EP0054894A1 - Surfactant-containing mixture for cleaning hard surfaces - Google Patents
Surfactant-containing mixture for cleaning hard surfaces Download PDFInfo
- Publication number
- EP0054894A1 EP0054894A1 EP81110471A EP81110471A EP0054894A1 EP 0054894 A1 EP0054894 A1 EP 0054894A1 EP 81110471 A EP81110471 A EP 81110471A EP 81110471 A EP81110471 A EP 81110471A EP 0054894 A1 EP0054894 A1 EP 0054894A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- surfactant
- weight
- cleaning
- alkyl radical
- mixture
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 79
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 45
- 238000004140 cleaning Methods 0.000 title claims abstract description 44
- 150000001298 alcohols Chemical class 0.000 claims abstract description 20
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 14
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 9
- -1 alkyl radical Chemical class 0.000 claims description 38
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 abstract description 16
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 6
- 229920000151 polyglycol Polymers 0.000 abstract description 6
- 239000010695 polyglycol Substances 0.000 abstract description 6
- 239000002518 antifoaming agent Substances 0.000 abstract description 5
- 239000011521 glass Substances 0.000 abstract description 5
- 150000003856 quaternary ammonium compounds Chemical class 0.000 abstract description 5
- 238000004851 dishwashing Methods 0.000 abstract description 4
- 229910052573 porcelain Inorganic materials 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 2
- 229920001515 polyalkylene glycol Polymers 0.000 abstract 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 abstract 1
- 150000001983 dialkylethers Chemical class 0.000 abstract 1
- 239000000306 component Substances 0.000 description 45
- 239000006260 foam Substances 0.000 description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 11
- 238000009472 formulation Methods 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000003599 detergent Substances 0.000 description 7
- 238000005187 foaming Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 235000019832 sodium triphosphate Nutrition 0.000 description 6
- 235000013405 beer Nutrition 0.000 description 5
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- 239000001226 triphosphate Substances 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 235000019795 sodium metasilicate Nutrition 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000002091 cationic group Chemical group 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
- 239000012459 cleaning agent Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000000645 desinfectant Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- IIVWHGMLFGNMOW-UHFFFAOYSA-N 2-methylpropane Chemical compound C[C](C)C IIVWHGMLFGNMOW-UHFFFAOYSA-N 0.000 description 1
- FNVUFDLOEJWHQE-UHFFFAOYSA-N 7-methyloctanamide Chemical compound CC(C)CCCCCC(N)=O FNVUFDLOEJWHQE-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Natural products CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- JMHWNJGXUIJPKG-UHFFFAOYSA-N CC(=O)O[SiH](CC=C)OC(C)=O Chemical compound CC(=O)O[SiH](CC=C)OC(C)=O JMHWNJGXUIJPKG-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
- FARBQUXLIQOIDY-UHFFFAOYSA-M Dioctyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(C)CCCCCCCC FARBQUXLIQOIDY-UHFFFAOYSA-M 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 102000014171 Milk Proteins Human genes 0.000 description 1
- 108010011756 Milk Proteins Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 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
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 235000014510 cooky Nutrition 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 235000015122 lemonade Nutrition 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical class NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000011182 sodium carbonates Nutrition 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 235000020023 weizenbier Nutrition 0.000 description 1
- 235000020017 wheat beer Nutrition 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
- C11D3/16—Organic compounds
- C11D3/24—Organic compounds containing halogen
- C11D3/245—Organic compounds containing halogen containing fluorine
-
- 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
- C11D1/835—Mixtures of non-ionic with cationic 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
- C11D1/835—Mixtures of non-ionic with cationic compounds
- C11D1/8355—Mixtures of non-ionic with cationic compounds containing a combination of non-ionic compounds differently alcoxylised or with different alkylated chains
-
- 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
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium 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
- C11D1/72—Ethers of polyoxyalkylene glycols
- C11D1/721—End blocked 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
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
Definitions
- the invention relates to a surfactant-containing mixture for the mechanical cleaning of hard surfaces, in particular bottles and dishes, in the alkaline to highly alkaline range of the cleaning liquor.
- the system must also have as little foam as possible be foam-free, as excessive foam formation can lead to malfunctions in the operating behavior of the system, for example if the dirt that accumulates in the foam layer cannot be removed sufficiently. Additional tendencies towards foam formation are caused by the impurities carried in by the items to be cleaned, especially by protein-containing residues on the items to be cleaned. In the case of bottle cleaning, this also applies in particular to the labels to be removed, which are introduced into the cleaning liquor through the glue residues and residues of printing inks, including the surfactant auxiliaries contained in the latter.
- non-ionic surfactants with a low-foaming characteristic as cleaning agents for hard surfaces in alkaline baths.
- These are, in particular, addition products of ethylene oxide and / or propylene oxide with amines, longer-chain fatty alcohols or alkylphenols, polyglycol ether formals or acetals or block copolymers of ethylene and propylene oxide.
- Such surfactant systems can be adjusted, in particular by suitable variation of the ethylene oxide and propylene oxide proportions, to the lowest possible foam tendency and increased cleaning action, with an excess of propylene oxide favoring the former property and an excess weight of ethylene oxide promoting the latter property.
- the object was therefore to improve the dirt-holding capacity of such mixtures without having to accept the disadvantage of substantivity, a minimal tendency to foam formation to be achieved even with extremely high liquor movements and / or extremely foam-promoting soiling.
- the non-ionic component A may be 3) a P olyalkylenglykoldialkylether of formula be, which contains ethylene oxide and optionally propylene oxide units, which can be arranged randomly or in blocks.
- R 1 is an alkyl radical with 6 to 22 carbon atoms, preferably with 8 to 18 carbon atoms
- R 3 is an alkyl radical with 1 to 4 carbon atoms, preferably the tert-butyl radical
- c is a statistical mean in the range from 5 to 20, preferably from 6 to 14
- d has a statistical mean in the range from 0 to 3, preferably 0.
- non-ionic surfactants can also be present as mixtures within groups A 1 ), A 2 ) or A 3 ), or else between groups A 1 ), A 2 ) and / or A 3 ).
- the non-ionic surfactants of group A 1 ) are preferred.
- the surfactant mixture contains a quaternary ammonium compound B of the formula as a cationic component in which R 4 and R 5 , identical or different, are an alkyl radical having 1 to 12 C atoms, preferably having 4 to 8 C atoms, in particular having 4 to 6 C atoms, R 6 is an alkyl radical having 1 to 8 C atoms Atoms, preferably 1 to 6 carbon atoms, and R 7 is an alkyl radical with 1 to 4 carbon atoms or a benzyl radical.
- A is an anion, preferably a chloride or bromide anion or one of the formula CH 3 OSO 3 - .
- Rf is a CF 3 - or (CF 3 ) 2 -CF radical
- R 8 is a lower alkyl radical
- R 9 is hydrogen or a lower alkyl radical (with a lower alkyl radical here being one with 1 to 3 carbon atoms, preferably a methyl - or ethyl radical should be understood)
- e is an integer from 5 to
- f is an integer from 0 to 4
- the composition of the surfactant mixtures is essential for the advantageous properties.
- the ratio of components A: B in the mixture A + B should be in the range from 20:80 to 95: 5% by weight, preferably 30:70 to 70: 30% by weight.
- the fluorinated alcohol C) is additionally present as an anti-foaming agent in an amount of 0.001 to 20% by weight, preferably 0.1 to 15% by weight, in the mixture according to the invention.
- fluorinated alcohols are solid, wax-like substances at room temperature. They can be added in bulk to the mixture of components A + B or its individual components, expediently with gentle heating and stirring.
- these fluorinated alcohols are advantageously introduced in a mixture with a solubilizer in which they have been predissolved. This is especially true when very small amounts of the fluorinated alcohol are to be used.
- a suitable solubilizer must be completely or at least largely homogeneously miscible with the surfactant mixture A + B or its individual components.
- the fluorinated alcohol C) should be largely or entirely soluble in this solubilizer be.
- An effective amount of such a solubilizer is preferably 1 to 1000 parts by weight per 1 part by weight of the fluorinated alcohol; however, this effective amount should not exceed 20% by weight of the total weight of components A + B.
- solubilizers are aliphatic ketones, such as dimethyl and diethyl ketone, carboxylic acid esters of aliphatic alcohols and diols, such as ethyl acetate, isobutyl acetate, ethylene glycol acetate, 2-ethylhexyl-2-ethylhexanoic acid ester, acid amides of longer-chain carboxylic acids, such as N- (2-ethyl) Isononanoic acid amide, polypropylene glycols with molecular weights> 600 and mixed polyglycols from units of ethylene and propylene oxide, ethylene and propylene glycol monoethers and the corresponding polyglycol ethers, such as methyl, ethyl and butyl monoethers of di-, tri- and tetraethylene glycol. Alkanols with 1 to 9 carbon atoms in a straight or branched chain should preferably be mentioned. As far as miscty
- the surfactant-containing mixtures according to the invention can be used as a mixture of components A + B + C, optionally including the solubilizer in undiluted, liquid form. However, they can also be used in the form of aqueous concentrates, for example for better meterability, if appropriate also with the addition of an organic solvent which is not a solubilizer in the abovementioned sense.
- components A and B can also first be added individually or together to the aqueous cleaning liquor and the fluorinated alcohol C can be replenished, a solubilizer being present here got to.
- component C can also be introduced premixed with one of the two components A or B, with the other being replenished.
- the application concentration is advantageously 0.05 to 10 g of the surfactant mixture A + B (without inclusion of C) per liter of cleaning liquor, preferably 0.1 to 2 g per liter.
- Such application concentrations are non-critical statements, since the amount depends to a certain extent on the type of surface to be cleaned and on the type and extent of the contaminants.
- further additives and auxiliaries can be added to the surfactant mixtures according to the invention in the production of commercially available formulations.
- these include dyes, fragrances, corrosion inhibitors and disinfectants.
- the known builders which are optionally also complexing agents, should also be mentioned here.
