolytes Phase separation through the salt effect.
- Builder salts also act as electrolytes Effect and are accordingly also suitable as phase separation aids.
- the means contain phase separation aids in amounts, based on the composition, from 0 to 30% by weight, preferably 1 to 20% by weight, in particular 3 to 15% by weight, extremely preferably 5 to 12% by weight.
- the agents according to the invention can contain anionic, nonionic, amphoteric or cationic surfactants or surfactant mixtures of one, more or all contain these classes of surfactants.
- the agents contain surfactants in quantities based on the Composition, from 0.01 to 30 wt .-%, preferably 0.1 to 20 wt .-%, in particular 1 to 14% by weight, most preferably 3 to 10% by weight.
- Suitable nonionic surfactants are, for example, C 8 -C 18 alkyl alcohol polyglycol ethers, alkyl polyglycosides and nitrogenous surfactants or mixtures thereof, in particular the first two.
- the compositions contain nonionic surfactants in amounts, based on the composition, of 0 to 30% by weight, preferably 0.1 to 20% by weight, in particular 0.5 to 14% by weight, extremely preferably 1 to 10% by weight .-%.
- C 8 -C 18 alkyl alcohol polypropylene glycol / polyethylene glycol ethers are preferred known nonionic surfactants. They can be represented by the formula II, R i O- (CH 2 CH (CH 3 ) O) p (CH 2 CH 2 O) e -H, in which R i is a linear or branched, aliphatic alkyl and / or alkenyl radical with 8 to 18 Carbon atoms, p stands for 0 or numbers from 1 to 3 and e stands for numbers from 1 to 20.
- the C 8 -C 18 alkyl alcohol polyglycol ethers of the formula II can be obtained by addition of propylene oxide and / or ethylene oxide to alkyl alcohols, preferably to fatty alcohols.
- Typical examples are polyglycol ethers of the formula II in which R i is an alkyl radical having 8 to 18 carbon atoms, p is 0 to 2 and e is a number from 2 to 7.
- End-capped C 8 -C 18 alkyl alcohol polyglycol ethers can also be used, ie compounds in which the free OH group in the formula II is etherified.
- C 8 -C 18 alkyl alcohol polyglycol ethers can be obtained by the relevant methods of preparative organic chemistry.
- C 8 -C 18 -Alkyl alcohol polyglycol ethers are preferably reacted in the presence of bases with alkyl halides, in particular butyl or benzyl chloride.
- Typical examples are mixed ethers of the formula II in which R i stands for an industrial fatty alcohol residue, preferably C 12/14 cocoalkyl residue, p for 0 and e for 5 to 10, which are sealed with a butyl group.
- Preferred nonionic surfactants are furthermore alkyl polyglycosides (APG) of the formula III, R ii O [G] x , in which R ii for a linear or branched, saturated or unsaturated alkyl radical having 8 to 22 carbon atoms, [G] for a glycosidically linked sugar radical and x stands for a number from 1 to 10.
- APG are non-ionic surfactants and are known substances that can be obtained using the relevant methods of preparative organic chemistry.
- the index number x in the general formula III indicates the degree of oligomerization (DP degree), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10.
- the value x for a certain alkylglycoside is an analytically determined arithmetic size, which usually represents a fractional number.
- Alkyl glycosides with an average degree of oligomerization x of 1.1 to 3.0 are preferably used. From an application point of view, those alkyl glycosides are preferred whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.6.
- the alkyl or alkenyl radical R ii (formula III) can be derived from primary alcohols having 8 to 18, preferably 8 to 14, carbon atoms. Typical examples are capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as those obtained in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from RoELEN's oxosynthesis.
- the alkyl or alkenyl radical R ii is preferably derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol. Elaidyl alcohol, petroselinyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and their technical mixtures should also be mentioned.
- Nitrogen-containing surfactants may be included as further nonionic surfactants, e.g. Fatty acid polyhydroxyamides, for example glucamides, and ethoxylates of alkylamines, vicinal diols and / or carboxamides, the alkyl groups with 10 to 22 carbon atoms, preferably have 12 to 18 carbon atoms.
- the degree of ethoxylation of these compounds is usually between 1 and 20, preferably between 3 and 10.
