EP0712436B1 - Low-foaming washing or cleaning agents - Google Patents
Low-foaming washing or cleaning agents Download PDFInfo
- Publication number
- EP0712436B1 EP0712436B1 EP94925395A EP94925395A EP0712436B1 EP 0712436 B1 EP0712436 B1 EP 0712436B1 EP 94925395 A EP94925395 A EP 94925395A EP 94925395 A EP94925395 A EP 94925395A EP 0712436 B1 EP0712436 B1 EP 0712436B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- weight
- fatty acid
- detergent
- cleaning formulation
- 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.)
- Expired - Lifetime
Links
- 238000005187 foaming Methods 0.000 title abstract description 20
- 239000012459 cleaning agent Substances 0.000 title description 12
- 238000005406 washing Methods 0.000 title description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 47
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 32
- 239000000194 fatty acid Substances 0.000 claims abstract description 32
- 229930195729 fatty acid Natural products 0.000 claims abstract description 32
- 239000003599 detergent Substances 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 16
- -1 alkane sulfonates Chemical class 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 28
- 238000004140 cleaning Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 150000004665 fatty acids Chemical class 0.000 claims description 11
- 238000009472 formulation Methods 0.000 claims description 11
- 229920000151 polyglycol Polymers 0.000 claims description 11
- 239000010695 polyglycol Substances 0.000 claims description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 9
- 239000000344 soap Substances 0.000 claims description 9
- 239000002736 nonionic surfactant Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 235000000346 sugar Nutrition 0.000 claims description 5
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 4
- 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 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 125000005456 glyceride group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 150000003871 sulfonates Chemical class 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 125000005599 alkyl carboxylate group Chemical group 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 125000000969 xylosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)CO1)* 0.000 claims 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000006260 foam Substances 0.000 description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 150000002191 fatty alcohols Chemical class 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 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 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- 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 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- SRBFZHDQGSBBOR-IOVATXLUSA-N Xylose Natural products O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229940071118 cumenesulfonate Drugs 0.000 description 3
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000007046 ethoxylation reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- UZZYXUGECOQHPU-UHFFFAOYSA-M n-octyl sulfate Chemical compound CCCCCCCCOS([O-])(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-M 0.000 description 3
- 229940067739 octyl sulfate Drugs 0.000 description 3
- 235000011118 potassium hydroxide Nutrition 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- UZZYXUGECOQHPU-UHFFFAOYSA-N sulfuric acid monooctyl ester Natural products CCCCCCCCOS(O)(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-N 0.000 description 3
- 235000019263 trisodium citrate Nutrition 0.000 description 3
- 229940038773 trisodium citrate Drugs 0.000 description 3
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 108091005804 Peptidases Proteins 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 239000004365 Protease Substances 0.000 description 2
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004851 dishwashing Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 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
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 235000003441 saturated fatty acids Nutrition 0.000 description 2
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- XPFJYKARVSSRHE-UHFFFAOYSA-K trisodium;2-hydroxypropane-1,2,3-tricarboxylate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].[Na+].[Na+].OC(=O)CC(O)(C(O)=O)CC(O)=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O XPFJYKARVSSRHE-UHFFFAOYSA-K 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-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
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- 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
- 241000173697 Euchloe naina Species 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 208000007976 Ketosis Diseases 0.000 description 1
- 229910017840 NH 3 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-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
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001323 aldoses Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001412 amines 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
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- ZXVOCOLRQJZVBW-UHFFFAOYSA-N azane;ethanol Chemical compound N.CCO ZXVOCOLRQJZVBW-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000010437 gem Substances 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 150000002584 ketoses Chemical class 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- UMELTKSLWXJXNZ-UHFFFAOYSA-N methyl 3,5-dinitrosalicylate Chemical compound COC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O UMELTKSLWXJXNZ-UHFFFAOYSA-N 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 210000002268 wool Anatomy 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0026—Low foaming or foam regulating 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
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
-
- 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
- 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
- C11D1/02—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
- C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
Definitions
- the invention relates to low-foaming detergents or cleaning agents, with liquid detergents and cleaning agents for hard surfaces being preferred. All non-textile surfaces occurring in the household and commercial sector, with the exception of dishes, are to be understood as cleaning agents for hard surfaces.
- the term general-purpose cleaner has become established for this type of cleaning agent. Low-foaming all-purpose cleaners are those that develop a low volume of foam when used manually, which significantly reduces within a few minutes.
- All-purpose cleaners have been known for a long time. These are essentially aqueous surfactant solutions of various types with or without the addition of builders and with or without the addition of water-soluble solvents or solubilizers.
- a disadvantage of manual application in practice has been its high foaming power. Although the consumer wants to perceive a certain amount of foam in the application solution at the beginning of his cleaning work to prove its effectiveness, the foam should then collapse as quickly as possible, so that once cleaned surfaces do not have to be wiped down.
- Liquid detergents also tend to have a high foaming capacity, which affects their applicability in washing machines.
- alkyl polyglycosides are known to be highly foaming surfactants; They are therefore used for products with the desired high foaming capacity, So recommended for manual dishwashing detergents or for washing hair.
- EP 0 070 074 B1 and 0 070 076 B2 describe such high-foaming washing and cleaning agents based on various APG-containing surfactant combinations. Consequently, these combinations are not recommended for the area of all-purpose cleaners.
- German published patent application DE 42 27 046 describes detergent mixtures based on fatty acid alkyl ester alkoxylates.
- WO-A-91 14 760 discloses low-foaming surfactant mixtures consisting of alkyl polyglycosides and fatty alcohol alkoxylates etherified with alkyl radicals.
- the object of the present invention was to provide washing or cleaning agents which at the same time have good cleaning properties, good biodegradability and a pronouncedly low foaming power.
- the criterion should be that initially formed foam visibly reduces within 2 minutes.
- the invention relates to water-containing washing or cleaning agents containing 0.1 to 50% by weight, preferably 1 to 20% by weight, of at least one alkyl polyglycoside of the formula I, R 1 -O- [Z] x (I), where R 1 is a branched or straight-chain, saturated or unsaturated alkyl group having 8 to 18 carbon atoms, Z is a sugar residue, preferably a glucose or Xylose radical and x represents integers from 1 to 10, and 0.05 to 50% by weight, preferably 1 to 20% by weight, of at least one fatty acid alkyl ester alkoxylate of the formula II, R 2 -CO 2 - (AO) y -R 3 (II), where R 2 is a branched or straight-chain, saturated or unsaturated alkyl group having 5 to 21 C atoms, AO is a C 2 -C 4 alkylene oxide unit, y is a number from 1 to 30 and R 3 represents a straight-chain or branched alkyl group
- the alkyl polyglycosides used in the agents according to the invention are known substances which can be obtained by the relevant methods of preparative organic chemistry; as a representative, reference is made to the documents EP 0 301 298 A1 and WO 90/3977.
- the alkyl polyglycosides can be from sugars or sugar residues, i.e. Derive aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose and xylose.
- the preferred alkyl polyglycosides are thus alkyl polyglucosides and alkyl polyxylosides.
- the alkyl radical R 1 in the formula (I) can be derived from primary branched and unbranched alcohols having 8 to 18 carbon atoms. Typical examples are myristyl alcohol, cetyl alcohol and their technical mixtures. However, preference is given to using alkylpolyglycosides of the formula (I) in which R 1 represents a carbon radical having 8 to 12, in particular 8 to 10, carbon atoms. In addition to lauryl alcohol, typical examples are, in particular, caprylic alcohol and capric alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
- the fatty acid alkyl ester alkoxylates of the formula (II) used in the agents according to the invention can be prepared by conventional methods, such as, for example, by esterification of fatty acid derivatives with alkoxylated methanol.
- this process has some disadvantages, it has two stages, the esterification takes a very long time and the products are colored by the high reaction temperatures.
- fatty acid methyl ester alkoxylates produced in this way often have relatively high OH numbers after the esterification, which can be problematic for some applications.
- the fatty acid alkyl ester alkoxylates of the formula (II) are preferably prepared by heterogeneously catalyzed direct alkoxylation of fatty acid alkyl esters with alkylene oxide, in particular ethylene oxide. This synthesis method is described in detail in WO 90/13533 and WO 91/15441. The resulting products are characterized by a low OH number, the reaction is carried out in one step and light-colored products are obtained. Those fatty acid alkyl ester alkoxylates of the formula (II) which are formed by ethoxylation of fatty acid methyl esters, ie in which A0 in the formula (II) is an ethylene oxide unit and R 3 is a methyl group, are preferably used.
- the fatty acid methyl esters used as starting materials can be obtained from natural oils and fats as well as produced synthetically.
- Fatty acid alkyl ester alkoxylates are preferably used in the all-purpose cleaners according to the invention, where y is a number from 5 to 25, in particular from 9 to 18.
- fatty acid alkyl ester alkoxylates are preferably used in the liquid detergents according to the invention, where R 2 is a branched or straight-chain, saturated alkyl group having 12 to 18 carbon atoms and y is a number from 3 to 15.
- liquid detergents and general-purpose cleaners according to the invention are to be used to remove lipophilic soiling, fatty acid alkyl ester alkoxylates with a low degree of ethoxylation in the range according to the invention are selected; if hydrophilic soiling is to be removed, the use of fatty acid alkyl ester ethoxylates with a higher degree of ethoxylation in the range according to the invention is expedient.