- the condensed phosphates such as tripolyphosphates and in particular pentasodium triphosphate, come into consideration.
- complex-forming aminopolycarboxylic acids and their salts such as, in particular, alkali metal salts of nitrilotriacetic acid and ethylenediaminetetraacetic acid, and also also complex-forming hydroxycarboxylic acids and polymeric carboxylic acids, such as citric acid, tartaric acid and the like.
- Another class of complex-forming odorants are polyphosphonic acid salts, such as, for example, the alkali salts of aminophosphonic acid.
- builders, such as silicates, for example sodium metasilicate, carbonates, bicarbonates, borates and citrates can also be added. With the aid of such additives, the mixtures according to the invention can optionally be converted into powder form and can also be used in this form.
- the surfactant-containing mixtures according to the invention are suitable for the mechanical cleaning of hard surfaces in alkaline liquors. This applies to cleaning in household dishwashers and so-called commercial cleaning systems.
- the mixtures are particularly suitable for industrial cleaning systems for hard surfaces, for example crockery and bottle washing systems, which operate under high mechanical liquor movements in continuous operation and in highly alkaline liquors at pH values of ⁇ 10, preferably 2 12.
- the necessary alkaline additives preferably sodium or potassium hydroxide for the highly alkaline pH range of the liquor, can be dissolved in the aqueous cleaning liquor before the surfactant-containing mixture according to the invention is introduced. However, they can also be added directly to the mixture and metered together with it.
- the alkaline agent is expediently added in the form of powder, flakes or cookies.
- the mixtures according to the invention have an extremely low tendency towards foaming which is indispensable for industrial cleaning systems. It is essential that the fluorinated alcohol C used as an anti-foaming agent is absolutely stable in the highly alkaline range. By adding it it is achieved that even with extremely high mechanical liquor movements, such as occur in the bottle cleaning systems of breweries, practically no foaming takes place. Even with heavily to extremely foam-promoting soiling, such as protein, milk, beer, lemonade and glue and surfactant components from labels, the foaming tendency is reduced to a minimum.
- the surfactant-containing mixtures have this extremely low tendency to foam formation not only at the working temperatures of such cleaning systems, that is above about 40 ° C, but also at low temperatures, so that when refilled with cold water and heating there is no formation of disruptive foam, which then leads to foam or can lead to system circulation problems.
- the surfactant mixtures according to the invention as cleaning agents for the mechanical cleaning of hard surfaces, in particular with regard to the high demands placed on industrial cleaning systems, also have the following significant advantages: the mixtures are not only resistant to alkali, but also together with alkali storage stable for long periods.
- the excellent dirt absorption capacity allows long service lives in the system until it is refilled without impairing the cleaning effect.
- Good wetting capacity and drainage behavior enable dirt to be removed quickly and thus a high throughput of items to be cleaned. The freedom from stains and streaks as well as high gloss of the cleaned goods is also guaranteed.
- the surfactant components are mixed together and then the fluorinated alcohol is stirred in at 30 to 40 ° C.
- the framework and auxiliary materials are placed in a mixing drum, where they are mixed well with the surfactant mixture.
- Self foam at 25 ° C (according to DIN standard 53 902): 10 ml self foam at 65 ° C (according to DIN standard 53 902): 0 ml drainage behavior after rinsing with water: no drips.
- the components of the surfactant-containing mixture are mixed and then intimately mixed with the framework and auxiliary substances that have already been mixed to form the powder.
- Own foam at 25 ° C (according to DIN standard 53 902): 20 ml own foam at 65 ° C (according to DIN standard 53 902): 0 ml foam at 65 ° C (according to DIN standard 53 902) with a load of 10 wt .-% beer: 0 ml maximum protein load (up to 30 ml foam): 7.2 g / 1 drainage behavior after rinsing with water: no droplets.
- the surfactant-containing formulation which has been premixed with one another in the order of the components is incorporated into this mixture.
- Own foam at 25 ° C (according to DIN standard 53 902): 10 ml own foam at 65 ° C (according to DIN standard 53 902): 0 ml Maximum protein load (up to 30 ml foam): 17.5 g / l drainage behavior after Rinse with water: no drops.
- Liquid bottle cleaner
- Demineralized water is initially introduced and then phosphoric acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are stirred in. Now the premixed surfactant-containing mixture is homogenized.
- Own foam at 25 ° C (according to DIN standard 53 902): 10 ml own foam at 65 ° C (according to DIN standard 53 902): 0 ml foam at 65 ° C (according to DIN standard 53 902) with a load of 10 wt .-% beer: 0 ml.
- Own foam at 25 ° C (according to DIN standard 53 902): 10 ml own foam at 65 ° C (according to DIN standard 53 902): 0 ml Maximum protein load (up to 30 ml foam): 9.0 g / l Drainage behavior after Rinse with water: no drops.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Es wird ein tensidhaltiges Gemisch beschrieben, das besonders für die maschinelle Reinigung von harten Oberflächen, insbesondere von Glas, Porzellan und dergleichen, im alkalischen Bereich der Reinigungsflotte geeignet ist. Dieses tensidlhaltige Gemisch besteht aus A) einem nicht-ionischen Tensid, das aus der Gruppe der Ethylenoxid- und Propylenoxid-Einheiten enthaltenden Polyalkylenglykolmonoalkylether, der Ethylenoxid- und gegebenenfalls Propylenoxid-Einheiten enthaltenden Polyglykoletherformale oder der Ethylenoxid- und gegebenenfalls Propylenoxid-Einheiten enthaltenden Polyalkylenglykoldialkylether ausgewählt ist, B) einer ausgewählten quaternären Ammoniumverbindung als kationischem Tensid, sowie C) einem fluorierten Alkohol als Antischaummittel. Diese Gemisch eignen sich in besonderer Weise für industrielle Geschirr- und Flaschenspülanlagen, die unter hohen mechanischen Flottenbewegungen im hochalkalischen pH-Bereich betrieben werden.A surfactant-containing mixture is described which is particularly suitable for the mechanical cleaning of hard surfaces, in particular glass, porcelain and the like, in the alkaline range of the cleaning liquor. This surfactant-containing mixture consists of A) a nonionic surfactant which is selected from the group consisting of the polyalkylene glycol monoalkyl ethers containing ethylene oxide and propylene oxide units, the polyglycol ether formals containing ethylene oxide and optionally propylene oxide units or the polyalkylene glycol dialkyl ether containing ethylene oxide and optionally propylene oxide units , B) a selected quaternary ammonium compound as a cationic surfactant, and C) a fluorinated alcohol as an anti-foaming agent. These mixtures are particularly suitable for industrial dishwashing and bottle washing systems that are operated with high mechanical liquor movements in the highly alkaline pH range.
Description
Die Erfindung betrifft ein tensidhaltiges Gemisch für die maschinelle Reinigung von harten Oberflächen, insbesondere von Flaschen und Geschirr im alkalischen bis hochalkalischen Bereich der Reinigungsflotte.The invention relates to a surfactant-containing mixture for the mechanical cleaning of hard surfaces, in particular bottles and dishes, in the alkaline to highly alkaline range of the cleaning liquor.
Für die Reinigung von Flaschen und sonstigen Gegenständen mit harten Oberflächen, wie Geschirr aus Porzellan, Keramik, Glas oder Kunststoff, ferner von anderen Glas- oder auch Metallgegenständen werden heute weitgehend maschinelle Reinigungsverfahren angewandt. Während bei Haushaltsspülmaschinen nur relativ geringe Flottenbewegungen entsprechend dem geringen Durchsatz an zu reinigendem Gut erforderlich sind, arbeiten gewerbliche und insbesondere industrielle Reinigungsanlagen bei großem Durchsatz mit sehr hohen Flottenbewegungen und Sprühintensitäten. Wegen der höheren Schmutzbelastungen werden dabei andie Qualität der eingesetzten tensidhaltigen Reinigungsmittel hinsichtlich ihres Reinigungs-, Schmutzaufnahme- und Netzvermögens hohe Anforderungen gestellt. Um die erforderliche schnelle Ablösung und Emulgierung der anhaftenden Verunreinigungen zu gewährleisten, wird in solchen gewerblichen und insbesondere in industriellen Reinigungsanlagen üblicherweise in hochalkalischen Flotten gearbeitet. Wegen der hohen mechanischen Flottenbewegungen muß das System auch möglichst schaumarm beziehungsweise schaumfrei sein, da übermäßige Schaumbildung zu Störungen im Betriebsverhalten der Anlage führen kann, beispielsweise, wenn der in der Schaumschicht sich ansammelnde Schmutz nicht ausreichend ausgetragen werden kann. Zusätzliche Tendenzen zur Schaumbildung werden durch die vom Reinigungsgut in die Flotte eingeschleppten Verunreinigungen, besonders durch proteinhaltige Reste am Reinigungsgut, hervorgerufen. Im Falle der Flaschenreinigung gilt dies besonders auch für die zu entfernenden Etiketten, die durch die Leimreste und Reste von Druckfarben einschließlich der in letzteren enthaltenen Tensid-Hilfsmittel in die Reinigungsflotte eingebracht werden.For cleaning bottles and other objects with hard surfaces, such as dishes made of porcelain, ceramics, glass or plastic, as well as other glass or metal objects, mechanical cleaning processes are largely used today. While only relatively small movements of the liquor are required in accordance with the low throughput of items to be cleaned in household dishwashers, commercial and in particular industrial cleaning systems work with high throughput with very high liquor movements and spray intensities. Because of the higher contamination levels, high demands are placed on the quality of the surfactant-containing cleaning agents used in terms of their cleaning, dirt absorption and wetting properties. In order to ensure the necessary rapid detachment and emulsification of the adhering impurities, work is usually carried out in highly alkaline liquors in such commercial and in particular in industrial cleaning plants. Because of the high mechanical movements of the liquor, the system must also have as little foam as possible be foam-free, as excessive foam formation can lead to malfunctions in the operating behavior of the system, for example if the dirt that accumulates in the foam layer cannot be removed sufficiently. Additional tendencies towards foam formation are caused by the impurities carried in by the items to be cleaned, especially by protein-containing residues on the items to be cleaned. In the case of bottle cleaning, this also applies in particular to the labels to be removed, which are introduced into the cleaning liquor through the glue residues and residues of printing inks, including the surfactant auxiliaries contained in the latter.