- the particularly suitable compounds include lauric acid, Myristic acid and palmitic acid monoethanolamides.
- Suitable anionic surfactants are the preferred C 8 -C 18 alkyl sulfates, C 8 -C 18 alkyl ether sulfates, ie the sulfation products of the alcohol ethers of the formula II, and / or C 8 -C 18 alkyl benzene sulfonates, but also C 8 -C 18 alkanesulfonates , C8-C 18 - ⁇ -olefin sulfonates, sulfonated C 8 -C 18 fatty acids, especially dodecylbenzenesulfonate, C 8 -C 22 carboxamide amide ether sulfates, sulfonic succinic acid mono- and di-C 1 -C 12 alkyl esters, C 8 -C 18 - Alkyl polyglycol ether carboxylates, C 8 -C 18 -N-acyl taurides, C 8 -C 18 -N sarcosinate
- compositions contain anionic surfactants in amounts, based on the composition, of 0 to 30% by weight, preferably 0.1 to 20% by weight, in particular 1 to 14% by weight, extremely preferably 2 to 10% by weight. %.
- the agents according to the invention can also contain soaps, ie alkali metal or ammonium salts of saturated or unsaturated C 6 -C 22 fatty acids.
- the soaps can be used in an amount of up to 5% by weight, preferably from 0.1 to 2% by weight.
- Suitable amphoteric surfactants are, for example, betaines of the formula (R iii ) (R iv ) (R v ) N + CH 2 COO - , in which R iii is an alkyl radical with 8 to 25, preferably 10 to 21, carbon atoms, which is optionally interrupted by heteroatoms or heteroatom groups, and iv and R v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C 10 -C 18 -alkyldimethylcarboxymethylbetaine and C 11 -C 17 -alkylamidopropyldimethylcarboxymethylbetaine.
- the compositions contain amphoteric surfactants in amounts, based on the composition, of 0 to 15% by weight, preferably 0.01 to 10% by weight, in particular 0.1 to 5% by weight.
- Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R vi ) (R vii ) (R viii ) (R ix ) N + X - , in which R vi to R ix for four identical or different types, in particular two long and two short-chain, alkyl radicals and X - represent an anion, in particular a halide ion, for example didecyldimethylammonium chloride, alkylbenzyldidecylammonium chloride and mixtures thereof.
- the compositions contain cationic surfactants in amounts, based on the composition, of 0 to 10% by weight, preferably 0.01 to 5% by weight, in particular 0.1 to 3% by weight.
- the agents according to the invention contain anionic and nonionic surfactants next to one another, preferably C 8 -C 18 alkylbenzenesulfonates, C 8 -C 18 alkyl sulfates and / or C 8 -C 18 alkyl ether sulfates in addition to C 8 -C 18 alkyl alcohol polyglycol ethers and / or alkyl polyglycosides, in particular C 8 -C 18 alkylbenzenesulfonates in addition to C 8 -C 18 alkyl alcohol polyglycol ethers.
- anionic and nonionic surfactants next to one another preferably C 8 -C 18 alkylbenzenesulfonates, C 8 -C 18 alkyl sulfates and / or C 8 -C 18 alkyl ether sulfates in addition to C 8 -C 18 alkyl alcohol polyglycol ethers.
- the agents according to the invention can also contain builders. Suitable builders are for example alkali metal gluconates, citrates, nitrilotriacetates, carbonates and bicarbonates, especially sodium gluconate, citrate and nitrilotriacetate as well as sodium and Potassium carbonate and bicarbonate, as well as alkali metal and alkaline earth metal hydroxides, especially sodium and potassium hydroxide, ammonia and amines, especially mono- and triethanolamine, or mixtures thereof. This also includes the salts of glutaric acid, Succinic acid, adipic acid, tartaric acid and benzene hexacarboxylic acid as well as phosphonates and Phosphates.
- Suitable builders are for example alkali metal gluconates, citrates, nitrilotriacetates, carbonates and bicarbonates, especially sodium gluconate, citrate and nitrilotriacetate as well as sodium and Potassium carbonate and bicarbonate
- the agents contain builders in amounts, based on the composition, of 0 to 20% by weight, preferably 0.01 to 12% by weight, in particular 0.1 to 8% by weight, extremely preferably 0.3 to 5% by weight, but the amount of sodium hexametaphosphate except for the agents used - is limited to 0 to 5 wt .-%.