- the above-mentioned liquid detergents and all-purpose cleaners additionally contain an anionic surfactant selected from the group of the C 6 -C 18 alkylbenzenesulfonates, C 6 -C 18 alkanesulfonates, C 6 -C 18 alkyl sulfates, C 6 -C 18 - Alkyl polyglycol ether sulfates, ⁇ -olefin sulfonates, C 6 -C 18 alkyl polyglycol ether sulfonates, glycerol ether sulfonates, glycerin ether sulfates, hydroxymixed ether sulfates, monoglyceride sulfates, sulfosuccinates, sulfotriglycerides, soaps, amide soaps, C 6 -C 6 fatty acid alkamides, C 6 -C 18 carboxylate alkoxide s
- an anionic surfactant
- liquid detergent or all-purpose cleaners additionally contain a further nonionic surfactant selected from the group of C 6 -C 18 -alkyl polyglycol ether, Zuckerester, C 6 -C 18 -Fettklarepolyglykolether, sorbitan fatty acid esters, C 6 -C 18 fatty acid partial glycerides as well as their Mixtures in a total amount of up to 30 wt .-%, based on the total amount of liquid detergent or all-purpose cleaner.
- a further nonionic surfactant selected from the group of C 6 -C 18 -alkyl polyglycol ether, Zuckerester, C 6 -C 18 -Fettkladilicates, sorbitan fatty acid esters, C 6 -C 18 fatty acid partial glycerides as well as their Mixtures in a total amount of up to 30 wt .-%, based on the total amount of liquid detergent or all-purpose cleaner.
- Particularly preferred embodiments contain anionic surfactants selected from the group of the C 6 -C 18 alkyl sulfates, the C 6 -C 18 alkyl polyglycol ether sulfates, the soaps and the C 6 -C 18 alkane sulfonates and their mixtures or nonionic surfactants selected from the group of the C 6 -C 18 alkyl polyglycol ether.
- the soaps to be used according to the invention are alkali, ammonium or alkanolammonium salts of saturated or unsaturated fatty acids with 8-22, preferably 10-18, carbon atoms.
- the soaps can either be added as such or, after the addition of appropriate fatty acids, can be formed by salt formation with bases such as NaOH, KOH, NH 3 , amines or alkanolamines.
- bases such as NaOH, KOH, NH 3 , amines or alkanolamines.
- the soaps are either completely neutralized or partly also in free form as fatty acids.
- the C 6 -C 18 alkyl ether sulfates are primarily addition products of 2-15 moles of ethylene oxide with C 6 -C 18 fatty alcohols, which are then sulfated.
- the C 6 -C 18 alkyl polyglycol ethers used as nonionic surfactants are primarily adducts of 2-10 mol ethylene oxide with C 6 -C 18 fatty alcohols.
- Auxiliaries customary in liquid detergents or all-purpose cleaners can optionally be added; these substances are builders, e.g. Glutaric acid, succinic acid, adipic acid, tartaric acid, benzene hexacarboxylic acid, gluconic acid, trisodium citrate; Solvents, e.g. Acetone, ethanol or glycerin, hydrotropes e.g. Cumene sulfonate, octyl sulfate, butyl glucoside, butylene glycol; Cleaning booster; Viscosity regulators, e.g. synthetic polymers such as polyacrylates; pH regulators, e.g. Citric acid, triethanolamine or NaOH; Preservatives, e.g. Glutaraldehyde; Dyes, fragrances and opacifiers.
- builders e.g. Glutaric acid, succinic acid, adipic acid, tartaric acid, benzene
- the pH of the all-purpose cleaners according to the invention is usually between 4 and 8.5, preferably between 6 and 8. However, a range between 7.0 and 7.5 is particularly preferred.
- the pH value at an application concentration of 10 g / l is preferably 7.3-7.8.
- the agents according to the invention are particularly suitable for cleaning hard surfaces such as e.g. Enamel, glass, PVC, linoleum, stone floors, e.g. Marble, terrazzo, unglazed clinker, ceramic tiles or sealed wooden floors, e.g. Parquet or floorboards.
- hard surfaces such as e.g. Enamel, glass, PVC, linoleum, stone floors, e.g. Marble, terrazzo, unglazed clinker, ceramic tiles or sealed wooden floors, e.g. Parquet or floorboards.
- the pH of the liquid detergents according to the invention is usually between 6.0 and 10.0, preferably between 7.0 and 9.0.
- the liquid detergents are suitable both for use in washing machines and for use in hand basins for washing high-quality textiles made of wool or silk.
- the test method described below according to "Seifen- ⁇ le-Fette-Wwachs", 112 , 371, (1986) was used to test the cleaning ability and provides very reproducible results.
- the cleaning agent to be tested was then placed in the form of a 1% by weight aqueous solution (10 g / l) on an artificially soiled plastic surface.
- a mixture of carbon black, machine oil, triglyceride, 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 impregnated with 10 ml of the 1% detergent solution to be tested and moved mechanically on the dirt-coated test surface, to which 10 ml of the 1% detergent solution to be tested was also applied. After 10 wiping movements, the cleaned test area was kept under running water and the loose dirt was removed.
- the cleaning effect of the plastic surface cleaned in this way was determined with the aid of a "Microcolor" remission color measuring device (Dr. B. Lange).
- the measurand is the degree of whiteness.
- the clean white plastic surface served as the white standard; the whiteness of the clean, white plastic surface corresponds to 100% RV (cleaning ability).
- the whiteness of a soiled and then cleaned plastic surface corresponds to a value between 0% and 100% RV.
- The% RV values represent mean values from triplicate determinations.
- the foaming behavior of the all-purpose cleaners according to the invention was tested as follows: The test product was placed in a large-volume serving glass. Then the amount of tap water was allowed to flow in freely from a height of 30 cm, which, together with the amount of product presented, gave an application concentration of the product of 10 g / l. The foam height in the beaker was read off immediately after the addition of water had ended.
- compositions were prepared by mixing the components together and then adjusting the desired pH. All percentages relate to percent by weight of active substance.
- Compositions 1 to 9 are shown in Table 1.
- Composition 1 (V) is not according to the invention and is used for comparison.
- the fatty acid alkyl ester alkoxylates are given in Table 1 in the following notation:
- Example: C 12 FSEO 15 Me stands for C 11 H 23 CO 2 (CH 2 CH 2 O) 15 CH 3 , methyl ester of C 12 fatty acid ethoxylated with 15 ethylene oxide units.
- EO stands for ethylene oxide
- PO stands for propylene oxide.
- the degrees of alkoxylation represent mean values.
- compositions 2 to 9 according to the invention are clearly superior to comparative composition 1 (V) in terms of cleaning ability and foam disintegration.
- Example 10 represents an all-purpose cleaner high concentrate, which is used in 0.1% solution.
- the agent had excellent foam properties (low foam values).
- an agent V was tested which had a C 13 -C 15 alcohol x 5 E0 instead of the fatty acid methyl ester.
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Abstract
Description
Die Erfindung betrifft schwach schäumende Wasch- oder Reinigungsmittel, wobei Flüssigwaschmittel und Reinigungsmittel für harte Oberflächen bevorzugt sind. Als Reinigungsmittel für harte Oberflächen sind alle im Haushalt- und Gewerbesektor auftretenden, nicht textilen Oberflächen, ausgenommen Geschirr, zu verstehen. Für diese Art von Reinigungsmitteln hat sich der Begriff Allzweckreiniger eingebürgert. Schwach schäumende Allzweckreiniger sind solche, die bei manueller Anwendung ein geringes Schaumvolumen entwickeln, das sich innerhalb weniger Minuten signifikant weiter verringert.The invention relates to low-foaming detergents or cleaning agents, with liquid detergents and cleaning agents for hard surfaces being preferred. All non-textile surfaces occurring in the household and commercial sector, with the exception of dishes, are to be understood as cleaning agents for hard surfaces. The term general-purpose cleaner has become established for this type of cleaning agent. Low-foaming all-purpose cleaners are those that develop a low volume of foam when used manually, which significantly reduces within a few minutes.
Allzweckreiniger sind seit langem bekannt. Es handelt sich dabei im wesentlichen um wäßrige Tensidlösungen unterschiedlichster Art mit oder ohne Zusatz an Buildern sowie mit oder ohne Zusatz an wasserlöslichen Lösungsmitteln oder Lösungsvermittlern. Nachteilig hat sich bei der manuellen Anwendung in der Praxis zunehmend deren hohes Schaumvermögen gezeigt. Der Verbraucher möchte zwar zum Nachweis der Wirksamkeit bei Beginn seiner Reinigungsarbeit ein gewisses Schäumen der Anwendungslösung wahrnehmen, der Schaum soll dann jedoch anschließend möglichst rasch zusammenfallen, damit einmal gereinigte Flächen nicht nachgewischt werden müssen.All-purpose cleaners have been known for a long time. These are essentially aqueous surfactant solutions of various types with or without the addition of builders and with or without the addition of water-soluble solvents or solubilizers. A disadvantage of manual application in practice has been its high foaming power. Although the consumer wants to perceive a certain amount of foam in the application solution at the beginning of his cleaning work to prove its effectiveness, the foam should then collapse as quickly as possible, so that once cleaned surfaces do not have to be wiped down.
Flüssigwaschmittel neigen häufig ebenfalls zu hohem Schaumvermögen, wodurch ihre Anwendbarkeit in Waschmaschinen beeinträchtigt wird.Liquid detergents also tend to have a high foaming capacity, which affects their applicability in washing machines.
Um diesem vermehrten Wunsch nach geringerem Schaumvermögen nachzukommen, sind einige Hersteller von Allzweckreinigern dazu übergegangen, den Tensidgehalt ihrer Produkte deutlich zu senken, was jedoch naturgemäß wiederum zu erheblichem Verlust an Reinigungsleistung führt. Der Anwender solcher Produkte muß die verringerte Reinigungswirkung durch vermehrten Aufwand an mechanischer Wischarbeit ausgleichen.In order to meet this increased desire for lower foaming power, some manufacturers of all-purpose cleaners have started to significantly reduce the surfactant content of their products, which in turn naturally leads to a considerable loss in cleaning performance. The user of such products must compensate for the reduced cleaning effect through increased mechanical wiping work.