Es ist bekannt, nicht-ionische Tenside mit schwach schäumender Charakterisitk als Reinigungsmittel für harte Oberflächen in alkalischen Bädern einzusetzen. Dies sind insbesondere Anlagerungsprodukte von Ethylenoxid und/oder Propylenoxid an Amine, längerkettige Fettalkohole oder Alkylphenole, Polyglykoletherformale oder -acetale oder Blockcopolymerisate des Ethylen-und Propylenoxids. Derartige Tensidsysteme können insbesondere durch geeignete Variation der Ethylenoxid- und Propylenoxid-Anteile auf möglichst geringe Schaumneigung und erhöhte Reinigungswirkung eingestellt werden, wobei ein übergewicht des Propylenoxidsdie erstere Eigenschaft, ein übergewicht des Ethylenoxids die letztere-Eigenschaft begünstigt. Jedoch stellt eine solche Einstellung dieser Eigenschaften immer einen Kompromiß dar, und es wäre wünschenswert, mehr von der einen Eigenschaft zu erhalten, ohne auf Anteile der anderen verzichten zu müssen. Bei maschinellen Reinigungsprozessen für Flaschen, Geschirr und dergleichen im industriellen Bereich, die unter hoher mechanischer Bewegung ablaufen, ist die Schaumarmut der genannten Tensidsysteme zwar sehr erwünscht, jedoch die Schmutzablösung in der zur Verfügung stehenden geringen Zeit beim Durchsatz des Reinigungsgutes und auch das Schmutzaufnahmevermögen häufig nicht ausreichend und verbesserungsbedürftig.It is known to use non-ionic surfactants with a low-foaming characteristic as cleaning agents for hard surfaces in alkaline baths. These are, in particular, addition products of ethylene oxide and / or propylene oxide with amines, longer-chain fatty alcohols or alkylphenols, polyglycol ether formals or acetals or block copolymers of ethylene and propylene oxide. Such surfactant systems can be adjusted, in particular by suitable variation of the ethylene oxide and propylene oxide proportions, to the lowest possible foam tendency and increased cleaning action, with an excess of propylene oxide favoring the former property and an excess weight of ethylene oxide promoting the latter property. However, such an adjustment of these properties is always a compromise, and it would be desirable to get more of one property without sacrificing portions of the other. In mechanical cleaning processes for bottles, dishes and the like in the industrial sector, which take place with high mechanical movement, this is the Low foam of the above-mentioned surfactant systems is very desirable, but the detachment of dirt in the short time available for the throughput of the items to be cleaned and also the dirt absorption capacity are often inadequate and in need of improvement.
Man hat bereits versucht, diesen Nachteil durch bestimmte Mischungen aus den genannten Klassen von nicht-ionischen Tensiden auszugleichen, wie in der DE-AS 27 23 139 beschrieben wird. Solche Mischungen besitzen zwar bei der erhöhten Arbeitstemperatur der Anlage eine vorteilhaft niedrige Schaumneigung, jedoch eine zu hohe Schaumneigung bei tieferen Temperaturen, was beim Befüllen und Aufheizen der Anlage von Nachteil ist. Ein Rückgriff auf anionische Tenside, die das Reinigungs- und Netzvermögen erhöhen würden, ist kaum möglich, da dadurch die Schaumneigung zu stark vergrößert wird. Es ist auch schon versucht worden, kationische Tenside mit langen Alkylketten zum Zwecke der Desinfektion in Flaschenreinigungsmittel einzubeziehen. In der DE-OS 24 49 354 wird dies beschrieben, wobei als kationische Tenside quaternäre Ammoniumsalze, die einen oder zwei langkettige Alkylreste oder Alkylarylreste im Molekül neben kurzkettigen Resten enthalten, eingesetzt werden. Da diese Art kationischer Tenside zu relativ starker Schaumbildung neigt, muß zusätzlich ein Entschäumer hinzugefügt werden, wofür dort Orthophosphorsäuremonoalkylester vorgesehen sind. Gegebenenfalls können nicht-ionische Tenside zusätzlich im Gemisch anwesend sein. Solche Formulierungen unter Einschluß kationischer, zumindest eine lange Alkylkette enthaltender quaternärer Ammoniumverbindungen haben jedoch den entscheidenden Nachteil, daß die genannten Verbindungen substantiv auf das Reinigungsgut aufziehen. Dadurch wird verhindert, daß die Flüssigkeit glatt abläuft, es bilden sich Tropfen, die dann beim Trocknen störende Ränder hinterlassen. Dieser Effekt, der beim Einsatz als Wäschenachbehandlungsmittel für Textilien sehr erwünscht ist, macht den Einsatz der genannten quaternären Ammoniumverbindungen in Geschirr- und Flaschenreinigungsmitteln für alkalische Flotten sehr problematisch. Auch wird, falls die genannten quaternären Ammoniumverbindungen in Abmischung mit nicht-ionischen Tensiden, wie ebenfalls in der DE-OS 24 49 354 und auch in der DE-OS 25 23 588 beschrieben ist, eingesetzt werden, keine nennenswerte Erhöhung des Schmutzaufnahmevermögens der nicht-ionischen Komponente erzielt.Attempts have already been made to compensate for this disadvantage by means of certain mixtures of the classes of nonionic surfactants mentioned, as described in DE-AS 27 23 139. Such mixtures have an advantageously low foam tendency at the elevated working temperature of the system, but an excessive foam tendency at lower temperatures, which is disadvantageous when filling and heating the system. It is hardly possible to use anionic surfactants, which would increase the cleaning and wetting properties, as this increases the tendency to foam too much. Attempts have also been made to include cationic surfactants with long alkyl chains in bottle detergents for disinfection. This is described in DE-OS 24 49 354, the quaternary ammonium salts which contain one or two long-chain alkyl radicals or alkylaryl radicals in the molecule in addition to short-chain radicals being used as cationic surfactants. Since this type of cationic surfactant tends to form relatively strong foams, a defoamer must also be added, for which orthophosphoric acid monoalkyl esters are provided there. If necessary, non-ionic surfactants can also be present in the mixture. Such formulations including cationic quaternary ammonium compounds containing at least one long alkyl chain, however, have the decisive disadvantage that the compounds mentioned absorb substantially onto the items to be cleaned. This prevents the liquid from running off smoothly, drops form, which then leave disruptive edges when drying. This effect, which is very desirable when used as a laundry aftertreatment agent for textiles, makes the use of the quaternary ammonium compounds mentioned in dishwashing detergent and bottle detergent very problematic for alkaline liquors. Also, if the quaternary ammonium compounds mentioned are used in a mixture with non-ionic surfactants, as also described in DE-OS 24 49 354 and also in DE-OS 25 23 588, there is no appreciable increase in the dirt-holding capacity of the non- ionic component.
Es bestand somit die Aufgabe, das Schmutzaufnahmevermögen solcher Gemische zu verbessern, ohne den Nachteil der Substantivität in Kauf nehmen zu müssen, wobei eine minimale Schaumbildungstendenz auch bei extrem hohen Flottenbewegungen und/oder extrem schaumfördernden Verschmutzungen erreicht werden soll.The object was therefore to improve the dirt-holding capacity of such mixtures without having to accept the disadvantage of substantivity, a minimal tendency to foam formation to be achieved even with extremely high liquor movements and / or extremely foam-promoting soiling.
Gemäß der Erfindung wird dies erreicht durch ein tensidhaltiges Gemisch, das dadurch gekennzeichnet ist, daß es besteht aus
- A) 20 bis 95 Gew.-% der Gewichtssumme des Gemisches A + B eines nicht-ionischen Tensids der Formel
- B) 5 bis 80 Gew.-% der Gewichtssunune des Gemisches A + B eines kationischen Tensids der Formel
- C) 0,001 bis 20 Gew.-%, bezogen auf die Gewichtssumme A + B = 100, eines fluorierten Alkohols der Formel
- A) 20 to 95% by weight of the total weight of the mixture A + B of a nonionic surfactant of the formula
- B) 5 to 80 wt .-% of the weight of the mixture A + B of a cationic surfactant of the formula
- C) 0.001 to 20 wt .-%, based on the total weight A + B = 100, of a fluorinated alcohol of the formula
Die Wirksamkeit dieser Mittel für die maschinelle Reinigung von Geschirr, Flaschen und anderen Glasgegehständen oder auch von Metallen in alkalischen Flotten, insbesondere auch in den im industriellen Bereich angewandten hochalkalischen Flotten, beruht auf der überraschenden Erkenntnis, daß durch die Einbeziehung von quaternären Ammoniumverbindungen mit ausschließlich kurzen bis mittleren Ketten im Molekül als kationische Komponente das Schmutzaufnahmevermögen solcher Gemische erheblich verbessert werden kann, wobei diese kationischen Tenside im alkalischen Bereich praktisch nicht substantiv auf das Reinigungsgut aufziehen, und daß ferner gleichzeitig solche Mittel infolge der als Antischaummittel hinzugefügten fluorierten Alkohole eine extrem niedrige Schaumneigung sowohl bei niedrigen als auch bei erhöhten Temperaturen und sowohl bei höchsten mechanischen Belastungen der Flotte als auch bei stark schaumfördernden Verschmutzungen aufweisen.The effectiveness of these agents for the mechanical cleaning of dishes, bottles and other glass objects or even metals in alkaline liquors, especially in the highly alkaline liquors used in the industrial sector, is based on the surprising finding that the inclusion of quaternary ammonium compounds with only short ones to medium chains in the molecule as a cationic component, the dirt-holding capacity of such mixtures can be considerably improved, these cationic surfactants practically not substantively absorbing the items to be cleaned in the alkaline range, and furthermore such agents, owing to the fluorinated alcohols added as anti-foaming agents, also have an extremely low tendency to foam at low as well as at elevated temperatures and both with the highest mechanical loads on the liquor and with strongly foam-promoting soiling.