- Electrolytes are the builder salts at the same time phase separation aids.
- the agents according to the invention can contain further auxiliaries and additives as are customary in such agents.
- auxiliaries and additives include in particular polymers, soil release agents, solvents (e.g. ethanol, isopropanol, glycol ether), solubilizers, hydrotropes (e.g. cumene sulfonate, octyl sulfate, butyl glucoside, butyl glycol), cleaning enhancers, viscosity regulators (e.g. synthetic polymers such as polysaccharides, polyacrylates, in nature occurring polymers and their derivatives such as xanthan gum, other polysaccharides and / or gelatin), pH regulators (e.g.
- the amount of such additives is usually not more than 12% by weight in the cleaning agent.
- the lower limit of use depends on the type of additive and can be up to 0.001% by weight and below, for example, for dyes.
- the amount of auxiliaries is preferably between 0.01 and 7% by weight, in particular 0.1 and 4% by weight.
- the pH of the agents according to the invention can be varied over a wide range, but a range from 2.5 to 12, in particular 5 to 10.5, is preferred.
- the pH of the agents according to the invention is to be understood as the pH of the agent in the form of the temporary emulsion.
- the agents according to the invention can be mixed directly from their raw materials, then mixing and finally standing the means for separating the temporary emulsion can be produced.
- test method described below according to Seifen- ⁇ le-Fette-Wachsen 1986 , 112 , p. 371 , which provides very reproducible results, was used to test the cleaning ability of the detergent compositions formulated according to the invention.
- the cleaning agent to be tested was then placed on an artificially soiled white plastic surface.
- a mixture of carbon black, machine oil, triglyceride of saturated fatty acids and low-boiling aliphatic hydrocarbon was used as artificial soiling for the dilute use of the cleaning agent.
- the test area of 26 x 28 cm was evenly coated with 2 g of the artificial soiling with the aid of a surface coater.
- a plastic sponge was each with 10 ml of the detergent solution to be tested soaked and mechanically on the also with 10 ml of the cleaning agent to be tested coated test surface moves. After 10 wiping movements, the cleaned test area Held under running water and the loose dirt removed. The cleaning effect, i.e. the whiteness of the so-called plastic surface was measured with a Color difference measuring device "Microcolor" (Dr. Lange) measured. The served as the white standard clean untreated white plastic surface.
- the test was carried out with the inventive cleaning agent E1 in diluted usage at a concentration of 6 MLL -1 and in undiluted.
- the test was carried out with a leading all-purpose cleaner in the German market with more than 10% by weight of surfactants (V1) in dilute application of 6 ml ⁇ l -1 as well as in undiluted application.
- the inventive cleaning agent E1 outperforms the significantly more surfactant-rich cleaner V1 both in the diluted application and in the undiluted application.
- phase I [% by weight]
- Phase II [% by weight] a) 0 6.2 c) ⁇ 0.05 3.3 d) 1.06 1.0 f) 11.5 8.9 j) ⁇ 0.05 7.9 k) ⁇ 0.05 1.6 1) 85.0 70.7
- the upper phase II contains almost the entire amount of surfactant (a, c), hydrophobic component (j) and perfume (k), while the lower phase I almost exclusively a part of the Contains phase separation aid (f) and the builder (d).
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
RiO-(CH2CH(CH3)O) p (CH2CH2O) e -H, beschrieben werden, in der Ri für einen linearen oder verzweigten, aliphatischen Alkyl- und/oder Alkenylrest mit 8 bis 18 Kohlenstoffatomen, p für 0 oder Zahlen von 1 bis 3 und e für Zahlen von 1 bis 20 steht.