Wegen ihrer ökologisch guten Eigenschaften erfreut sich der Einsatz von Alkylpolyglycosiden (APG's) in Wasch- und Reinigungsmittel wachsender Beliebtheit. Alkylpolyglycoside sind aber als stark schäumende Tenside bekannt; sie werden deshalb für Produkte mit wunschgemäß hohem Schaumvermögen, also z.B. für manuell anzuwendende Geschirrspülmittel oder für die Haarwäsche empfohlen. EP 0 070 074 B1 und 0 070 076 B2 beschreiben derartige hochschäumende Wasch- und Reinigungsmittel auf Basis verschiedener APG-haltiger Tensidkombinationen. Folgerichtig werden diese Kombinationen auch nicht für das Gebiet der Allzweckreiniger empfohlen.Because of their ecologically good properties, the use of alkyl polyglycosides (APG's) in washing and cleaning agents is becoming increasingly popular. However, alkyl polyglycosides are known to be highly foaming surfactants; They are therefore used for products with the desired high foaming capacity, So recommended for manual dishwashing detergents or for washing hair. EP 0 070 074 B1 and 0 070 076 B2 describe such high-foaming washing and cleaning agents based on various APG-containing surfactant combinations. Consequently, these combinations are not recommended for the area of all-purpose cleaners.
Auch spezielle kurzkettige C8-C10-Alkylglucoside (z.B. Triton(R)CG-110 von Rohm & Haas) sind seit langem als gut schäumende und schaumstabile nichtionische Tenside bekannt. Schwach schäumende Reinigungsmittel mit einem Gehalt an Alkypolyglucosiden für maschinelle Reinigungsarbeiten, insbesondere Geschirrspülen, werden in WO 88/09369 beschrieben. Die Schaumarmut wird in diesen Mitteln durch Mitverwendung von konventionellen, schwachschäumenden Fettalkoholalkoxylaten, die einen HLB-Wert von etwa 10 oder weniger aufweisen und Propylenoxideinheiten enthalten können, erreicht.Special short-chain C 8 -C 10 alkyl glucosides (eg Triton ( R ) CG-110 from Rohm & Haas) have also been known for a long time as good foaming and foam-stable nonionic surfactants. Low-foaming cleaning agents containing alkypolyglucosides for machine cleaning work, in particular dishwashing, are described in WO 88/09369. In these agents, low-foaming is achieved by using conventional, low-foaming fatty alcohol alkoxylates, which have an HLB value of about 10 or less and can contain propylene oxide units.
In der deutschen Offenlegungsschrift DE 42 27 046 werden Detergens-Mischungen auf Basis von Fettsäurealkylesteralkoxylaten beschrieben.German published patent application DE 42 27 046 describes detergent mixtures based on fatty acid alkyl ester alkoxylates.
WO-A-91 14 760 offenbart schwachschäumende Tensidgemische bestehend aus Alkylpolyglycosiden und mit Alkylresten veretherten Fettalkoholalkoxylaten.WO-A-91 14 760 discloses low-foaming surfactant mixtures consisting of alkyl polyglycosides and fatty alcohol alkoxylates etherified with alkyl radicals.
Aufgabe der vorliegenden Erfindung war es, Wasch- oder Reinigungsmittel zu schaffen, welche zugleich ein gutes Reinigungsvermögen, gute biologische Abbaubarkeit und ein ausgeprägt schwaches Schäumvermögen besitzen. Bei der Verwendung zur manuellen Reinigung von harten Oberflächen soll als Kriterium gelten, daß sich anfänglich gebildeter Schaum innerhalb von 2 Minuten sichtbar verringert.The object of the present invention was to provide washing or cleaning agents which at the same time have good cleaning properties, good biodegradability and a pronouncedly low foaming power. When used for the manual cleaning of hard surfaces, the criterion should be that initially formed foam visibly reduces within 2 minutes.
Überraschenderweise wurde nun gefunden, daß mit Hilfe von Kombinationen bestimmter als stark schäumend bekannter C8-C18-Alkylpolyglycoside mit bestimmten Fettsäurealkylesteralkoxylaten Flüssigwaschmittel und Allzweckreiniger mit hohem Reinigungsvermögen und extrem schwachem Schaumverhalten bereitgestellt werden können.Surprisingly, it has now been found that with the aid of combinations of certain C 8 -C 18 alkyl polyglycosides known to be highly foaming with certain fatty acid alkyl ester alkoxylates, liquid detergents and all-purpose cleaners with high cleaning power and extremely low foaming behavior can be provided.
Gegenstand der Erfindung sind wasserhaltige Wasch- oder Reinigungsmittel, enthaltend 0,1 bis 50 Gew.-%, vorzugsweise 1 bis 20 Gew.-%, mindestens eines Alkylpolyglycosids der Formel I, R1-O-[Z]x (I), wobei R1 eine verzweigte oder geradkettige, gesättigte oder ungesättigte Alkylgruppe mit 8 bis 18 C-Atomen, Z einen Zuckerrest, vorzugsweise einen Glucose- oder Xylose-Rest und x ganze Zahlen von 1 bis 10, darstellt und 0,05 bis 50 Gew.-%, vorzugsweise 1 bis 20 Gew.-%, mindestens eines Fettsäurealkylesteralkoxylats der Formel II, R2-CO2-(AO)y-R3 (II), wobei R2 für eine verzweigte oder geradkettige, gesättigte oder ungesättigte Alkylgruppe mit 5 bis 21 C-Atomen, AO für eine C2-C4-Alkylenoxideinheit, y für eine Zahl von 1 bis 30 und R3 für eine geradkettige oder verzweigte Alkylgruppe mit 1 bis 6 C-Atomen steht.The invention relates to water-containing washing or cleaning agents containing 0.1 to 50% by weight, preferably 1 to 20% by weight, of at least one alkyl polyglycoside of the formula I, R 1 -O- [Z] x (I), where R 1 is a branched or straight-chain, saturated or unsaturated alkyl group having 8 to 18 carbon atoms, Z is a sugar residue, preferably a glucose or Xylose radical and x represents integers from 1 to 10, and 0.05 to 50% by weight, preferably 1 to 20% by weight, of at least one fatty acid alkyl ester alkoxylate of the formula II, R 2 -CO 2 - (AO) y -R 3 (II), where R 2 is a branched or straight-chain, saturated or unsaturated alkyl group having 5 to 21 C atoms, AO is a C 2 -C 4 alkylene oxide unit, y is a number from 1 to 30 and R 3 represents a straight-chain or branched alkyl group having 1 to 6 carbon atoms.
Die in den erfindungsgemäßen Mitteln eingesetzten Alkylpolyglycoside stellen bekannte Stoffe dar, die nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden können; stellvertretend sei hier auf die Schriften EP 0 301 298 Al und WO 90/3977 verwiesen. Die Alkylpolyglycoside können sich von Zuckern bzw. Zuckerresten, d.h. Aldosen bzw. Ketosen mit 5 oder 6 Kohlenstoffatomen, vorzugsweise der Glucose und der Xylose ableiten. Die bevorzugten Alkylpolyglycoside sind somit Alkylpolyglucoside und Alkylpolyxyloside.The alkyl polyglycosides used in the agents according to the invention are known substances which can be obtained by the relevant methods of preparative organic chemistry; as a representative, reference is made to the documents EP 0 301 298 A1 and WO 90/3977. The alkyl polyglycosides can be from sugars or sugar residues, i.e. Derive aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose and xylose. The preferred alkyl polyglycosides are thus alkyl polyglucosides and alkyl polyxylosides.
Der Index x in der Formel (I) gibt den Oligomerisierungsgrad (DP-Grad), d.h. die Verteilung von Mono- und Oligoglycosiden an und steht für eine Zahl zwischen 1 und 10. Während x in einer gegebenen Verbindung stets ganzzahlig sein muß und hier vor allem die Werte x = 1 bis 6 annehmen kann, ist der Wert x für ein bestimmtes Alkylpolyglycosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkylpolyglycoside mit einem mittleren Oligomerisierungsgrad von 1,1 bis 3,0, vorzugsweise 1,1 bis 1,7 eingesetzt.The index x in formula (I) indicates the degree of oligomerization (DP degree), i.e. the distribution of mono- and oligoglycosides is present and stands for a number between 1 and 10. While x must always be an integer in a given compound and here can assume the values x = 1 to 6, the value x is for a certain alkyl polyglycoside an analytically calculated quantity, which usually represents a fractional number. Alkyl polyglycosides with an average degree of oligomerization of 1.1 to 3.0, preferably 1.1 to 1.7, are preferably used.