Die als Bestandteil eingesetzten nicht-ionischen Tenside A) sind bekannt. Es handelt sich dabei um
- A 1) Anlagerungsprodukte von Alkoholen mit 6 bis 22 Kohlenstoffatomen an Ethylenoxid und Propylenoxid, wobei diese Ethylenoxid- und Propylenoxid-Einheiten in Form von Blöcken vorliegen und zumindest ein Teil, vorzugsweise das gesamte Propylenoxid, nach Anlagerung des Ethylenoxids aufkondensiert wird. Derartige Kondensationsprodukte sind insbesondere aus ihrer Anwendung bei Waschmitteln für Textilien bekannt, beispielsweise aus der DE-AS 11 35 122. Sie entsprechen der allgemeinen Formel
- A 2) Polyglykoletherformale der allgemeinen Formel
- A 1 ) adducts of alcohols having 6 to 22 carbon atoms with ethylene oxide and propylene oxide, these ethylene oxide and propylene oxide units being in the form of blocks and at least a part, preferably the entire propylene oxide, is condensed after the ethylene oxide has been added. Such condensation products are known in particular from their use in detergents for textiles, for example from DE-AS 11 35 122. They correspond to the general formula
- A 2) P olyglykoletherformale of the general formula
Schließlich kann die nicht-ionische Komponente A 3) auch ein Polyalkylenglykoldialkylether der Formel
Die vorgenannten nicht-ionischen Tenside können auch als Gemische innerhalb der Gruppen A1), A 2) oder A 3) , oder aber auch zwischen den Gruppen A1), A2) und/oder A3) vorliegen. Bevorzugt sind die nicht-ionischen Tenside der Gruppe A1).The aforementioned non-ionic surfactants can also be present as mixtures within groups A 1 ), A 2 ) or A 3 ), or else between groups A 1 ), A 2 ) and / or A 3 ). The non-ionic surfactants of group A 1 ) are preferred.
Als kationische Komponente enthält das Tensidgemisch eine quaternäre Ammoniumverbindung B der Formel
Die im erfindungsgemäßen tensidhaltigen Gemisch als Antischaummittel eingesetzten fluorierten Alkohole der Formel
Von den im erfindungsgemäßen tensidischen Gemisch eingesetzten fluorierten Alkoholen sind bevorzugt diejenigen zu nennen, bei denen in der obengenannten Formel Rf = CF3, e = 5 bis 13 und g = 0 ist, wobei f die Werte 1 bis 4, insbesondere den Wert 2, annimmt. Von der Herstellung her sind insbesondere diejenigen fluorierten Alkohole bevorzugt, in denen Rf = CF3 ist und e ungeradzahlige Werte, also 5, 7, 9, 11 und 13 annimmt.Of the fluorinated alcohols used in the surfactant mixture according to the invention, preference should be given to those in which Rf = CF 3 , e = 5 to 13 and g = 0 in the above formula, where f is from 1 to 4, in particular from 2, assumes. From the point of view of manufacture, those fluorinated alcohols are particularly preferred in which Rf = CF 3 and e takes on odd values, ie 5, 7, 9, 11 and 13.
Die Zusammensetzung der tensidischen Gemische ist von wesentlicher Bedeutung für die vorteilhaften Eigenschaften. 'Um die erforderliche optimale Kombination von Schmutzaufnahmevermögen, geringstmöglicher Schaumneigung und Nicht-Substantivität zu erzielen, soll das Verhältnis der Komponenten A : B im Gemisch A + B im Bereich von 20 : 80 bis 95 : 5 Gew.-%, vorzugsweise 30 : 70 bis 70 : 30 Gew.-%, liegen. Bezogen auf die Gewichtssumme der Komponenten A + B = 100 ist zusätzlich der fluorierte Alkohol C) als Antischaummittel in einer Menge von 0,001 bis 20 Gew.-%, vorzugsweise von 0,1 bis 15 Gew.-% im erfindungsgemäßen Gemisch anwesend. Solche fluorierten Alkohole stellen bei Raumtemperatur feste, wachsartige Substanzen dar. Sie können in Substanz dem Gemisch der Komponenten A + B oder dessen Einzelkomponenten zugesetzt werden, zweckmäßig unter gelindem Erwärmen und Rühren. Vorteilhafterweise werden diese fluorierten Alkohole aber im Gemisch mit einem Lösungsvermittler eingebracht, in dem sie vorgelöst worden sind. Dies gilt vor allem dann, wenn sehr kleine Mengen des fluorierten Alkohols zum Einsatz gelangen sollen. Ein geeigneter Lösungsvermittler muß mit dem TensidGemisch A + B oder dessen Einzelkomponenten vollständig oder zumindest weitgehend homogen mischbar sein. Ebenso soll der fluorierte Alkohol C) in diesem Lösungsvermittler weitgehend oder gänzlich löslich sein. Eine effektive Menge eines solchen Lösungsvermittlers liegt vorzugsweise bei 1 bis 1000 Gew.-Teilen pro 1 Gew.-Teil des fluorierten Alkohols; diese effektive Menge soll jedoch 20 Gew.-% der Gewichtssumme der Komponenten A + B nicht übersteigen.The composition of the surfactant mixtures is essential for the advantageous properties. In order to achieve the required optimal combination of dirt absorption capacity, the lowest possible foam tendency and non-substantivity, the ratio of components A: B in the mixture A + B should be in the range from 20:80 to 95: 5% by weight, preferably 30:70 to 70: 30% by weight. Based on the total weight of components A + B = 100, the fluorinated alcohol C) is additionally present as an anti-foaming agent in an amount of 0.001 to 20% by weight, preferably 0.1 to 15% by weight, in the mixture according to the invention. Such fluorinated alcohols are solid, wax-like substances at room temperature. They can be added in bulk to the mixture of components A + B or its individual components, expediently with gentle heating and stirring. However, these fluorinated alcohols are advantageously introduced in a mixture with a solubilizer in which they have been predissolved. This is especially true when very small amounts of the fluorinated alcohol are to be used. A suitable solubilizer must be completely or at least largely homogeneously miscible with the surfactant mixture A + B or its individual components. Likewise, the fluorinated alcohol C) should be largely or entirely soluble in this solubilizer be. An effective amount of such a solubilizer is preferably 1 to 1000 parts by weight per 1 part by weight of the fluorinated alcohol; however, this effective amount should not exceed 20% by weight of the total weight of components A + B.
Beispiele für solche Lösungsvermittler sind aliphatische Ketone, wie Dimethyl- und Diethylketon, Carbonsäureester aliphatischer Alkohole und Diole, wie Essisäureethylester, -isobutylester, Ethylenglykolacetat, 2-Ethylhexyl-2-ethylhexansäureester, Säureamide längerkettiger Carbonsäuren, wie beispielsweise N-(2-Ethylhexyl)-iso- nonansäureamid, Polypropylenglykole mit Molgewichten >600 und Mischpolyglykole aus Einheiten von Ethylen-und Propylenoxid, Ethylen- und Propylenglykolmonoether sowie die entsprechenden Polyglykolether, wie Methyl-, Ethyl- und Butylmonoether des Di-, Tri- und Tetraethylenglykols. Vorzugsweise sind Alkanole mit 1 bis 9 C-Atomen in gerader oder verzweigter Kette zu nennen. Soweit miteinander mischbar, sind auch Gemische solcher Lösungsvermittler geeignet.Examples of such solubilizers are aliphatic ketones, such as dimethyl and diethyl ketone, carboxylic acid esters of aliphatic alcohols and diols, such as ethyl acetate, isobutyl acetate, ethylene glycol acetate, 2-ethylhexyl-2-ethylhexanoic acid ester, acid amides of longer-chain carboxylic acids, such as N- (2-ethyl) Isononanoic acid amide, polypropylene glycols with molecular weights> 600 and mixed polyglycols from units of ethylene and propylene oxide, ethylene and propylene glycol monoethers and the corresponding polyglycol ethers, such as methyl, ethyl and butyl monoethers of di-, tri- and tetraethylene glycol. Alkanols with 1 to 9 carbon atoms in a straight or branched chain should preferably be mentioned. As far as miscible with one another, mixtures of such solubilizers are also suitable.
Die erfindungsgemäßen tensidhaltigen Gemische können als Gemisch der Komponenten A + B + C, gegebenenfalls unter Einschluß des Lösungsvermittlers in unverdünnter, flüssiger Form eingesetzt werden. Sie können aber auch, beispielsweise zwecks besserer Dosierbarkeit, in Form wäßriger Konzentrate Verwendung finden, gegebenenfalls auch unter Zusatz eines organischen Lösungsmittels, das kein Lösungsvermittler im obengenannten Sinne ist. Ebenso können auch zunächst die Komponenten A und B einzeln oder zusammen der wäßrigen Reinigungsflotte zugegeben und der fluorierte Alkohol C nachdosiert werden, wobei hier ein Lösungsvermittler zugegen sein muß. Es kann aber auch die Komponente C mit einer der beiden Komponenten A oder B vorgemischt eingebracht werden, wobei die jeweils andere nachdosiert wird.The surfactant-containing mixtures according to the invention can be used as a mixture of components A + B + C, optionally including the solubilizer in undiluted, liquid form. However, they can also be used in the form of aqueous concentrates, for example for better meterability, if appropriate also with the addition of an organic solvent which is not a solubilizer in the abovementioned sense. Likewise, components A and B can also first be added individually or together to the aqueous cleaning liquor and the fluorinated alcohol C can be replenished, a solubilizer being present here got to. However, component C can also be introduced premixed with one of the two components A or B, with the other being replenished.