Die C8-C18-Alkylalkoholpolyglykolether der Formel II kann man durch Anlagerung von Propylenoxid und/oder Ethylenoxid an Alkylalkohole, vorzugsweise an Fettalkohole, erhalten. Typische Beispiele sind Polyglykolether der Formel II, in der Ri für einen Alkylrest mit 8 bis 18 Kohlenstoffatomen, p für 0 bis 2 und e für Zahlen von 2 bis 7 steht. Bevorzugte Vertreter sind beispielsweise C10-C14-Fettalkohol+1PO+6EO-ether (p = 1, e = 6) und C12-C18-Fettalkohol+7EO-ether (p = 0, e = 7) sowie deren Mischungen.
Es können auch endgruppenverschlossene C8-C18-Alkylalkoholpolyglykolether eingesetzt werden, d.h. Verbindungen in denen die freie OH-Gruppe in der Formel II verethert ist. Die endgruppenverschlossenen C8-C18-Alkylalkoholpolyglykolether können nach einschlägigen Methoden der präparativen organischen Chemie erhalten werden. Vorzugsweise werden C8-C18-Alkylalkohopolyglykolether in Gegenwart von Basen mit Alkylhalogeniden, insbesondere Butyl- oder Benzylchlorid, umgesetzt. Typische Beispiele sind Mischether der Formel II, in der Ri für einen technischen Fettalkoholrest, vorzugsweise C12/14-Kokosalkylrest, p für 0 und e für 5 bis 10 stehen, die mit einer Butylgruppe verschlossen sind.
x = 1 bis 6 annehmen kann, ist der Wert x für ein bestimmtes Alkylglykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkylglykoside mit einem mittleren Oligomerisierungsgrad x von 1,1 bis 3,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche Alkylglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1,7 ist und insbesondere zwischen 1,2 und 1,6 liegt. Als glykosidische Zucker wird vorzugsweise Xylose, insbesondere aber Glucose verwendet.
Der Alkyl- bzw. Alkenylrest Rii (Formel III) kann sich von primären Alkoholen mit 8 bis 18, vorzugsweise 8 bis 14 Kohlenstoffatomen ableiten. Typische Beispiele sind Capronalkohol, Caprylalkohol, Caprinalkohol und Undecylalkohol sowie deren technische Gemische, wie sie beispielsweise im Verlauf der Hydrierung von technischen Fettsäuremethylestern oder im Verlauf der Hydrierung von Aldehyden aus der RoELENschen Oxosynthese anfallen. Vorzugsweise leitet sich der Alkyl- bzw. Alkenylrest Rii aber von Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol oder Oleylalkohol ab. Weiterhin sind Elaidylalkohol, Petroselinylalkohol, Arachidylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol sowie deren technische Gemische zu nennen.
Als Komponenten wurden eingesetzt
[Gew.-%] | E1 | E2 | E3 | E4 | E5 | E6 | E7 |
a) | 4 | 4 | 4 | 5 | 4 | 4 | 4 |
b) | - | 1 | - | 2 | 1 | - | - |
c) | 2 | 2 | 2 | - | 2 | 2 | 2 |
d) | 1 | 0,75 | 1 | 1 | 1 | 1 | - |
e) | - | - | - | - | - | - | 0,5 |
f) | 9 | 6,5 | 10 | 9 | 8 | 10 | 10 |
g) | - | - | - | - | 2 | - | - |
h) | - | 5 | - | - | - | 1 | - |
i) | - | - | 5 | - | - | - | - |
j) | 5 | - | - | 5 | 5 | 4 | 5 |
k) | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
l) | ad 100 | ad 100 | ad 100 | ad 100 | ad 100 | ad 100 | ad 100 |
pH-Wert | 9,3 | 8,6 | 9,3 | 9,3 | 9,5 | 9,3 | 9,5 |
E1 | Phase I [Gew.-%] | Phase II [Gew.-%] |
a) | 0 | 6,2 |
c) | < 0,05 | 3,3 |
d) | 1,06 | 1,0 |
f) | 11,5 | 8,9 |
j) | < 0,05 | 7,9 |
k) | <0,05 | 1,6 |
1) | 85,0 | 70,7 |
Claims (14)
- Verwendung eines wäßrigen flüssigen mehrphasigen tensidhaltigen Reinigungsmittels mit wenigstens zwei kontinuierlichen Phasen, das mindestens eine untere wäßrige Phase I sowie eine mit dieser Phase nicht mischbare obere wäßrige Phase II aufweist und sich durch Schütteln temporär in eine Emulsion überführen läßt, dadurch gekennzeichnet, daß es 0 bis 5 Gew.-% Natriumhexametaphosphat enthält.