Der Alkylrest R1 in der Formel (I) kann sich von primären verzweigten und unverzweigten Alkoholen mit 8 bis 18 Kohlenstoffatomen ableiten. Typische Beispiele sind Myristylalkohol, Cetylalkohol sowie deren technische Gemische. Vorzugsweise werden jedoch Alkylpolyglycoside der Formel (I) eingesetzt, in denen R1 einen Kohlenstoffrest mit 8 bis 12, insbesondere 8 bis 10 Kohlenstoffatomen, darstellt. Typische Beispiele sind neben Laurylalkohol insbesondere Caprylalkohol und Caprinalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hydrierung von technischen Fettsäuremethylestern oder im Verlauf der Hydrierung von Aldehyden aus der Roelen'schen-Oxosynthese anfallen.The alkyl radical R 1 in the formula (I) can be derived from primary branched and unbranched alcohols having 8 to 18 carbon atoms. Typical examples are myristyl alcohol, cetyl alcohol and their technical mixtures. However, preference is given to using alkylpolyglycosides of the formula (I) in which R 1 represents a carbon radical having 8 to 12, in particular 8 to 10, carbon atoms. In addition to lauryl alcohol, typical examples are, in particular, caprylic alcohol and capric alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
Die in den erfindungsgemäßen Mitteln eingesetzten Fettsäurealkylesteralkoxylate der Formel (II) können durch konventionelle Methoden hergestellt werden, wie z.B. durch Veresterung von Fettsäurederivaten mit alkoxyliertem Methanol. Dieses Verfahren ist jedoch mit einigen Nachteilen verbunden, es verläuft zweistufig, die Veresterung dauert sehr lange und die Produkte sind durch die hohen Reaktionstemperaturen gefärbt. Außerdem besitzen solchermaßen hergestellte Fettsäuremethylesteralkoxylate häufig nach der Veresterung relativ hohe OH-Zahlen, was für manche Anwendungen problematisch sein kann. Vorzugsweise werden die Fettsäurealkylesteralkoxylate der Formel (II) durch eine heterogen katalysierte Direktalkoxylierung von Fettsäurealkylester mit Alkylenoxid, insbesondere Ethylenoxid, hergestellt. Dieses Syntheseverfahren ist in WO 90/13533 und WO 91/15441 ausführlich beschrieben. Die dabei entstehenden Produkte zeichnen sich durch eine niedrige OH-Zahl aus, die Reaktion wird einstufig durchgeführt und man erhält hellfarbige Produkte. Vorzugsweise werden solche Fettsäurealkylesteralkoxylate der Formel (II) eingesetzt, die durch Ethoxylierung von Fettsäuremethylester entstehen, d.h. in denen A0 in der Formel (II) für eine Ethylenoxideinheit und R3 für eine Methylgruppe steht. Die als Ausgangsstoffe dienenden Fettsäuremethylester können sowohl aus natürlichen Ölen und Fetten gewonnen als auch auf synthetischem Wege hergestellt werden.The fatty acid alkyl ester alkoxylates of the formula (II) used in the agents according to the invention can be prepared by conventional methods, such as, for example, by esterification of fatty acid derivatives with alkoxylated methanol. However, this process has some disadvantages, it has two stages, the esterification takes a very long time and the products are colored by the high reaction temperatures. In addition, fatty acid methyl ester alkoxylates produced in this way often have relatively high OH numbers after the esterification, which can be problematic for some applications. The fatty acid alkyl ester alkoxylates of the formula (II) are preferably prepared by heterogeneously catalyzed direct alkoxylation of fatty acid alkyl esters with alkylene oxide, in particular ethylene oxide. This synthesis method is described in detail in WO 90/13533 and WO 91/15441. The resulting products are characterized by a low OH number, the reaction is carried out in one step and light-colored products are obtained. Those fatty acid alkyl ester alkoxylates of the formula (II) which are formed by ethoxylation of fatty acid methyl esters, ie in which A0 in the formula (II) is an ethylene oxide unit and R 3 is a methyl group, are preferably used. The fatty acid methyl esters used as starting materials can be obtained from natural oils and fats as well as produced synthetically.
In den erfindungsgemäßen Allzweckreinigern werden vorzugsweise Fettsäurealkylesteralkoxylate verwendet, wobei y für eine Zahl von 5 bis 25, insbesondere von 9 bis 18 steht. In den erfindungsgemäßen Flüssigwaschmitteln hingegen werden vorzugsweise Fettsäurealkylesteralkoxylate verwendet, wobei R2 für eine verzweigte oder geradkettige, gesättigte Alkylgruppe mit 12 bis 18 C-Atomen und y für eine Zahl von 3 bis 15 steht.Fatty acid alkyl ester alkoxylates are preferably used in the all-purpose cleaners according to the invention, where y is a number from 5 to 25, in particular from 9 to 18. In contrast, fatty acid alkyl ester alkoxylates are preferably used in the liquid detergents according to the invention, where R 2 is a branched or straight-chain, saturated alkyl group having 12 to 18 carbon atoms and y is a number from 3 to 15.
Sollen die erfindungsgemäßen Flüssigwaschmittel und Allzweckreiniger zur Entfernung lipophiler Anschmutzungen verwendet werden, wählt man Fettsäurealkylesteralkoxylate mit im erfindungsgemäßen Bereich liegendem niedrigen Ethoxylierungsgrad; sollen hydrophile Anschmutzungen entfernt werden, ist der Einsatz von Fettsäurealkyesterethoxylaten mit im erfindungsgemäßen Bereich liegenden höheren Ethoxylierungsgrad zweckmäßig.If the liquid detergents and general-purpose cleaners according to the invention are to be used to remove lipophilic soiling, fatty acid alkyl ester alkoxylates with a low degree of ethoxylation in the range according to the invention are selected; if hydrophilic soiling is to be removed, the use of fatty acid alkyl ester ethoxylates with a higher degree of ethoxylation in the range according to the invention is expedient.
In einer bevorzugten Ausführungsform der Erfindung beinhalten obengenannte Flüssigwaschmittel und Allzweckreiniger zusätzlich ein anionisches Tensid ausgewählt aus der Gruppe der C6-C18-Alkylbenzolsulfonate, C6-C18-Alkansulfonate, C6-C18-Alkylsulfate, C6-C18-Alkylpolyglykolethersulfate, α-Olefinsulfonate, C6-C18-Alkylpolyglykolethersulfonate, Glycerinethersulfonate, Glycerinethersulfate, Hydroxymischethersulfate, Monoglyceridsulfate, Sulfosuccinate, Sulfotriglyceride, Seifen, Amidseifen, C6-C18-Fettsäureamid-ethersulfate, C6-C18-Alkylcarboxylate, Fettsäureisethionate, N-C6-C18-Acyl-Sarcosinate, N-C6-C18-Acyl-Tauride, C6-C18-Alkyloligoglucosidsulfate, C6-C18-Alkyl-phosphate sowie deren Mischungen in einer Gesamtmenge von bis zu 40 Gew.-% bezogen auf das Gesamtgewicht des Flüssigwaschmittels oder Allzweckreinigers.In a preferred embodiment of the invention, the above-mentioned liquid detergents and all-purpose cleaners additionally contain an anionic surfactant selected from the group of the C 6 -C 18 alkylbenzenesulfonates, C 6 -C 18 alkanesulfonates, C 6 -C 18 alkyl sulfates, C 6 -C 18 - Alkyl polyglycol ether sulfates, α-olefin sulfonates, C 6 -C 18 alkyl polyglycol ether sulfonates, glycerol ether sulfonates, glycerin ether sulfates, hydroxymixed ether sulfates, monoglyceride sulfates, sulfosuccinates, sulfotriglycerides, soaps, amide soaps, C 6 -C 6 fatty acid alkamides, C 6 -C 18 carboxylate alkoxide sulfate NC 6 -C 18 acyl sarcosinates, NC 6 -C 18 acyl taurides, C 6 -C 18 alkyl oligoglucoside sulfates, C 6 -C 18 alkyl phosphates and mixtures thereof in a total amount of up to 40% by weight. % based on the total weight of the liquid detergent or all-purpose cleaner.
In einer weiteren bevorzugten Ausführungsform enthalten die erfindungsgemäßen Flüssigwaschmittel oder Allzweckreiniger zusätzlich ein weiteres nichtionisches Tensid ausgewählt aus der Gruppe der C6-C18-Alkylpolyglykolether, Zuckerester, C6-C18-Fettsäurepolyglykolether, Sorbitanfettsäureester, C6-C18-Fettsäurepartialglyceride sowie deren Mischungen in einer Gesamtmenge von bis zu 30 Gew.-%, bezogen auf die Gesamtmenge des Flüssigwaschmittels oder Allzweckreinigers.In a further preferred embodiment of the present invention liquid detergent or all-purpose cleaners additionally contain a further nonionic surfactant selected from the group of C 6 -C 18 -alkyl polyglycol ether, Zuckerester, C 6 -C 18 -Fettsäurepolyglykolether, sorbitan fatty acid esters, C 6 -C 18 fatty acid partial glycerides as well as their Mixtures in a total amount of up to 30 wt .-%, based on the total amount of liquid detergent or all-purpose cleaner.
Besonders bevorzugte Ausführungsformen enthalten Aniontenside ausgewählt aus der Gruppe der C6-C18-Alkylsulfate, der C6-C18-Alkylpolyglykolethersulfate, der Seifen und der C6-C18-Alkansulfonate sowie deren Mischungen bzw. nichtionische Tenside ausgewählt aus der Gruppe der C6-C18-Alkylpolyglycolether.Particularly preferred embodiments contain anionic surfactants selected from the group of the C 6 -C 18 alkyl sulfates, the C 6 -C 18 alkyl polyglycol ether sulfates, the soaps and the C 6 -C 18 alkane sulfonates and their mixtures or nonionic surfactants selected from the group of the C 6 -C 18 alkyl polyglycol ether.
Bei den erfindungsgemäß einzusetzenden Seifen handelt es sich um Alkali-, Ammonium- oder Alkanolammoniumsalze von gesättigten oder ungesättigten Fettsäuren mit 8 - 22, vorzugsweise 10 - 18 C-Atomen. Die Seifen können entweder als solche zugegeben werden oder nach Zugabe von entsprechenden Fettsäuren durch Salzbildung mit Basen wie z.B. NaOH, KOH, NH3, Aminen oder Alkanolaminen gebildet werden. In Abhängigkeit des eingestellten pH-Werts der erfindungsgemäßen Mittel liegen die Seifen entweder vollständig neutralisiert oder teilweise auch in freier Form als Fettsäure vor.The soaps to be used according to the invention are alkali, ammonium or alkanolammonium salts of saturated or unsaturated fatty acids with 8-22, preferably 10-18, carbon atoms. The soaps can either be added as such or, after the addition of appropriate fatty acids, can be formed by salt formation with bases such as NaOH, KOH, NH 3 , amines or alkanolamines. Depending on the adjusted pH of the agents according to the invention, the soaps are either completely neutralized or partly also in free form as fatty acids.