Die Anwendungskonzentration liegt zweckmäßigerweise bei 0,05 bis 10 g des Tensidgemisches A + B (ohne Einschluß von C) pro Liter Reinigungsflotte, vorzugsweise bei 0,1 bis 2 g pro Liter. Solche Anwendungskonzentrationen sind nicht-kritische Angaben, da sich die Menge in gewissem Ausmaß nach der Art der zu reinigenden Oberfläche und nach Art und Umfang der Verunreinigungen richtet.The application concentration is advantageously 0.05 to 10 g of the surfactant mixture A + B (without inclusion of C) per liter of cleaning liquor, preferably 0.1 to 2 g per liter. Such application concentrations are non-critical statements, since the amount depends to a certain extent on the type of surface to be cleaned and on the type and extent of the contaminants.
Den erfindungsgemäßen tensidischen Gemischen können gegebenenfalls bei der Herstellung handelsüblicher Formulierungen weitere Zusatz- und Hilfsstoffe beigegeben werden. Dies sind beispielsweise Farbstoffe, Duftstoffe, Korrosionsinhibitoren und Desinfektionsmittel. Insbesondere sind hier ferner zu nennen die bekannten Gerüststoffe, die gegebenenfalls gleichzeitig Komplexbildner sind. Hier kommen beispielsweise in Betracht die kondensierten Phosphate, wie Tripolyphosphate und insbesondere das Pentanatriumtriphosphat. Ferner sind dies komplexbildend wirkende Aminopolycarbonsäuren und deren Salze, wie vor allem Alkalisalze der Nitrilotriessigsäure und der Ethylendiamintetraessigsäure, weiterhin auch komplexbildende Hydroxycarbonsäuren und polymere Carbonsäuren, wie Zitronensäure, Weinsäure und dergleichen. Eine weitere Klasse von komplexbildenden Gerüs-tstoffen stellen polyphosphonsaure Salze, wie beispielsweise die Alkalisalze von Aminophosphonsäure dar. Schließlich können auch Gerüststoffe, wie Silikate, beispielsweise Natriummetasilikat, Carbonate, Bicarbonate, Borate und Citrate hinzugefügt werden. Mit Hilfe solcher Zusatzstoffe können die erfindungsgemäßen Gemische gegebenenfalls in Pulverform überführt werden und in dieser Form auch zum Einsatz'gelangen.If appropriate, further additives and auxiliaries can be added to the surfactant mixtures according to the invention in the production of commercially available formulations. These include dyes, fragrances, corrosion inhibitors and disinfectants. In particular, the known builders, which are optionally also complexing agents, should also be mentioned here. Here, for example, the condensed phosphates, such as tripolyphosphates and in particular pentasodium triphosphate, come into consideration. Furthermore, these are complex-forming aminopolycarboxylic acids and their salts, such as, in particular, alkali metal salts of nitrilotriacetic acid and ethylenediaminetetraacetic acid, and also also complex-forming hydroxycarboxylic acids and polymeric carboxylic acids, such as citric acid, tartaric acid and the like. Another class of complex-forming odorants are polyphosphonic acid salts, such as, for example, the alkali salts of aminophosphonic acid. Finally, builders, such as silicates, for example sodium metasilicate, carbonates, bicarbonates, borates and citrates, can also be added. With the aid of such additives, the mixtures according to the invention can optionally be converted into powder form and can also be used in this form.
Die erfindungsgemäßen tensidhaltigen Gemische sind geeignet zur maschinellen Reinigung harter Oberflächen in alkalischen Flotten. Dies gilt für die Reinigung in Haushaltsgeschirrspülmaschinen und sogenannten gewerblichen Reinigungsanlagen. Die Gemische sind aber besonders geeignet für industrielle Reinigungsanlagen für harte Oberflächen, beispielsweise Geschirr- und Flaschenspülanlagen, die unter hohen mechanischen Flottenbeweungen im Dauerbetrieb und in hochalkalischen Flotten bei pH-Werten von ≧ 10, vorzugsweise 2 12, arbeiten.The surfactant-containing mixtures according to the invention are suitable for the mechanical cleaning of hard surfaces in alkaline liquors. This applies to cleaning in household dishwashers and so-called commercial cleaning systems. However, the mixtures are particularly suitable for industrial cleaning systems for hard surfaces, for example crockery and bottle washing systems, which operate under high mechanical liquor movements in continuous operation and in highly alkaline liquors at pH values of ≧ 10, preferably 2 12.
Die erforderlichen alkalischen Zusätze, für den hochalkalischen pH-Bereich der Flotte vorzugsweise Natrium-oder Kaliumhydroxid, können in der wäßrigen Reinigungsflotte vor Einbringen des erfindungsgemäßen tensidhaltigen Gemisches gelöst werden. Sie können aber auch dem Gemisch direkt zugesetzt und zusammen mit diesem dosiert werden. Zweckmäßig erfolgt der Zusatz des alkalischen Mittels in Form von Pulver, Schuppen oder Plätzchen.The necessary alkaline additives, preferably sodium or potassium hydroxide for the highly alkaline pH range of the liquor, can be dissolved in the aqueous cleaning liquor before the surfactant-containing mixture according to the invention is introduced. However, they can also be added directly to the mixture and metered together with it. The alkaline agent is expediently added in the form of powder, flakes or cookies.
Neben der hierfür erforderlichen hohen Alkalistabilität weisen die erfindungsgemäßen Gemische eine für industrielle Reinigungsanlagen unerläßliche, extrem niedrige Schaumbildungstendenz auf. Dabei ist es von wesentlicher Bedeutung, daß auch der als Antischaummittel eingesetzte fluorierte Alkohol C im hochalkalischen Bereich absolut stabil ist. Durch dessen Zusatz wird erreicht, daß auch bei extrem hohen mechanischen Flottenbewegungen, wie sie beispielsweise in den Flaschenreinigungsanlagen von Brauereien auftreten, praktisch keine Schaumbildung stattfindet. Auch bei stark bis extrem schaumfördernden Verschmutzungen, wie beispielsweise bei Eiweiß, Milch, Bier, Limonade sowie Leim und tensidischen Bestandteilen aus Etiketten, wird die Schaumbildungstendenz auf ein Minimum herabgesetzt. Die tensidhaltigen Gemische besitzen diese außerordentlich niedrige Schaumbildungstendenz nicht nur bei den Arbeitstemperaturen solcher Reinigungsanlagen, das heißt oberhalb von etwa 40 °C, sondern auch bei niedrigen Temperaturen, so daß bei Neubefüllung mit kaltem Wasser und Aufheizen keine Bildung von störendem Schaum erfolgt, der dann zum überschäumen oder zu Störungen der Zirkulation der Anlage führen kann.In addition to the high alkali stability required for this, the mixtures according to the invention have an extremely low tendency towards foaming which is indispensable for industrial cleaning systems. It is essential that the fluorinated alcohol C used as an anti-foaming agent is absolutely stable in the highly alkaline range. By adding it it is achieved that even with extremely high mechanical liquor movements, such as occur in the bottle cleaning systems of breweries, practically no foaming takes place. Even with heavily to extremely foam-promoting soiling, such as protein, milk, beer, lemonade and glue and surfactant components from labels, the foaming tendency is reduced to a minimum. The surfactant-containing mixtures have this extremely low tendency to foam formation not only at the working temperatures of such cleaning systems, that is above about 40 ° C, but also at low temperatures, so that when refilled with cold water and heating there is no formation of disruptive foam, which then leads to foam or can lead to system circulation problems.
Neben den bereits genannten Vorteilen weisen die erfindungsgemäßen tensidischen Gemische als Reinigungsmittel für die maschinelle Reinigung harter Oberflächen, insbesondere bezüglich der hohen Anforderungen, die in industriellen Reinigungsanlagen gestellt werden, noch folgende bedeutsamen Vorteile auf: Die Gemische sind nicht nur beständig gegen Alkali, sondern auch zusammen mit Alkali über lange Zeiträume lagerstabil. Das ausgezeichnete Schmutzaufnahmevermögen gestattet lange Standzeiten in der Anlage bis zu deren Neubefüllung ohne Beeinträchtigung der Reinigungswirkung. Gutes Netzvermögen und Ablaufverhalten ermöglicht eine schnelle Schmutzablösung und somit einen hohen Durchsatz an Reinigungsgut. Ebenso ist die Freiheit von Flecken und Schlieren sowie hoher Glanz des gereinigten Gutes gewährleistet. Dies macht die erfindungsgemäßen Gemische beispielsweise außerordentlich geeignet zur Reinigung von Flaschen in Brauereien mit sehr hohem Flaschendurchsatz, wobei wegen der weitgehenden Schaumfreiheit ein problemloser Austrag der abgelösten Etiketten möglich ist und außerdem festgestellt wird, daß bei Befüllung der gereinigten Flaschen mit schäumenden Getränken keine Beeinträchtigung durch Schaumzusammenbruch eintritt.In addition to the advantages already mentioned, the surfactant mixtures according to the invention as cleaning agents for the mechanical cleaning of hard surfaces, in particular with regard to the high demands placed on industrial cleaning systems, also have the following significant advantages: the mixtures are not only resistant to alkali, but also together with alkali storage stable for long periods. The excellent dirt absorption capacity allows long service lives in the system until it is refilled without impairing the cleaning effect. Good wetting capacity and drainage behavior enable dirt to be removed quickly and thus a high throughput of items to be cleaned. The freedom from stains and streaks as well as high gloss of the cleaned goods is also guaranteed. This makes the mixtures according to the invention, for example, extremely suitable for cleaning bottles in breweries with a very high bottle throughput, with the detached labels being able to be easily removed because of the largely lack of foam and, moreover, it is found that when the cleaned bottles are filled with foaming beverages, there is no impairment due to foam breakdown entry.