- Verwendung eines Mittels nach Anspruch 1, dadurch gekennzeichnet, daß die kontinuierlichen Phasen I und II durch eine scharfe Grenzfläche gegeneinander abgegrenzt sind.
- Verwendung eines Mittels nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß eine oder beide der kontinuierlichen Phasen I und II Teile, bevorzugt 0,1 bis 25 Vol.-%, insbesondere 0,2 bis 15 Vol.-%, bezogen auf das Volumen der jeweiligen kontinuierlichen Phase, der jeweils anderen Phase als Dispergens enthalten.
- Verwendung eines Mittels nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß Phase I in Mengen von 0,1 bis 25 Vol.-%, bevorzugt 0,2 bis 15 Vol.-%, bezogen auf das Volumen der Phase II, in Phase II emulgiert ist.
- Verwendung eines Mittels nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß neben den kontinuierlichen Phasen I und II ein Teil der beiden Phasen als Emulsion einer der beiden Phasen in der anderen Phase vorliegt, wobei diese Emulsion durch zwei scharfe Grenzflächen, eine obere und eine untere, gegenüber den nicht an der Emulsion beteiligten Teilen der Phasen I und II abgegrenzt ist.
- Verwendung eines Mittels nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das Mittel Phase I und Phase II in einem Volumenverhältnis von 90 : 10 bis 10 : 90, vorzugsweise 75 : 25 bis 25 : 75, insbesondere 65 : 35 bis 35 : 65 enthält.
- Verwendung eines Mittels nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das Mittel zusätzlich Hydrophobkomponenten aus der Gruppe der Dialkylether mit gleichen oder verschiedenen C4- bis C14-Alkylresten, insbesondere Dioctylether, Kohlenwasserstoffe mit einem Siedebereich von 100 bis 300°C, insbesondere 140 bis 280°C, etherische Öle, insbesondere Limonen und Pine Oil, und deren Mischungen, insbesondere Mischungen von zwei oder drei der genannten Hydrophobkomponenten, enthält.
- Verwendung eines Mittels nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß das Mittel zusätzlich Phasentrennmittel, bevorzugt aus der Gruppe der Alkalimetall- und Erdalkalimetallchloride und -sulfate, insbesondere Natrium- und Kaliumchlorid und -sulfat, sowie Ammoniumchlorid und-sulfat bzw. deren Mischungen, enthält.
- Verwendung eines Mittels nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß das Mittel anionisches Tensid, bevorzugt aus der Gruppe der C8-C18-Alkylsulfate, der C8-C18-Alkylethersulfate und C8-C18-Alkylbenzolsulfonate und deren Mischungen, enthält.
- Verwendung eines Mittels nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß das Mittel nichtionisches Tensid, bevorzugt aus der Gruppe der C8-C18-Alkylalkoholpolyglykolether, der Alkylpolyglykoside und deren Mischungen, enthält.
- Verwendung eines Mittels nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß das Mittel anionisches und nichtionisches Tensid, vorzugsweise C8-C18-Alkylbenzolsulfonate, C8-C18-Alkylsulfate und/oder C8-C18-Alkylethersulfate neben C8-C18-Alkylalkoholpolyglykolethern und/oder Alkylpolyglykosiden, insbesondere C8-C18-Alkylbenzolsulfonate neben C8-C18-Alkylalkoholpolyglykolethern, enthält.
- Verwendung eines Mittels nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß das Mittel ein oder mehrere kationische Tenside enthält.
- Verwendung eines Mittels nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß das Mittel zusätzlich Builder, bevorzugt aus der Gruppe der Alkalimetallgluconate, -citrate, -nitrilotriacetate, -carbonate und -bicarbonate sowie Alkalimetall- und Erdalkalimetallhydroxide, Ammoniak und Amine, insbesondere Mono- und Triethanolamin bzw. deren Mischungen, enthält.