Bei den C6-C18-Alkylethersulfaten handelt es sich in erster Linie um Anlagerungsprodukte von 2 - 15 Mol Ethylenoxid an C6-C18-Fettalkohole, welche anschließend sulfatiert werden. Bei den als nichtionische Tenside eingesetzten C6-C18-Alkylpolyglykolethern handelt es sich in erster Linie um Anlagerungsprodukte von 2 - 10 Mol Ethylenoxid an C6-C18-Fettalkohole.The C 6 -C 18 alkyl ether sulfates are primarily addition products of 2-15 moles of ethylene oxide with C 6 -C 18 fatty alcohols, which are then sulfated. The C 6 -C 18 alkyl polyglycol ethers used as nonionic surfactants are primarily adducts of 2-10 mol ethylene oxide with C 6 -C 18 fatty alcohols.
Fakultativ können weiterhin in Flüssigwaschmitteln oder Allzweckreinigern übliche Hilfsstoffe zugesetzt werden; bei diesen Stoffen handelt es sich um Builder, z.B. Glutarsäure, Bernsteinsäure, Adipinsäure, Weinsäure, Benzolhexacarbonsäure, Gluconsäure, Trinatriumcitrat; Lösungsmittel, z.B. Aceton, Ethanol oder Glycerin, Hydrotrope, z.B. Cumolsulfonat, Octylsulfat, Butylglucosid, Butylenglykol; Reinigungsverstärker; Viskositätsregler, z.B. synthetische Polymere wie Polyacrylate; pH-Regulatoren, z.B. Zitronensäure, Triethanolamin oder NaOH; Konservierungsmittel, z.B. Glutaraldehyd; Farb- und Duftstoffe sowie Trübungsmittel.Auxiliaries customary in liquid detergents or all-purpose cleaners can optionally be added; these substances are builders, e.g. Glutaric acid, succinic acid, adipic acid, tartaric acid, benzene hexacarboxylic acid, gluconic acid, trisodium citrate; Solvents, e.g. Acetone, ethanol or glycerin, hydrotropes e.g. Cumene sulfonate, octyl sulfate, butyl glucoside, butylene glycol; Cleaning booster; Viscosity regulators, e.g. synthetic polymers such as polyacrylates; pH regulators, e.g. Citric acid, triethanolamine or NaOH; Preservatives, e.g. Glutaraldehyde; Dyes, fragrances and opacifiers.
Der pH-Wert der erfindungsgemäBen Allzweckreiniger liegt üblicherweise zwischen 4 und 8,5, vorzugsweise zwischen 6 und 8. Besonders bevorzugt ist jedoch ein Bereich zwischen 7,0 und 7,5. Der pH-Wert bei einer Anwendungskonzentration von 10 g/l liegt vorzugsweise bei 7,3 - 7,8.The pH of the all-purpose cleaners according to the invention is usually between 4 and 8.5, preferably between 6 and 8. However, a range between 7.0 and 7.5 is particularly preferred. The pH value at an application concentration of 10 g / l is preferably 7.3-7.8.
Die erfindungsgemäßen Mittel eignen sich besonders zum Reinigen von harten Oberflächen wie z.B. Emaille, Glas, PVC, Linoleum, Steinböden, wie z.B. Marmor, Terrazzo, nicht glasierten Klinker, Keramik-Fliesen oder versiegelten Holzfußböden, wie z.B. Parkett oder Dielen.The agents according to the invention are particularly suitable for cleaning hard surfaces such as e.g. Enamel, glass, PVC, linoleum, stone floors, e.g. Marble, terrazzo, unglazed clinker, ceramic tiles or sealed wooden floors, e.g. Parquet or floorboards.
Der pH-Wert der erfindungsgemäßen Flüssigwaschmittel liegt üblicherweise zwischen 6,0 und 10,0, vorzugsweise zwischen 7,0 und 9,0.The pH of the liquid detergents according to the invention is usually between 6.0 and 10.0, preferably between 7.0 and 9.0.
Die Flüssigwaschmittel eignen sich sowohl für den Einsatz in Waschmaschinen als auch für den Einsatz im Handwaschbecken zum Waschen von hochwertigen Textilien aus Wolle oder Seide.The liquid detergents are suitable both for use in washing machines and for use in hand basins for washing high-quality textiles made of wool or silk.
Zum Nachweis der Vorteile der erfindungsgemäßen Allzweckreiniger gegenüber bekannten Allzweckreinigern für harte Oberflächen wurden Vergleichsversuche hinsichtlich des Reinigungsvermögens und des Schaumzerfalls angestellt.To demonstrate the advantages of the all-purpose cleaners according to the invention over known all-purpose cleaners for hard surfaces, comparative tests were carried out with regard to the cleaning ability and the foam breakdown.
Zur Prüfung des Reinigungsvermögens diente die unten nach "Seifen-Öle-Fette-Wachse", 112, 371, (1986) beschriebene Testmethode, die sehr gut reproduzierbare Ergebnisse liefert. Danach wurde das zu prüfende Reinigungsmittel in Form einer 1 Gew.-%igen wäßrigen Lösung (10 g/l) auf eine künstlich angeschmutzte Kunststoffoberfläche gegeben. Als künstliche Anschmutzung für die verdünnte Anwendung des Reinigungmittels wurde ein Gemisch aus Ruß, Maschinenöl, Triglycerid gesättigter Fettsäuren und niedersiedendem aliphatischen Kohlenwasserstoff verwendet. Die Testfläche von 26 x 28 cm wurde mit Hilfe eines Flächenstreichers gleichmäßig mit 2 g der künstlichen Anschmutzung beschichtet.The test method described below according to "Seifen-Öle-Fette-Wwachs", 112 , 371, (1986) was used to test the cleaning ability and provides very reproducible results. The cleaning agent to be tested was then placed in the form of a 1% by weight aqueous solution (10 g / l) on an artificially soiled plastic surface. A mixture of carbon black, machine oil, triglyceride, 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.
Ein Kunststoffschwamm wurde jeweils mit 10 ml der zu prüfenden 1 %igen Reinigungsmittellösung getränkt und mechanisch auf der schmutzbeschichteten Testfläche bewegt, auf die ebenfalls 10 ml der zu prüfenden, 1 %igen Reinigungsmittellösung aufgebracht waren. Nach 10 Wischbewegungen wurde die gereinigte Testfläche unter fließendes Wasser gehalten und der lose sitzende Schmutz entfernt. Die Reinigungswirkung der so gereinigten Kunststoffoberfläche wurde mit Hilfe eines Remissionsfarbmeßgerätes "Microcolor" (Dr. B. Lange) ermittelt. Die Meßgröße ist dabei der Weißgrad. Als Weiß-Standard diente die saubere weiße Kunststoffoberfläche; der Weißgrad der sauberen, weißen Kunststoffoberfläche entspricht 100 % RV (Reinigungsvermögen). Der Weißgrad einer angeschmutzten und anschließend gereinigten Kunststoffoberfläche entspricht demgemäß einem Wert zwischen 0 % und 100 % RV. Die % RV-Werte stellen jeweils Mittelwerte aus Dreifachbestimmungen dar.A plastic sponge was impregnated with 10 ml of the 1% detergent solution to be tested and moved mechanically on the dirt-coated test surface, to which 10 ml of the 1% detergent solution to be tested was also applied. After 10 wiping movements, the cleaned test area was kept under running water and the loose dirt was removed. The cleaning effect of the plastic surface cleaned in this way was determined with the aid of a "Microcolor" remission color measuring device (Dr. B. Lange). The measurand is the degree of whiteness. The clean white plastic surface served as the white standard; the whiteness of the clean, white plastic surface corresponds to 100% RV (cleaning ability). The whiteness of a soiled and then cleaned plastic surface corresponds to a value between 0% and 100% RV. The% RV values represent mean values from triplicate determinations.
Die Meßwerte wurden in Relation zum Reinigungsergebnis eines als Standard benutzten leistungsstarken Allzweckreinigers gesetzt.
Die als Standard benutzte leistungsstarke Formulierung hatte die Zusammensetzung:
- 8 %
- Alkylbenzolsulfonat-Na-Salz
- 2 %
- Addukt von C12-C14-Alkylepoxid + Ethylenglykol + 10 Mol Ethylenoxid
- 2 %
- Na-gluconat
- 0,1 %
- Polyethylenglykol mit einem Molgewicht von ca. 600000 (Polyox WSR 205 der Fa. UCC)
- 8th %
- Alkylbenzenesulfonate Na salt
- 2%
- Adduct of C 12 -C 14 alkyl epoxide + ethylene glycol + 10 moles of ethylene oxide
- 2%
- Na gluconate
- 0.1%
- Polyethylene glycol with a molecular weight of approx. 600,000 (Polyox WSR 205 from UCC)
Das Schaumverhalten der erfindungsgemäßen Allzweckreiniger wurde folgendermaßen geprüft: Das Prüfprodukt wurde in ein weitlumiges Becfierglas vorgelegt. Sodann wurde darauf aus 30 cm Höhe im freien Fall die Menge an Leitungswasser zuflieBen gelassen, die mit der Menge an vorgelegtem Produkt eine Anwendungskonzentration des Produkts von 10 g/l ergibt. Die Schaumhöhe im Becherglas wurde unmittelbar nach Beendigung der Wasserzugabe abgelesen.The foaming behavior of the all-purpose cleaners according to the invention was tested as follows: The test product was placed in a large-volume serving glass. Then the amount of tap water was allowed to flow in freely from a height of 30 cm, which, together with the amount of product presented, gave an application concentration of the product of 10 g / l. The foam height in the beaker was read off immediately after the addition of water had ended.
Die folgenden Zusammensetzungen wurden durch Zusammenmischen der Komponenten und anschließende Einstellung des gewünschten pH-Wertes hergestellt. Alle Prozentangaben beziehen sich auf Gewichtsprozent Aktivsubstanz.The following compositions were prepared by mixing the components together and then adjusting the desired pH. All percentages relate to percent by weight of active substance.
Die Zusammensetzungen 1 bis 9 sind Tabelle 1 zu entnehmen. Die Zusammensetzung 1 (V) ist nicht erfindungsgemäß und dient zum Vergleich.Compositions 1 to 9 are shown in Table 1. Composition 1 (V) is not according to the invention and is used for comparison.