Unter "Gegenständen mit harter Oberfläche" im Sinne des Anwendungszwecks der erfindungsgemäßen tensidhaltigen Gemische sollen hier vornehmlich verstanden werden alle Arten von Geschirr und Flaschen aus Glas, Porzellan, Keramik und Kunststoff sowie auch andere Gegenstände aus den genannten Materialien oder auch aus Metallen."Objects with a hard surface" in the sense of the intended use of the surfactant-containing mixtures according to the invention are to be understood here primarily as all types of dishes and bottles made of glass, porcelain, ceramic and plastic, as well as other objects made from the materials mentioned or from metals.
Die Erfindung wird durch folgende Beispiele erläutert:
- In den in den folgenden Beispielen eingesetzten Tensidgemischen sind folgende Komponenten enthalten (C7-11* etc. bedeutet Kettenschnitt R' im genannten Bereich):
- Nicht-ionische Tenside der Formel A1): --------------------------------------
- Nicht-ionische Tenside der Formel A2) : --------------------------------------
- Nicht-ionische Tenside der Formel A 3): --------------------------------------
- Kationische Tenside der Formel B): -----------------------------------
- h) Trimethylbenzylammoniumchlorid
- i) Tetrabutylammoniumchlorid
- j) Dibutyldimethylammoniumchlorid
- k) Dihexyldimethylammoniumchlorid
- 1) Dioctyldimethylammoniumchlorid
- Fluorierte Alkohole der Formel C): ----------------------------------
- The surfactant mixtures used in the following examples contain the following components (C 7-11 * etc. means chain cut R 'in the range mentioned):
- Non-ionic surfactants of formula A 1 ): --------------------------------------
- Non-ionic surfactants of formula A 2 ): --------------------------------------
- Non-ionic surfactants of formula A 3 ): --------------------------------------
- Cationic surfactants of formula B): -----------------------------------
- h) trimethylbenzylammonium chloride
- i) Tetrabutylammonium chloride
- j) dibutyldimethylammonium chloride
- k) Dihexyldimethylammonium chloride
- 1) Dioctyldimethylammonium chloride
- Fluorinated alcohols of formula C): ----------------------------------
An den genannten Gemischen werden folgende Eigenschaften gemessen (alle Messungen wurden an Reinigungsflotten durchgeführt, die, mit Ausnahme der pulverförmigen Formulierungen, mit NaOH auf einen pH-Wert von 13 eingestellt sind) :
- a) Schaumverhalten der Tensidmischung:
- ----------------------------------Gemessen wird in wäßriger Lösung nach DIN-Norm 53 902 bei 25 °C und 65 °C.
- ß) Schaumverhalten mit 10 Gew.-% Belastung durch Bier:
- --------------------------------------------------Gemessen wird in einer wäßrigen Reinigungsflotte, die 10 Gew.-% Weizenbier enthält (Export-Weizen der Klosterbrauerei Raitenhaslach-Burghausen) bei 65 °C nach DIN-Norm 53 902.
- a) Foaming behavior of the surfactant mixture:
- ---------------------------------- It is measured in aqueous solution according to DIN standard 53 902 at 25 ° C and 65 ° C.
- ß) Foam behavior with 10% by weight of beer:
- -------------------------------------------------- Measurements are taken in an aqueous cleaning liquor containing 10% by weight of wheat beer (export wheat from the Raitenhaslach-Burghausen monastery brewery) at 65 ° C according to DIN standard 53 902.
Y) Ermittlung der Schmutzaufnahmegrenze:
- ------------------------------------Die Schmutzaufnahmegrenze durch Prüfung des Schaumvermögens bei steigender Schmutzbelastung wird ermittelt, indem die Reinigungsflotte stufenweise mit einem Testschäumer versetzt wird. Als Testschäumer wird ein verquirltes Ei verwendet, das in Portionen von 0,2 g/l Flotte zugegeben wird. Bei der Schaumprüfung nach DIN-Norm 53 902 ist die Schmutzaufnahmegrenze erkennbar an einem plötzlichen Schaumanstieg der Reinigungsflotte. Als Schaumobergrenze wird 30 ml (bei 65 °C) gewählt.
- δ) Prüfung des Ablaufverhaltens in gereinigten Flaschen -----------------------------------------------Saubere 0,5 1-Bierflaschen werden mit 100 ml der Reinigungsflotte gefüllt und nach Verschließen mit einem Korkstopfen fünfmal kräftig geschüttelt. Nach kurzer Wirkzeit (ca. 1 Minute) wird erneut fünfmal der Schüttelvorgang wiederholt und dann die tensidhaltige Reinigungsflotte ausgegossen. Es folgt vier- bis fünfmal hintereinander Nachspülung mit jeweils 100 ml destilliertem Wasser, -bis pH 7 erreicht ist.
- ------------------------------------ The dirt absorption limit by checking the foaming capacity with increasing dirt load is determined by the Cleaning liquor is gradually added with a test foam. A whisked egg is used as the test frother, which is added in portions of 0.2 g / l liquor. In the foam test according to DIN standard 53 902, the dirt absorption limit can be recognized by a sudden foam increase in the cleaning liquor. 30 ml (at 65 ° C) is selected as the upper foam limit.
- δ) Checking the drainage behavior in cleaned bottles ------------------------------------------ ----- Clean 0.5 liter beer bottles are filled with 100 ml of the cleaning liquor and shaken vigorously five times after closing with a cork stopper. After a short period of action (approx. 1 minute), the shaking process is repeated five times and the detergent-containing cleaning liquor is then poured out. This is followed by rinsing four to five times in succession, each with 100 ml of distilled water, until pH 7 is reached.
Visuelle Beobachtung des Ablaufverhaltens an der Flascheninnenwandung:
- Tropfenbildung deutet auf Substantivität an den Flaschenwandungen hin.
- Drop formation indicates substantivity on the bottle walls.
Ermittlung des Schaumvolumens in ml nach DIN-Norm 53 902 bei verschiedenen Zusätzen an fluorierten Alkoholen (Komponenten m bis q) in Gew.-% (bezogen auf die Summe nicht-ionische + kationische Bestandteile A + B = 100 %).Determination of the foam volume in ml according to DIN standard 53 902 with various additions of fluorinated alcohols (components m to q) in% by weight (based on the sum of non-ionic + cationic components A + B = 100%).
Mischung aus 50 Gew.-% Komponente f und 50 Gew.-% Komponente k; 1,5 g/l wäßrige Flotte.
Mischung aus 30 Gew.-% Komponente d und 70 Gew.-% Komponente j; 1,5 g/l wäßrige Flotte.
Mischung aus 60 Gew.-% Komponente e und 40 Gew.-% Komponente 1; 1,5 g/l wäßrige Flotte.
Pulverförmiger Spritzreiniger:
- ------------------------------5 Gew.-% tensidhaltiges Gemisch aus 34 Gew.-Teilen Komponente g, 66 Gew.-Teilen Komponente k und 1 Gew.-Teil Komponente n;
- Gerüst- und Hilfsstoffe: 65 Gew.-% Natriummetasilikat, 20 Gew.-% Natriumhydroxid (pulverisiert), 10 Gew.-% Natriumcarbonat.
- ------------------------------ 5% by weight surfactant-containing mixture of 34 parts by weight component g, 66 parts by weight Parts of component k and 1 part by weight of component n;
- Builders and auxiliaries: 65% by weight sodium metasilicate, 20% by weight sodium hydroxide (powdered), 10% by weight sodium carbonate.
Zunächst werden die Tensid-Komponenten miteinander vermischt und dann der fluorierte Alkohol bei 30 bis 40 °C eingerührt. Die Gerüst- und Hilfsstoffe werden in eine Mischtrommel gegeben und dort mit der Tensid-Mischung gut vermischt.First the surfactant components are mixed together and then the fluorinated alcohol is stirred in at 30 to 40 ° C. The framework and auxiliary materials are placed in a mixing drum, where they are mixed well with the surfactant mixture.
Gemessen wird an einer Reinigungsflotte mit 20 g/1 der Gesamtformulierung (= 1 g/l Tensidgemisch A + B) in vollentsalztem Wasser, pH 12,8.The measurement is carried out on a cleaning liquor with 20 g / 1 of the total formulation (= 1 g / l of surfactant mixture A + B) in demineralized water, pH 12.8.
Eigenschaum bei 25 °C (nach DIN-Norm 53 902): 10 ml Eigenschaum bei 65 °C (nach DIN-Norm 53 902): 0 ml Ablaufverhalten nach dem Klarspülen mit Wasser: keine Tropfenbildung.Self foam at 25 ° C (according to DIN standard 53 902): 10 ml self foam at 65 ° C (according to DIN standard 53 902): 0 ml drainage behavior after rinsing with water: no drips.
--------------------------------10 Gew.-% tensidhaltiges Gemisch aus 78 Gew.-Teilen Komponente a, 22 Gew.-Teilen Komponente i und 11 Gew.-Teilen Komponente q; Gerüst- und Hilfsstoffe: 25 Gew.-% Pentanatriumtriphosphat, 25 Gew.-% Natriummetasilikat, 25 Gew.-% Natriumcarbonat und 15 Gew.-% Natriumhydroxid (pulverisiert).-------------------------------- 10 wt .-% surfactant-containing mixture of 78 parts by weight of component a, 22 wt . Parts of component i and 11 parts by weight of component q; Builders and auxiliaries: 25% by weight of pentasodium triphosphate, 25% by weight of sodium metasilicate, 25% by weight of sodium carbonate and 15% by weight of sodium hydroxide (powdered).
Zunächst werden die Komponenten des tensidhaltigen Gemisches gemischt und anschließend mit den bereits vermengten Gerüst- und Hilfsstoffen innig zum Pulver vermischt.First, the components of the surfactant-containing mixture are mixed and then intimately mixed with the framework and auxiliary substances that have already been mixed to form the powder.
Gemessen wird an einer Reinigungsflotte mit 5 g/l der Gesamtformulierung (= 0,45 g/l Tensidgemisch A + B) in vollentsalztem Wasser, pH 12,4.Measurement is carried out on a cleaning liquor with 5 g / l of the total formulation (= 0.45 g / l of surfactant mixture A + B) in demineralized water, pH 12.4.