- Verwendung eines wäßrigen flüssigen mehrphasigen tensidhaltigen Reinigungsmittels mit wenigstens zwei kontinuierlichen Phasen, das mindestens eine untere wäßrige Phase I sowie eine mit dieser Phase nicht mischbare obere wäßrige Phase II ausweist und sich durch Schütteln temporär in eine Emulsion überführen läßt, zur Reinigung harter Oberflächen.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
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DE19811386 | 1998-03-16 | ||
DE19811386A DE19811386A1 (de) | 1998-03-16 | 1998-03-16 | Wäßriges mehrphasiges Reinigungsmittel |
DE19859774 | 1998-12-23 | ||
DE1998159774 DE19859774A1 (de) | 1998-12-23 | 1998-12-23 | Wäßriges mehrphasiges Reinigungsmittel |
EP99911758A EP1064349B1 (de) | 1998-03-16 | 1999-03-09 | Wässriges mehrphasiges reinigungsmittel |
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EP99911758A Division EP1064349B1 (de) | 1998-03-16 | 1999-03-09 | Wässriges mehrphasiges reinigungsmittel |
Publications (2)
Publication Number | Publication Date |
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EP1126019A1 true EP1126019A1 (de) | 2001-08-22 |
EP1126019B1 EP1126019B1 (de) | 2003-06-04 |
Family
ID=26044653
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Application Number | Title | Priority Date | Filing Date |
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EP99911758A Expired - Lifetime EP1064349B1 (de) | 1998-03-16 | 1999-03-09 | Wässriges mehrphasiges reinigungsmittel |
EP01103811A Revoked EP1126019B1 (de) | 1998-03-16 | 1999-03-09 | Verwendung eines wässrigen mehrphasigen Reinigungsmittels zur Reinigung harter Oferflächen |
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EP99911758A Expired - Lifetime EP1064349B1 (de) | 1998-03-16 | 1999-03-09 | Wässriges mehrphasiges reinigungsmittel |
Country Status (8)
Country | Link |
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US (1) | US6440924B1 (de) |
EP (2) | EP1064349B1 (de) |
JP (1) | JP2002506925A (de) |
AT (2) | ATE242313T1 (de) |
CA (1) | CA2324075A1 (de) |
DE (2) | DE59905562D1 (de) |
ES (2) | ES2200994T3 (de) |
WO (1) | WO1999047635A2 (de) |
Cited By (1)
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EP3593896A4 (de) * | 2017-03-07 | 2020-12-23 | Kurita Water Industries Ltd. | Wasserbehandlungschemikalie, verfahren zur herstellung davon und verfahren zum waschen einer polyamidbasierten umkehrosmosemembran |
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US6720300B1 (en) | 1998-10-26 | 2004-04-13 | Reckitt Benckiser N.V. | Liquid cleaning agent or detergent composition |
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DE19936727A1 (de) | 1999-08-06 | 2001-02-08 | Henkel Kgaa | Niotensidbasiertes wäßriges mehrphasiges Reinigungsmittel |
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DE10012949A1 (de) | 2000-03-16 | 2001-09-27 | Henkel Kgaa | Kieselsäureester-Mischungen |
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ITCR20060016A1 (it) * | 2006-06-07 | 2007-12-08 | Silvia Palladini | Formulazioni di detersivi a basso impatto ambientale |
FR2917094B1 (fr) * | 2007-06-08 | 2011-05-06 | Dalta | Composition destinee a etre impregnee dans des lingettes pour le nettoyage et/ou le lustrage de surface contaminee |
US8980813B2 (en) | 2008-02-21 | 2015-03-17 | S. C. Johnson & Son, Inc. | Cleaning composition having high self-adhesion on a vertical hard surface and providing residual benefits |
US9410111B2 (en) | 2008-02-21 | 2016-08-09 | S.C. Johnson & Son, Inc. | Cleaning composition that provides residual benefits |