Die Fettsäurealkylesteralkoxylate werden in Tabelle 1 in folgender Schreibweise wiedergegeben:
Beispiel: C12FSEO15Me steht für
C11H23CO2(CH2CH2O)15CH3, Methylester der mit 15 Ethylenoxideinheiten ethoxylierten C12-Fettsäure.
EO steht für Ethylenoxid, PO steht für Propylenoxid. Die Alkoxylierungsgrade stellen dabei Mittelwerte dar.
Example: C 12 FSEO 15 Me stands for
C 11 H 23 CO 2 (CH 2 CH 2 O) 15 CH 3 , methyl ester of C 12 fatty acid ethoxylated with 15 ethylene oxide units.
EO stands for ethylene oxide, PO stands for propylene oxide. The degrees of alkoxylation represent mean values.
Es zeigt sich, daß die erfindungsgemäßen Zusammensetzungen 2 bis 9 gegenüber der Vergleichszusammensetzung 1 (V) hinsichtlich Reinigungsvermögen und Schaumzerfall eine deutliche Überlegenheit aufweisen.It can be seen that compositions 2 to 9 according to the invention are clearly superior to comparative composition 1 (V) in terms of cleaning ability and foam disintegration.
Die folgenden Beispiele zeigen weitere bevorzugte Formulierungen und Einsatzmöglichkeiten für die beanspruchten Allzweckreiniger.The following examples show further preferred formulations and possible uses for the claimed general-purpose cleaners.
- 45,0 Gew.-%45.0% by weight
- C8 - C10-Alkylpolyglucosid, DP = 1,6C 8 -C 10 alkyl polyglucoside, DP = 1.6
- 20,0 Gew.-%20.0% by weight
- C12-Fettsäuremethylester x 13 EOC 12 fatty acid methyl ester x 13 EO
- 5,0 Gew.-%5.0% by weight
- PalmkernfettsäurePalm kernel fatty acid
- 1,0 Gew.-%1.0% by weight
- Zitronensäurecitric acid
- 10,0 Gew.-%10.0% by weight
-
Cumolsulfonat
Kalilauge zur Einstellung des pH-Wertes des Fertigproduktes auf pH 8 Farb- und DuftstoffeCumene sulfonate
Potash lye to adjust the pH of the finished product to pH 8 colors and fragrances - ad 100,0 Gew.-%ad 100.0% by weight
- Wasserwater
Das Beispiel 10 stellt ein Allzweckreiniger-Hochkonzentrat dar, welches in 0,1 %iger Lösung zur Anwendung kommt.Example 10 represents an all-purpose cleaner high concentrate, which is used in 0.1% solution.
- 3,0 Gew.-%3.0% by weight
- C8 - C10-Alkylpolyglucosid, DP = 1,6C 8 -C 10 alkyl polyglucoside, DP = 1.6
- 1 Gew.-%1% by weight
- ButylpolyglucosidButyl polyglucoside
- 1 Gew.-%1% by weight
- C12-Fettsäuremethylester x 12 E0C 12 fatty acid methyl ester x 12 E0
- 0,5 Gew.-%0.5% by weight
- PalmkernfettsäurePalm kernel fatty acid
- 2,0 Gew.-%2.0% by weight
- Methacrylsäure-(Stearylalkohol-20 EO-ester)ester/Acrylsäure-Copolymer (Acrysol ICS-1 der Fa. Rohm & Haas)Methacrylic acid (stearyl alcohol-20 EO-ester) ester / acrylic acid copolymer (Acrysol ICS-1 from Rohm & Haas)
- 0,05 Gew.-%0.05% by weight
- Polyethylenoxid, MG 600000Polyethylene oxide, MW 600000
- 2,0 Gew.-%2.0% by weight
-
Butylglykol
Natronlauge zur Einstellung auf pH 8 Farb- und Duftstoffe, KonservierungsmittelButyl glycol
Sodium hydroxide solution for adjustment to pH 8 colors and fragrances, preservative - ad 100,0 Gew.-%ad 100.0% by weight
- Wasserwater
- 0,2 Gew.-%0.2% by weight
- C10-Alkylpolyglucosid, DP = 1,6C 10 alkyl polyglucoside, DP = 1.6
- 0,05 Gew.-%0.05% by weight
- C10-C12-Fettsäuremethylester x 17 E0C 10 -C 12 fatty acid methyl ester x 17 E0
- 7,0 Gew.-%7.0% by weight
-
Ethanol
Ammoniak zur Einstellung auf pH 8,3Ethanol
Ammonia to adjust to pH 8.3 - ad 100,0 Gew.-%ad 100.0% by weight
- Wasserwater
Es handelt sich hierbei um einen Allzwecksprühreiniger, der unverdünnt mittels Handsprühpumpe appliziert wird. Bei dieser Angebotsform erfolgt die Bestimmung des Schaumzerfalls durch visuelle Abmusterung des Sprühvorganges: die zu reinigende angesprühte Fläche zeigte unmittelbar nach Applikation des Sprühreinigers keine Schaumbläschen.It is an all-purpose spray cleaner that is applied undiluted using a hand spray pump. In this form of offer, foam decay is determined by visual sampling of the spraying process: the sprayed surface to be cleaned showed no foam bubbles immediately after application of the spray cleaner.
- 5 Gew.-%5% by weight
- C10-Alkylpolyglucosid, DP = 1,6C 10 alkyl polyglucoside, DP = 1.6
- 4 Gew.-%4% by weight
- C12-Fettsäuremethylester x 6 E0C 12 fatty acid methyl ester x 6 E0
- 2 Gew.-%2% by weight
- OctylsulfatOctyl sulfate
- 5 Gew.-%5% by weight
- EthanolEthanol
- 3 Gew.-%3% by weight
-
Trinatriumcitrat
Zitronensäure zur Einstellung auf pH 5,5Trisodium citrate
Citric acid to adjust to pH 5.5 - ad 100,0 Gew.-%ad 100.0% by weight
- Wasserwater
- 12 Gew.-%12% by weight
- C10-Alkylpolyxylosid, DP = 1,4C 10 alkyl polyxyloside, DP = 1.4
- 8 Gew.-%8% by weight
- C12-Fettsäuremethylester x 11 E0C 12 fatty acid methyl ester x 11 E0
- 2 Gew.-%2% by weight
- C12-FettalkoholsulfatC 12 fatty alcohol sulfate
- 5 Gew.-%5% by weight
-
Ethanol
Kalilauge zur Einstellung auf pH 7-7,5Ethanol
Potash lye to adjust to pH 7-7.5 - ad 100,0 Gew.-%ad 100.0% by weight
- Wasserwater
- 6 Gew.-%6% by weight
- C10-Alkylpolyxylosid, DP = 1,4C 10 alkyl polyxyloside, DP = 1.4
- 8 Gew.-%8% by weight
- C12-Fettsäuremethylester x 11 EOC 12 fatty acid methyl ester x 11 EO
- 6 Gew.-%6% by weight
- C12-C14-Fettalkoholether(2 EO) sulfatC 12 -C 14 fatty alcohol ether (2 EO) sulfate
- 5 Gew.-%5% by weight
-
Ethanol
NaOH zur Einstellung auf pH 7-7,5Ethanol
NaOH to adjust to pH 7-7.5 - ad 100,0 Gew.-%ad 100.0% by weight
- Wasserwater
- 10 Gew.-%10% by weight
- C8-Alkylpolyxylosid, DP = 1,4C 8 alkyl polyxyloside, DP = 1.4
- 8 Gew.-%8% by weight
- C12-Fettsäuremethylester x 11 EOC 12 fatty acid methyl ester x 11 EO
- 2 Gew.-%2% by weight
- Decanol x 3 EODecanol x 3 EO
- 1,5 Gew.-%1.5% by weight
- KokosfettsäureCoconut fatty acid
- 5 Gew.-%5% by weight
-
Ethanol
NaOH zur Einstellung auf pH 7-7,5Ethanol
NaOH to adjust to pH 7-7.5 - ad 100,0 Gew.-%ad 100.0% by weight
- Wasserwater
- 10 Gew.-%10% by weight
- C8-C10-Alkylpolyglucosid, DP = 1,6C 8 -C 10 alkyl polyglucoside, DP = 1.6
- 8 Gew.-%8% by weight
- C8-C16-Fettsäuremethylester x 18 POC 8 -C 16 fatty acid methyl ester x 18 PO
- 2 Gew.-%2% by weight
- C13-C18-sec-Alkansulfonat, Na-Salz Hostapur SAS 60 der Fa. HoechstC 13 -C 18 -sec-alkanesulfonate, Na salt Hostapur SAS 60 from Hoechst
- 3 Gew.-%3% by weight
- CumolsulfonatCumene sulfonate
- 1,5 Gew.-%1.5% by weight
- KokosfettsäureCoconut fatty acid
- 5 Gew.-%5% by weight
-
Ethanol
NaOH zur Einstellung auf pH 7-7,5Ethanol
NaOH to adjust to pH 7-7.5 - ad 100,0 Gew.-%ad 100.0% by weight
- Wasserwater
- 1,5 Gew.-%1.5% by weight
- APG 600 (C12-C14-Alkylpolyglucosid der Fa. Henkel, DP = 1,4)APG 600 (C 12 -C 14 alkyl polyglucoside from Henkel, DP = 1.4)
- 1,5 Gew.-%1.5% by weight
- C12-Fettsäuremethylester x 15 EOC 12 fatty acid methyl ester x 15 EO
- 1 Gew.-%1% by weight
- Methacrylsäure-(Stearylalkohol-20 EO-ester)ester/Acrylsäure-Copolymer (Acrysol ICS-1 der Fa. Rohm + Haas)Methacrylic acid (stearyl alcohol-20 EO-ester) ester / acrylic acid copolymer (Acrysol ICS-1 from Rohm + Haas)
- 50 Gew.-%50% by weight
-
Quarzmehl
Triethanolamin zur Einstellung auf pH 8Quartz flour
Triethanolamine to adjust to pH 8 - ad 100,0 Gew.-%ad 100.0% by weight
- Wasserwater
- 4,0 Gew.-%4.0% by weight
- C10-Alkylpolyglucosid, DP = 1,6C 10 alkyl polyglucoside, DP = 1.6
- 5,0 Gew.-%5.0% by weight
- C12-Fettsäuremethylester x 17 EOC 12 fatty acid methyl ester x 17 EO
- 1,0 Gew.-%1.0% by weight
- OctylsulfatOctyl sulfate
- 4,0 Gew.-%4.0% by weight
- EthanolEthanol
- 2,0 Gew.-%2.0% by weight
-
Tri-Natrium-Citrat
Citronensäure zur Einstellung des pH's auf 4,8Tri-sodium citrate
Citric acid to adjust the pH to 4.8 - ad 100,0 Gew.-%ad 100.0% by weight
- Wasserwater
Wäßriges Flüssigwaschmittel M1 mit geringer Schaumneigung:
- 8,0 Gew.-%
- C12-C14-Alkylpolyglucosid, DP=1,4
- 10,0 Gew.-%
- C12-C18-Fettsäuremethylester x 3 EO
- 5,0 Gew.-%
- C12-Alkylbenzolsulfonat
- 5,0 Gew.-%
- Ethanol
- 8,0 Gew.-%
- Glycerin
- 0,5 Gew.-%
- Protease
- 5,0 Gew.-%
- Tri-Natrium-Citrat
- 0,1 Gew.-%
- Farb- und Duftstoffe
- ad 100,0 Gew.-%
- Wasser
- 8.0% by weight
- C 12 -C 14 alkyl polyglucoside, DP = 1.4
- 10.0% by weight
- C 12 -C 18 fatty acid methyl ester x 3 EO
- 5.0% by weight
- C 12 alkyl benzene sulfonate
- 5.0% by weight
- Ethanol
- 8.0% by weight
- Glycerin
- 0.5% by weight
- Protease
- 5.0% by weight
- Tri-sodium citrate
- 0.1% by weight
- Dyes and fragrances
- ad 100.0% by weight
- water
Das Mittel besaß hervorragende Schaumeigenschaften (niedrige Schaumwerte).The agent had excellent foam properties (low foam values).