Eigenschaum bei 25 °C (nach DIN-Norm 53 902): 20 ml Eigenschaum bei 65 °C (nach DIN-Norm 53 902): 0 ml Schaum bei 65 °C (nach DIN-Norm 53 902) mit Belastung durch 10 Gew.-% Bier: 0 ml Maximale Eiweißbelastung (bis 30 ml Schaum): 7,2 g/1 Ablaufverhalten nach dem Klarspülen mit Wasser: keine Tropfenbildung.Own foam at 25 ° C (according to DIN standard 53 902): 20 ml own foam at 65 ° C (according to DIN standard 53 902): 0 ml foam at 65 ° C (according to DIN standard 53 902) with a load of 10 wt .-% beer: 0 ml maximum protein load (up to 30 ml foam): 7.2 g / 1 drainage behavior after rinsing with water: no droplets.
Pulverförmiger Geschirr-Reiniger:
- ---------------------------------2 Gew.-% tensidhaltiges Gemisch aus 68 Gew.-Teilen Komponente b, 32 Gew.-Teilen Komponente j und 5 Gew.-Teilen Komponente p;
- Gerüst- und Hilfsstoffe: 41,5 Gew.-% Natriummetasilikat, 35 Gew.-% Pentanatriumtriphosphat, 20 Gew.-% Natriumcarbonat und 1,5 Gew.-% Natriumdichlorisocyanurat (als Desinfektionsmittel).
- --------------------------------- 2% by weight surfactant-containing mixture of 68 parts by weight of component b, 32 Parts by weight of component j and 5 parts by weight of component p;
- Builders and auxiliaries: 41.5% by weight sodium metasilicate, 35% by weight pentasodium triphosphate, 20% by weight sodium carbonate and 1.5% by weight sodium dichloroisocyanurate (as disinfectant).
Zuerst werden die pulverförmigen Komponenten vermischt. In dieses Gemisch wird die tensidhaltige Formulierung eingearbeitet, welche zuvor miteinander in der Reihenfolge der Komponenten vorgemischt worden ist.First the powdery components are mixed. The surfactant-containing formulation which has been premixed with one another in the order of the components is incorporated into this mixture.
Gemessen wird an einer Reinigungsflotte mit 50 g/1 Gesamtformulierung (= 0,95 g/1 Tensidgemisch A + B) in vollentsalztem Wasser, pH 12,8.Measurement is carried out on a cleaning liquor with 50 g / 1 total formulation (= 0.95 g / 1 surfactant mixture A + B) in demineralized water, pH 12.8.
Eigenschaum bei 25 °C (nach DIN-Norm 53 902): 10 ml Eigenschaum bei 65 °C (nach DIN-Norm 53 902): 0 ml Maximale Eiweißbelastung (bis 30 ml Schaum): 17,5 g/l Ablaufverhalten nach dem Klarspülen mit Wasser: keine Tropfenbildung.Own foam at 25 ° C (according to DIN standard 53 902): 10 ml own foam at 65 ° C (according to DIN standard 53 902): 0 ml Maximum protein load (up to 30 ml foam): 17.5 g / l drainage behavior after Rinse with water: no drops.
----------------------------20 Gew.-% tensidhaltiges Gemisch aus 76 Gew.-Teilen Komponente c, 24 Gew.-Teilen Komponente k, 8 Gew.-Teilen Polypropylenglykol (MG 3000) und 0,05 Gew.-Teilen Komponente o; Gerüst- und Hilfsstoffe: 35 Gew.-% Phosphorsäure (85 gew.- %ig), 20 Gew.-% 2-Phosphonobutan-1,2,4-tricarbonsäure und 25 Gew.-% vollentsalztes Wasser.---------------------------- 20% by weight surfactant-containing mixture of 76 parts by weight of component c, 24 parts by weight of component k, 8 parts by weight of polypropylene glycol (MW 3000) and 0.05 part by weight of component o; Builders and auxiliaries: 35% by weight phosphoric acid (85% by weight), 20% by weight 2-phosphonobutane-1,2,4-tricarboxylic acid and 25% by weight deionized water.
Bei der Herstellung wird vollentsalztes Wasser vorgelegt und anschließend Phosphorsäure und 2-Phosphono- butan-1,2,4-tricarbonsäure eingerührt. Nun wird die bereits vorgemischte tensidhaltige Mischung einhomogenisiert.Demineralized water is initially introduced and then phosphoric acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are stirred in. Now the premixed surfactant-containing mixture is homogenized.
Gemessen wird an einer Reinigungsflotte mit 10 g/l Gesamtformulierung (= 1,85 g/l Tensidgemisch A + B) in NaOH, pH 13.Measurements are taken on a cleaning liquor with 10 g / l total formulation (= 1.85 g / l surfactant mixture A + B) in NaOH, pH 13.
Eigenschaum bei 25 °C (nach DIN-Norm 53 902): 10 ml Eigenschaum bei 65 °C (nach DIN-Norm 53 902): 0 ml Schaum bei 65 °C (nach DIN-Norm 53 902) mit Belastung durch 10 Gew.-% Bier: 0 ml.Own foam at 25 ° C (according to DIN standard 53 902): 10 ml own foam at 65 ° C (according to DIN standard 53 902): 0 ml foam at 65 ° C (according to DIN standard 53 902) with a load of 10 wt .-% beer: 0 ml.
Ablaufverhalten nach dem Klarspülen mit Wasser: keine Tropfenbildung.Drainage behavior after rinsing with water: no drop formation.
Flüssiger Geschirr-Reiniger:
- ----------------------------5 Gew.-% tensidhaltiges Gemisch aus 50 Gew.-Teilen Kom- ponente e, 25 Gew.-Teilen Komponente 1, 25 Gew.-Teilen Komponente h und 2 Gew.-Teilen Komponente m;
- Gerüst- und Hilfsstoffe: 10 Gew.-% Phosphorsäure (85 gew.-%ig), 5 Gew.-% Pentanatriumtriphosphat und 80 Gew.-% vollentsalztes Wasser.
- ---------------------------- 5 wt .-% surfactant-containing mixture of 50 parts by weight of com - ponent e, 25 wt Parts of component 1, 25 parts by weight of component h and 2 parts by weight of component m;
- Builders and auxiliaries: 10% by weight phosphoric acid (85% by weight), 5% by weight pentasodium triphosphate and 80% by weight deionized water.
Pentanatriumtriphosphat wird in vollentsalztem Wasser gelöst, anschließend werden Phosphorsäure und zum Schluß das tensidhaltige Gemisch zugegeben. Gemessen wird an einer Reinigungsflotte mit 10 g/1 Gesamtformulierung (= 0,5 g/l Tensidgemisch A + B) in NaOH, pH 13.Pentasodium triphosphate is dissolved in deionized water, then phosphoric acid and finally the mixture containing surfactants are added. Measurement is carried out on a cleaning liquor with 10 g / 1 total formulation (= 0.5 g / l surfactant mixture A + B) in NaOH, pH 13.
Eigenschaum bei 25 °C (nach DIN-Norm 53 902): 10 ml Eigenschaum bei 65 °C (nach DIN-Norm 53 902): 0 ml Maximale Eiweißbelastung (bis 30 ml Schaum): 9,0 g/l Ablaufverhalten nach dem Klarspülen mit Wasser: keine Tropfenbildung.Own foam at 25 ° C (according to DIN standard 53 902): 10 ml own foam at 65 ° C (according to DIN standard 53 902): 0 ml Maximum protein load (up to 30 ml foam): 9.0 g / l Drainage behavior after Rinse with water: no drops.