US8993502B2 (en) | 2008-02-21 | 2015-03-31 | S. C. Johnson & Son, Inc. | Cleaning composition having high self-adhesion to a vertical hard surface and providing residual benefits |
US9481854B2 (en) | 2008-02-21 | 2016-11-01 | S. C. Johnson & Son, Inc. | Cleaning composition that provides residual benefits |
ES2422261T5 (es) * | 2008-02-21 | 2017-05-12 | S.C. Johnson & Son, Inc. | Composición para limpieza que tiene alta autoadhesión y que proporciona beneficios residuales |
US8143206B2 (en) * | 2008-02-21 | 2012-03-27 | S.C. Johnson & Son, Inc. | Cleaning composition having high self-adhesion and providing residual benefits |
JP2012255121A (ja) * | 2011-06-10 | 2012-12-27 | Niitaka:Kk | 濃縮液体洗剤、パウチ入り濃縮液体洗剤及び被洗浄物の洗浄方法 |
US20130029894A1 (en) * | 2011-07-27 | 2013-01-31 | Jean-Luc Philippe Bettiol | Multiphase liquid detergent composition |
US8927473B2 (en) | 2011-12-30 | 2015-01-06 | Walter Geslak | Color indication of effectiveness of immiscible liquid suspension |
JP6205123B2 (ja) * | 2012-11-30 | 2017-09-27 | 株式会社ニイタカ | 濃縮液体洗剤及び被洗浄物の洗浄方法 |
CN105483720B (zh) * | 2015-12-29 | 2018-03-16 | 马鞍山采石矶涂料有限公司 | 一种环保型水性脱脂剂及其制备方法 |
EP4050088A1 (de) | 2021-02-26 | 2022-08-31 | The Procter & Gamble Company | Flüssige handspülmittelzusammensetzung |
WO2022182690A1 (en) | 2021-02-26 | 2022-09-01 | The Procter & Gamble Company | Liquid hand dishwashing detergent composition |
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1999
- 1999-03-09 ES ES01103811T patent/ES2200994T3/es not_active Expired - Lifetime
- 1999-03-09 JP JP2000536818A patent/JP2002506925A/ja not_active Ceased
- 1999-03-09 AT AT01103811T patent/ATE242313T1/de not_active IP Right Cessation
- 1999-03-09 EP EP99911758A patent/EP1064349B1/de not_active Expired - Lifetime
- 1999-03-09 EP EP01103811A patent/EP1126019B1/de not_active Revoked
- 1999-03-09 WO PCT/EP1999/001507 patent/WO1999047635A2/de active IP Right Grant
- 1999-03-09 CA CA002324075A patent/CA2324075A1/en not_active Abandoned
- 1999-03-09 US US09/646,320 patent/US6440924B1/en not_active Expired - Fee Related
- 1999-03-09 DE DE59905562T patent/DE59905562D1/de not_active Expired - Lifetime
- 1999-03-09 ES ES99911758T patent/ES2200511T3/es not_active Expired - Lifetime
- 1999-03-09 DE DE59905877T patent/DE59905877D1/de not_active Revoked
- 1999-03-09 AT AT99911758T patent/ATE240387T1/de not_active IP Right Cessation
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Cited By (2)
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EP3593896A4 (de) * | 2017-03-07 | 2020-12-23 | Kurita Water Industries Ltd. | Wasserbehandlungschemikalie, verfahren zur herstellung davon und verfahren zum waschen einer polyamidbasierten umkehrosmosemembran |
US11400420B2 (en) | 2017-03-07 | 2022-08-02 | Kurita Water Industries Ltd. | Water treatment chemical, method for preparing same, and method for washing polyamide reverse osmosis membrane |
Also Published As
Publication number | Publication date |
---|---|
DE59905562D1 (de) | 2003-06-18 |
EP1064349A2 (de) | 2001-01-03 |
EP1126019B1 (de) | 2003-06-04 |
ES2200511T3 (es) | 2004-03-01 |
US6440924B1 (en) | 2002-08-27 |
DE59905877D1 (de) | 2003-07-10 |
ATE242313T1 (de) | 2003-06-15 |
EP1064349B1 (de) | 2003-05-14 |
ES2200994T3 (es) | 2004-03-16 |
WO1999047635A2 (de) | 1999-09-23 |
ATE240387T1 (de) | 2003-05-15 |
CA2324075A1 (en) | 1999-09-23 |
WO1999047635A3 (de) | 2000-01-20 |
JP2002506925A (ja) | 2002-03-05 |
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