Wäßriges Flüssigwaschmittel M2 mit geringer Schaumneigung:
- 9,0 Gew.-%
- C12-C14-Alkylpolyglucosid, DP=1,4
- 9,0 Gew.-%
- C12-C18-Fettsäuremethylester x 5 EO
- 6,0 Gew.-%
- Ethanol
- 5,0 Gew.-%
- Glycerin
- 0,5 Gew.-%
- Tri-Natrium-Citrat
- ad 100,0 Gew.-%
- Wasser
- 9.0% by weight
- C 12 -C 14 alkyl polyglucoside, DP = 1.4
- 9.0% by weight
- C 12 -C 18 fatty acid methyl ester x 5 EO
- 6.0% by weight
- Ethanol
- 5.0% by weight
- Glycerin
- 0.5% by weight
- Tri-sodium citrate
- ad 100.0% by weight
- water
- WasserhärteWater hardness
- : 16 °d: 16 ° d
- Dosierungdosage
- : 0,8 g/l: 0.8 g / l
- Temperaturtemperature
- : 60 °C: 60 ° C
- SchaumnotenFoam notes
-
:
0 bedeutet, daß kein Schaum am unteren Rand des Bullauges der Waschmaschine zu sehen ist.
3 bedeutet, daß die Schaumhöhe die Hälfte des Bullauges erreicht hat.
5 bedeutet, daß das gesamte Bullauge mit Schaum bedeckt ist.:
0 means that there is no foam at the bottom of the washing machine's porthole.
3 means that the foam height has reached half of the porthole.
5 means that the entire porthole is covered with foam.
Als Vergleichsbeispiel wurde ein Mittel V getestet, das anstatt des Fettsäuremethylesters einen C13-C15-Alkohol x 5 E0 aufwies.
Claims (8)
- A water-containing detergent or cleaning formulation containing0.1 to 50% by weight and preferably 1 to 20% by weight of at least one alkyl polyglycoside corresponding to formula (I): R1-O-[Z]x (I), where R1 is a linear or branched, saturated or unsaturated alkyl group containing 8 to 18 carbon atoms, Z is a sugar unit, preferably a glucose or xylose unit, and x is an integer of 1 to 10, and0.05 to 50% by weight and preferably 1 to 20% by weight of at least one fatty acid alkyl ester alkoxylate corresponding to formula (II): R2CO2-(AO)y-R3 (II), where R2 is a branched or linear, saturated or unsaturated alkyl group containing 5 to 21 carbon atoms, AO is a C2-4 alkylene oxide unit, y is a number of 1 to 30 and R3 is a linear or branched alkyl group containing 1 to 6 carbon atoms.
- A detergent or cleaning formulation as claimed in claim 1, characterized in that, in the alkyl polyglycoside corresponding to formula I, R1 is an alkyl group containing 8 to 12 carbon atoms and in the fatty acid alkyl ester alkoxylate corresponding to formula II, AO is an ethylene oxide unit and R3 is a methyl group.
- A detergent or cleaning formulation as claimed in claims 1 and 2, characterized in that it contains an anionic surfactant selected from the group consisting of C6-18 alkyl benzene sulfonates, C6-18 alkane sulfonates, C6-18 alkyl sulfates, C6-18 alkyl polglycol ether sulfates, α-olefin sulfonates, C6-18 alkyl polyglycol ether sulfonates, glycerol ether sulfonates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride sulfates, sulfosuccinates, sulfotriglycerides, soaps, amide soaps, C6-18 fatty acid amide ether sulfates, C6-18 alkyl carboxylates, fatty acid isethionates, N-C6-18-acyl sarcosinates, N-C6-18-acyl taurides, C6-18 alkyl oligoglucoside sulfates, C6-18 alkyl phosphates and mixtures thereof in a total quantity of up to 40% by weight, based on the detergent/ cleaning formulation as a whole.
- A detergent or cleaning formulation as claimed in claims 1 to 3, characterized in that it contains another nonionic surfactant selected from the group consisting of C6-18 alkyl polyglycol ethers, sugar esters, C6-18 fatty acid polyglycol ethers, sorbitan fatty acid esters, C6-18 fatty acid partial glycerides and mixtures thereof in a total quantity of up to 30% by weight, based on the detergent/ cleaning formulation as a whole.
- A detergent or cleaning formulation as claimed in claim 3, characterized in that the anionic surfactant is selected from the group of C6-18 alkyl sulfates, C6-18 alkyl polyglycol ether sulfates, soaps and C6-18 alkane sulfonates and mixtures thereof.
- A detergent as claimed in claim 4, characterized in that the nonionic surfactant is selected from the group of C6-18 alkyl polyglycol ethers.
- The use of the detergent or cleaning formulation claimed in any of claims 1 to 6, as a multipurpose cleaner for cleaning hard surfaces, a fatty acid alkyl ester alkoxylate in which y is a number of 5 to 25 and, more particularly, 9 to 18 preferably being used.