Claims (4)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT81110471T ATE8658T1 (en) | 1980-12-23 | 1981-12-16 | SURFACTANT MIXTURE FOR CLEANING HARD SURFACES. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3048641 | 1980-12-23 | ||
DE19803048641 DE3048641A1 (en) | 1980-12-23 | 1980-12-23 | "TENSIDE-CONTAINING MIXTURE FOR CLEANING HARD SURFACES" |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0054894A1 true EP0054894A1 (en) | 1982-06-30 |
EP0054894B1 EP0054894B1 (en) | 1984-07-25 |
Family
ID=6120063
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP81110471A Expired EP0054894B1 (en) | 1980-12-23 | 1981-12-16 | Surfactant-containing mixture for cleaning hard surfaces |
Country Status (6)
Country | Link |
---|---|
US (1) | US4443364A (en) |
EP (1) | EP0054894B1 (en) |
JP (1) | JPS58109599A (en) |
AT (1) | ATE8658T1 (en) |
CA (1) | CA1160535A (en) |
DE (2) | DE3048641A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0119641B1 (en) * | 1983-02-11 | 1987-05-13 | Unilever N.V. | Aqueous alkaline cleaning composition |
EP0276050A1 (en) * | 1987-01-09 | 1988-07-27 | ICI France SA | Surfactant compositions, washing and defoaming processes |
WO1991017233A1 (en) * | 1990-05-09 | 1991-11-14 | Henkel Kommanditgesellschaft Auf Aktien | Use of a combination of ionic and non-ionic tensides |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59157196A (en) * | 1983-02-28 | 1984-09-06 | ダイキン工業株式会社 | Solvent composition |
JPS60223900A (en) * | 1984-04-23 | 1985-11-08 | アサヒビール株式会社 | Method of deterging coil of draught beer barrel dispenser |
DE3439519A1 (en) * | 1984-10-29 | 1986-04-30 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR IMPROVING THE CORROSION BEHAVIOR OF DISINFECTANT SOLUTIONS |
US4606850A (en) * | 1985-02-28 | 1986-08-19 | A. E. Staley Manufacturing Company | Hard surface cleaning composition and cleaning method using same |
USH269H (en) | 1985-03-11 | 1987-05-05 | A. E. Staley Manufacturing Company | Disinfectant and/or sanitizing cleaner compositions |
US4954316A (en) * | 1987-10-03 | 1990-09-04 | Globus Alfred R | Stable, active chlorine containing anti-microbial compositions |
DE4027446C1 (en) * | 1990-08-30 | 1992-04-02 | Kali-Chemie Ag, 3000 Hannover, De | |
DE4100306A1 (en) * | 1991-01-08 | 1992-07-09 | Henkel Kgaa | GRAIN-SHAPED, EASILY SOLUBLE DRY CONCENTRATES OF INGREDIENTS FROM DETERGENT AND / OR CLEANING AGENTS AND METHOD FOR THE PRODUCTION THEREOF |
US5382376A (en) * | 1992-10-02 | 1995-01-17 | The Procter & Gamble Company | Hard surface detergent compositions |
ATE187760T1 (en) * | 1993-04-19 | 2000-01-15 | Reckitt & Colman Inc | ALL-PURPOSE CLEANING AGENT COMPOSITION |
ATE283910T1 (en) | 1997-03-20 | 2004-12-15 | Procter & Gamble | CLEANING PRODUCT FOR USE WITH CLEANING UTENSIL, CONSISTING OF HIGHLY ABSORBENT MATERIAL AND CONTAINER THEREOF |
GB9817345D0 (en) * | 1998-08-11 | 1998-10-07 | Reckitt & Colman Inc | Improvements in or related to organic compositions |
GB9817457D0 (en) | 1998-08-12 | 1998-10-07 | Reckitt & Colman Inc | Improvements in or related to organic compositions |
GB2381531A (en) * | 2001-11-02 | 2003-05-07 | Reckitt Benckiser Inc | Hard surface cleaning and disinfecting compositions |
US20080287331A1 (en) * | 2007-05-18 | 2008-11-20 | Hai-Hui Lin | Low voc cleaning composition for cleaning printing blankets and ink rollers |
DE102012013969B4 (en) * | 2012-07-13 | 2017-09-14 | Oxea Gmbh | Process for the preparation of a mixture of positionally isomeric aliphatic isononanoic acids starting from 2-ethylhexanol |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3171861A (en) * | 1957-06-11 | 1965-03-02 | Minnesota Mining & Mfg | Fluorinated aliphatic alcohols |
DE1939252A1 (en) * | 1968-08-02 | 1970-02-05 | Procter & Gamble | Low foaming detergent |
US4065409A (en) * | 1975-08-01 | 1977-12-27 | Corporate Brands, Inc. | Hard surface detergent composition |
GB2004534A (en) * | 1977-09-23 | 1979-04-04 | Hoechst Ag | Suppression of foaming of liquid media |
US4174304A (en) * | 1975-08-01 | 1979-11-13 | Bullen Chemical Company Midwest, Inc. | Surfactant system |
EP0008096A2 (en) * | 1978-08-09 | 1980-02-20 | Hoechst Aktiengesellschaft | Process for the synthesis of 2-(perfluoroalkyl)-ethanols |
EP0040713A1 (en) * | 1980-05-12 | 1981-12-02 | Henkel Kommanditgesellschaft auf Aktien | Use of mixed formals of alkylpolyglycol ethers as foam suppressing agents |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB873214A (en) * | 1958-08-20 | 1961-07-19 | British Nylon Spinners Ltd | Non-ionic detergent compositions |
GB994607A (en) * | 1963-10-09 | 1965-06-10 | Du Pont | Process for preparing fluoroalkanols |
DE2523588C2 (en) * | 1975-05-28 | 1983-11-10 | Hoechst Ag, 6230 Frankfurt | Polyglycol ether mixed formals and their use as caustic alkali-resistant wetting agents, detergents and cleaning agents |
US4284532A (en) * | 1979-10-11 | 1981-08-18 | The Procter & Gamble Company | Stable liquid detergent compositions |
-
1980
- 1980-12-23 DE DE19803048641 patent/DE3048641A1/en not_active Withdrawn
-
1981
- 1981-12-14 US US06/330,768 patent/US4443364A/en not_active Expired - Fee Related
- 1981-12-16 DE DE8181110471T patent/DE3165128D1/en not_active Expired
- 1981-12-16 AT AT81110471T patent/ATE8658T1/en not_active IP Right Cessation
- 1981-12-16 EP EP81110471A patent/EP0054894B1/en not_active Expired
- 1981-12-22 JP JP56206278A patent/JPS58109599A/en active Granted
- 1981-12-22 CA CA000392972A patent/CA1160535A/en not_active Expired
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3171861A (en) * | 1957-06-11 | 1965-03-02 | Minnesota Mining & Mfg | Fluorinated aliphatic alcohols |
DE1939252A1 (en) * | 1968-08-02 | 1970-02-05 | Procter & Gamble | Low foaming detergent |
FR2014933A1 (en) * | 1968-08-02 | 1970-04-24 | Procter & Gamble | |
US4065409A (en) * | 1975-08-01 | 1977-12-27 | Corporate Brands, Inc. | Hard surface detergent composition |
US4174304A (en) * | 1975-08-01 | 1979-11-13 | Bullen Chemical Company Midwest, Inc. | Surfactant system |
GB2004534A (en) * | 1977-09-23 | 1979-04-04 | Hoechst Ag | Suppression of foaming of liquid media |
DE2742853A1 (en) * | 1977-09-23 | 1979-04-12 | Hoechst Ag | PROCESS FOR SUPPRESSING THE FOAM OF LIQUID MEDIA |
EP0008096A2 (en) * | 1978-08-09 | 1980-02-20 | Hoechst Aktiengesellschaft | Process for the synthesis of 2-(perfluoroalkyl)-ethanols |
EP0040713A1 (en) * | 1980-05-12 | 1981-12-02 | Henkel Kommanditgesellschaft auf Aktien | Use of mixed formals of alkylpolyglycol ethers as foam suppressing agents |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0119641B1 (en) * | 1983-02-11 | 1987-05-13 | Unilever N.V. | Aqueous alkaline cleaning composition |
EP0276050A1 (en) * | 1987-01-09 | 1988-07-27 | ICI France SA | Surfactant compositions, washing and defoaming processes |
WO1991017233A1 (en) * | 1990-05-09 | 1991-11-14 | Henkel Kommanditgesellschaft Auf Aktien | Use of a combination of ionic and non-ionic tensides |
Also Published As
Publication number | Publication date |
---|---|
DE3165128D1 (en) | 1984-08-30 |
ATE8658T1 (en) | 1984-08-15 |
CA1160535A (en) | 1984-01-17 |
JPS58109599A (en) | 1983-06-29 |
JPH0225960B2 (en) | 1990-06-06 |
DE3048641A1 (en) | 1982-07-15 |
EP0054894B1 (en) | 1984-07-25 |
US4443364A (en) | 1984-04-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0054895B1 (en) | Mixture of surfactants for the cleaning of hard surfaces | |
EP0054894B1 (en) | Surfactant-containing mixture for cleaning hard surfaces | |
EP0254208B1 (en) | Low foaming and/or foam inhibiting mixtures of tensides and their use | |
EP0300305B1 (en) | Use of hydroxyalkylpolyethylene glycol ethers as rinsing agents for use in mechanical dish washing | |
EP0197434B1 (en) | Rinsing agents for use in mechanical dish washing | |
EP0019173B1 (en) | Use of alkoxylated alcohols as biodegradable and low-foaming surface-active agents in dish-washing agents for dish-washers | |
EP0489777B1 (en) | Anti-foaming agents stable in alkali | |
CH624989A5 (en) | ||
EP0946697B1 (en) | Mixtures of alkoxylates with antifoaming and disinfectant effect and use thereof in cleaning compositions | |
EP0343503A1 (en) | Foam-depressing polyglycol ethers for cleaning products | |
DE1080250B (en) | laundry detergent | |
WO1994007977A2 (en) | Clear rinse for machine dish washing | |
DE1243313B (en) | Liquid detergent concentrate | |
EP0694606B1 (en) | Mixtures of alkoxylates as foam depressing agent and use thereof | |
EP0326795B1 (en) | Use of polyglycol ethers as anti-foaming agents in detergents | |
DE69902094T2 (en) | CHEMICAL CLEANING COMPOSITION | |
DE2502433A1 (en) | DETERGENTS AND DETERGENTS, IN PARTICULAR FOR THE REMOVAL OF GREASE AND OIL STAINS | |
EP0708815B1 (en) | Use of fatty acid n-alykl polyhydroxyalkylamides in the processing of clear-rinsing agents for the machine-cleaning of hard surfaces | |
CH635614A5 (en) | Liquid detergent and process for its preparation | |
EP0343504A1 (en) | Foam-depressing polyglycol ethers for cleaning products | |
EP0095136B1 (en) | Rinsing agents for use in mechanical dishwashing | |
DE3638459A1 (en) | DETERGENT COMPOSITION FOR REMOVING OILY DIRT | |
DE1944569C3 (en) | Cleaning agents with foam-suppressing additives | |
EP0025147B1 (en) | Liquid low-phosphate non-polluting detergent | |
DE3512120A1 (en) | Clear rinsing agent for mechanical dishwashing |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT NL SE |
|
17P | Request for examination filed |
Effective date: 19821215 |
|
ITF | It: translation for a ep patent filed |
Owner name: ING. C. GREGORJ S.P.A. |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
REF | Corresponds to: |
Ref document number: 8658 Country of ref document: AT Date of ref document: 19840815 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 3165128 Country of ref document: DE Date of ref document: 19840830 |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
ITTA | It: last paid annual fee | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19891116 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19891122 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19891127 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19891130 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19891206 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19891231 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19900208 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19900219 Year of fee payment: 9 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19901216 Ref country code: AT Effective date: 19901216 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19901217 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Effective date: 19901231 Ref country code: CH Effective date: 19901231 Ref country code: BE Effective date: 19901231 |
|
BERE | Be: lapsed |
Owner name: HOECHST A.G. Effective date: 19901231 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19910701 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee | ||
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19910830 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19910903 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
EUG | Se: european patent has lapsed |
Ref document number: 81110471.0 Effective date: 19910910 |