- The use of the detergent or cleaning formulation claimed in any of claims 1 to 6 as a liquid detergent, a fatty acid alkyl ester alkoxylate in which R2 is a linear or branched, saturated alkyl group containing 12 to 18 carbon atoms and y is a number of 3 to 15, preferably being used.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4326112A DE4326112A1 (en) | 1993-08-04 | 1993-08-04 | Detergent for hard surfaces |
| DE4326112 | 1993-08-04 | ||
| PCT/EP1994/002466 WO1995004803A1 (en) | 1993-08-04 | 1994-07-26 | Low-foaming washing or cleaning agents |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0712436A1 EP0712436A1 (en) | 1996-05-22 |
| EP0712436B1 true EP0712436B1 (en) | 1997-03-19 |
Family
ID=6494403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94925395A Expired - Lifetime EP0712436B1 (en) | 1993-08-04 | 1994-07-26 | Low-foaming washing or cleaning agents |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5753606A (en) |
| EP (1) | EP0712436B1 (en) |
| JP (1) | JPH09501195A (en) |
| DE (2) | DE4326112A1 (en) |
| ES (1) | ES2099628T3 (en) |
| WO (1) | WO1995004803A1 (en) |
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| AU6306594A (en) * | 1994-05-12 | 1995-11-23 | R & C Products Pty Limited | Liquid dishwashing composition |
| DE19502454A1 (en) * | 1995-01-27 | 1996-08-01 | Henkel Kgaa | Liquid detergent |
| GB9606913D0 (en) | 1996-04-02 | 1996-06-05 | Unilever Plc | Surfactant blends processes for preparing them and particulate detergent compositions containing them |
| WO1999064659A1 (en) * | 1998-06-10 | 1999-12-16 | Cognis Corporation | Alkyl polyglycosides and alkyl sulfates as penetrants in mercerizing baths |
| DE19830267A1 (en) * | 1998-07-07 | 2000-01-13 | Henkel Kgaa | Hand dishwashing liquid |
| DE19843384A1 (en) | 1998-09-22 | 2000-03-23 | Cognis Deutschland Gmbh | Reducing viscosity of aqueous surfactant systems using alkoxylated carboxylic acid esters preferably obtained in presence of calcined hydrotalcite |
| DE19851453A1 (en) | 1998-11-09 | 2000-05-11 | Cognis Deutschland Gmbh | Rinse aid for automatic dishwashing |
| US6648983B1 (en) * | 1998-11-10 | 2003-11-18 | The Procter & Gamble Company | Process of cleaning enamel surfaces |
| DE19853110A1 (en) * | 1998-11-18 | 2000-05-25 | Cognis Deutschland Gmbh | Gel-shaped detergent for flush toilets |
| DE19856727A1 (en) | 1998-12-09 | 2000-06-15 | Cognis Deutschland Gmbh | All-purpose cleaner |
| DE19910704B4 (en) * | 1999-03-10 | 2006-04-20 | Cognis Ip Management Gmbh | Cosmetic preparations and their use |
| EP1175473B1 (en) * | 1999-04-30 | 2005-10-12 | Colgate-Palmolive Company | Liquid cleaning compositions containing a methyl ethoxylated ester |
| DE19927075C1 (en) * | 1999-06-15 | 2001-07-19 | Cognis Deutschland Gmbh | Process for the permanent deformation of keratin fibers and the use of alkoxylated carboxylic acid esters and partial glycerides for the production of corrugating and fixing agents |
| DE19937294C2 (en) * | 1999-08-06 | 2003-04-10 | Cognis Deutschland Gmbh | Mouth and dentifrices and use of alkoxylated carboxylic acid esters |
| US6432395B1 (en) | 1999-11-04 | 2002-08-13 | Cogent Environmental Solutions Ltd. | Cleaning composition containing naturally-derived components |
| US6384010B1 (en) | 2000-06-15 | 2002-05-07 | S.C. Johnson & Son, Inc. | All purpose cleaner with low organic solvent content |
| US20020107166A1 (en) * | 2000-08-23 | 2002-08-08 | Morris Timothy C. | Liquid detergent compositions |
| DE10114172A1 (en) * | 2001-03-23 | 2002-09-26 | Cognis Deutschland Gmbh | New polyethylene glycol hydroxy mixed ethers, used in laundry, dish-washing and other detergents, has linear or branched alkyl and/or alkenyl group, hydroxyalkyl and/or hydroxyalkenyl group and ethylene oxide units |
| FR2831539B1 (en) * | 2001-10-25 | 2005-02-11 | Seppic Sa | USE OF ALKYLPOLYGLYCOSIDES AS EMULSIFYING AGENTS FOR THE PREPARATION OF OIL-IN-WATER EMULSION CONTAINING MINERAL FILLERS OR PIGMENTS, AND OIL-IN-WATER EMULSIONS CONTAINING SUCH ALKYLPOLYGLYCOSIDES |
| US6849751B2 (en) * | 2001-12-20 | 2005-02-01 | The Procter & Gamble Company | Alkyl-capped alkoxylated esters and compositions comprising same |
| CA2453192A1 (en) * | 2003-06-26 | 2004-12-26 | John G. Lenhart | Cleaning formulations and methods for manufacturing the same |
| DE10357389B4 (en) * | 2003-12-07 | 2005-12-15 | Benda, Jürgen Michael | Process for cleaning soapstone |
| US7205268B2 (en) | 2005-02-04 | 2007-04-17 | Unilever Home & Personal Care Usa Division Of Conopco, Inc. | Low-foaming liquid laundry detergent |
| US20060223736A1 (en) * | 2005-03-30 | 2006-10-05 | R. Lewis Technologies, Inc. | Dye and scent pouches and methods of making the same |
| US7291582B2 (en) * | 2005-09-20 | 2007-11-06 | Conopco, Inc., D/B/A Unilever | Liquid laundry detergent with an alkoxylated ester surfactant |
| ATE486921T1 (en) * | 2006-06-08 | 2010-11-15 | Unilever Nv | LIQUID DETERGENT WITH ESTER ALKOXYLATE AS SURFACTANT AND UREA |
| WO2009052088A2 (en) * | 2007-10-16 | 2009-04-23 | Ansul Incorporated | Fluoroalkenyl poly [1,6]glycosides |
| JP5244382B2 (en) * | 2007-12-28 | 2013-07-24 | ライオン株式会社 | Liquid detergent composition |
| JP5331412B2 (en) * | 2007-12-28 | 2013-10-30 | ライオン株式会社 | Liquid detergent composition |
| DE102009034544A1 (en) * | 2009-07-23 | 2011-01-27 | Cognis Ip Management Gmbh | surfactant mixture |
| AU2011323838B2 (en) | 2010-10-25 | 2016-06-02 | Stepan Company | Alkoxylated fatty esters and derivatives from natural oil metathesis |
| MY165143A (en) | 2011-10-03 | 2018-02-28 | Lion Corp | Detergent and liquid detergent for textile products |
| DE102012221021A1 (en) * | 2012-11-19 | 2014-05-22 | Henkel Ag & Co. Kgaa | Detergents and cleaning agents with alkyl polypentosides |
| JP2017517611A (en) | 2014-06-30 | 2017-06-29 | ザ プロクター アンド ギャンブル カンパニー | Laundry detergent composition |
| WO2016023145A1 (en) | 2014-08-11 | 2016-02-18 | The Procter & Gamble Company | Laundry detergent |
| US20160120387A1 (en) * | 2014-10-29 | 2016-05-05 | The Procter & Gamble Company | Hard surface premoistened wipes, cleaning implements and methods thereof |
| EP3144373B1 (en) * | 2015-09-16 | 2018-12-26 | Kolb Distribution Ltd. | Neutral aqueous cleaning composition |
| US10329522B2 (en) * | 2016-05-19 | 2019-06-25 | Ecolab Usa Inc. | Cleaning compositions for use with calcite-based stone |
| RU2019117744A (en) * | 2016-11-08 | 2020-12-10 | Басф Се | COMPOSITION SUITABLE AS A SURFACE-ACTIVE SUBSTANCE |
| KR102042507B1 (en) * | 2018-07-24 | 2019-11-08 | (주)피스코 | Liquid laundry detergenet composition |
| CA3124906A1 (en) * | 2019-02-25 | 2020-09-03 | Clariant International Ltd | Fatty acid derivatives for improving the effect of agrochemical actives |
| CH716229B1 (en) | 2019-05-26 | 2023-05-15 | Fama Holding Ag | Agents with alkoxylated fatty acid alkyl esters. |
| CN117730137A (en) * | 2021-07-16 | 2024-03-19 | 巴斯夫欧洲公司 | Premix comprising alkyl polyglycoside for preparing liquid detergent formulations |
| WO2024249227A1 (en) * | 2023-06-02 | 2024-12-05 | Dow Global Technologies Llc | Personal care rinse off formulation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0030096B2 (en) * | 1979-12-04 | 1993-07-14 | Imperial Chemical Industries Plc | Detergent composition |
| AU556758B2 (en) * | 1981-07-13 | 1986-11-20 | Procter & Gamble Company, The | Foaming compositions based on alkylpolysaccharide |
| DE3275201D1 (en) * | 1981-07-13 | 1987-02-26 | Procter & Gamble | Foaming surfactant compositions |
| EP0105556A1 (en) * | 1982-09-30 | 1984-04-18 | THE PROCTER & GAMBLE COMPANY | Liquid detergent composition containing nonionic and ionic surfactants |
| WO1988009369A1 (en) * | 1987-05-18 | 1988-12-01 | Staley Continental, Inc. | Low foaming detergent composition |
| DE3723826A1 (en) * | 1987-07-18 | 1989-01-26 | Henkel Kgaa | METHOD FOR PRODUCING ALKYL GLYCOSIDES |
| DE3833780A1 (en) * | 1988-10-05 | 1990-04-12 | Henkel Kgaa | METHOD FOR THE DIRECT PRODUCTION OF ALKYL GLYCOSIDES |
| DE3914131A1 (en) * | 1989-04-28 | 1990-10-31 | Henkel Kgaa | USE OF CALCINATED HYDROTALCITES AS CATALYSTS FOR ETHOXYLATION OR PROPOXYLATION OF FATTY ACID ESTERS |
| JPH078991B2 (en) * | 1989-07-18 | 1995-02-01 | 花王株式会社 | Neutral liquid detergent composition |
| DE4009533A1 (en) * | 1990-03-24 | 1991-09-26 | Henkel Kgaa | LOW-EFFICIENT NON-ionic surfactant mix |
| DE4010606A1 (en) * | 1990-04-02 | 1991-10-10 | Henkel Kgaa | USE OF HYDROPHOBIC HYDROTALCITES AS CATALYSTS FOR THE ETHOXYLATION OR PROPOXYLATION |
| DE4114141A1 (en) * | 1991-04-30 | 1992-11-05 | Huels Chemische Werke Ag | AQUEOUS SURFACTANT PREPARATIONS WITH INCREASED VISCOSITY |
| DE4117689A1 (en) * | 1991-05-29 | 1992-12-03 | Henkel Kgaa | LIQUID, POURABLE AND PUMPABLE SURFACTANT PREPARATION |
| DE4227046A1 (en) * | 1991-08-15 | 1993-02-18 | Lion Corp | Detergent compsn. contg. fatty acid ester of polyoxyalkylene alkyl ether - prepd. from fatty acid alkyl ester and alkylene oxide in presence of magnesia carrying metal ions as catalyst |
-
1993
- 1993-08-04 DE DE4326112A patent/DE4326112A1/en not_active Withdrawn
-
1994
- 1994-07-26 ES ES94925395T patent/ES2099628T3/en not_active Expired - Lifetime
- 1994-07-26 JP JP7506184A patent/JPH09501195A/en active Pending
- 1994-07-26 US US08/596,086 patent/US5753606A/en not_active Expired - Fee Related
- 1994-07-26 EP EP94925395A patent/EP0712436B1/en not_active Expired - Lifetime
- 1994-07-26 WO PCT/EP1994/002466 patent/WO1995004803A1/en not_active Ceased
- 1994-07-26 DE DE59402172T patent/DE59402172D1/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US5753606A (en) | 1998-05-19 |
| JPH09501195A (en) | 1997-02-04 |
| WO1995004803A1 (en) | 1995-02-16 |
| DE4326112A1 (en) | 1995-02-09 |
| ES2099628T3 (en) | 1997-05-16 |
| EP0712436A1 (en) | 1996-05-22 |
| DE59402172D1 (en) | 1997-04-24 |
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