EP0131138B1 - Use of fatty acid cyanamides as surface-active agents in the cleaning of hard surfaces - Google Patents
Use of fatty acid cyanamides as surface-active agents in the cleaning of hard surfaces Download PDFInfo
- Publication number
- EP0131138B1 EP0131138B1 EP84106289A EP84106289A EP0131138B1 EP 0131138 B1 EP0131138 B1 EP 0131138B1 EP 84106289 A EP84106289 A EP 84106289A EP 84106289 A EP84106289 A EP 84106289A EP 0131138 B1 EP0131138 B1 EP 0131138B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fatty acid
- water
- surfactant
- cleaning
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000194 fatty acid Substances 0.000 title claims abstract description 66
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 65
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 65
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 48
- -1 fatty acid cyanamides Chemical class 0.000 title claims description 77
- 238000004140 cleaning Methods 0.000 title claims description 17
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims description 25
- 239000003945 anionic surfactant Substances 0.000 claims description 16
- 239000002736 nonionic surfactant Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- 125000000129 anionic group Chemical group 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 11
- 239000002280 amphoteric surfactant Substances 0.000 claims description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229920000620 organic polymer Polymers 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000003599 detergent Substances 0.000 abstract description 12
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 9
- 229920003169 water-soluble polymer Polymers 0.000 abstract description 6
- 239000012459 cleaning agent Substances 0.000 description 31
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 16
- 150000002191 fatty alcohols Chemical class 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000003086 colorant Substances 0.000 description 10
- 239000003205 fragrance Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000003760 tallow Substances 0.000 description 7
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- 244000060011 Cocos nucifera Species 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000007792 addition Methods 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 150000002170 ethers Chemical class 0.000 description 6
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- 235000019832 sodium triphosphate Nutrition 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- 239000004435 Oxo alcohol Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 230000000845 anti-microbial effect Effects 0.000 description 4
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- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004851 dishwashing Methods 0.000 description 4
- 150000004676 glycans Chemical class 0.000 description 4
- 239000003752 hydrotrope Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
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- 239000005017 polysaccharide Substances 0.000 description 4
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- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- MBEGFNBBAVRKLK-UHFFFAOYSA-N sodium;iminomethylideneazanide Chemical compound [Na+].[NH-]C#N MBEGFNBBAVRKLK-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- JBVOQKNLGSOPNZ-UHFFFAOYSA-N 2-propan-2-ylbenzenesulfonic acid Chemical compound CC(C)C1=CC=CC=C1S(O)(=O)=O JBVOQKNLGSOPNZ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 101100116570 Caenorhabditis elegans cup-2 gene Proteins 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 101100116572 Drosophila melanogaster Der-1 gene Proteins 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000004996 alkyl benzenes Chemical class 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229940077388 benzenesulfonate Drugs 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
- 229940071118 cumenesulfonate Drugs 0.000 description 3
- 238000007046 ethoxylation reaction Methods 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229940055577 oleyl alcohol Drugs 0.000 description 3
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000151 polyglycol Polymers 0.000 description 3
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- 239000000843 powder Substances 0.000 description 3
- 150000003333 secondary alcohols Chemical class 0.000 description 3
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- 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 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229920006318 anionic polymer Polymers 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000011086 high cleaning Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
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- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 229910052698 phosphorus Inorganic materials 0.000 description 2
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- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
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- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 2
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- 238000009472 formulation Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- BAYPQSYNYDEBIB-UHFFFAOYSA-N hexadecyl-dimethyl-propylazanium Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)CCC BAYPQSYNYDEBIB-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000003165 hydrotropic effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical class [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229940080237 sodium caseinate Drugs 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229940071104 xylenesulfonate Drugs 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/65—Mixtures of anionic with cationic compounds
- C11D1/652—Mixtures of anionic compounds with carboxylic amides or alkylol amides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/37—Mixtures of compounds all of which are anionic
-
- 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
- C11D1/50—Derivatives of urea, thiourea, cyanamide, guanidine or urethanes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
Definitions
- acyl cyanamides in particular the fatty acid cyanamides and their properties as soap-like wetting and dispersing agents, have been known since the 1930s. So describe the German Patent 708,428 and British Patent 428,091 di- "rsteltung the acylcyanamides and a method for treating textiles with these substances.
- non-ionic surfactants and synthetic anionic surfactants have also been described as the active constituents of cleaning agents, for example the combination of ethoxylated diols and alkylbenzenesulfonate or alkanesulfonate (German Offenlegungsschrift 27 09 890).
- a further increase in activity is achieved by adding certain water-soluble polymers from the group of polyethylene glycols, polyvinyl alcohols, polyvinyl pyrrolidones and cellulose ethers.
- the fatty acid cyanamides in particular those having 8 to 18 carbon atoms in the fatty acid residue, in the form of their water-soluble salts are outstandingly suitable as a surfactant for cleaning hard surfaces and as a component of cleaning agents for hard surfaces.
- the use of the fatty acid cyanamides together with another synthetic surfactant leads to a pronounced increase in activity; Such an increase in activity also occurs when the fatty acid cyanamides are used together with small amounts of water-soluble polymeric substances, even if no further surfactants are present.
- Agents for cleaning hard surfaces are understood to mean solid, powder, paste and liquid agents which are used in the household, in industry and by commercial cleaning companies for the gentle cleaning of contaminated surfaces.
- dishwashing agents for manual cleaning of dishes
- cleaning agents for hard surfaces made of metal-lacquered wood, plastic, ceramic products such as porcelain, tiles, tiles, glass and the like are understood.
- These cleaning agents can be used undiluted or diluted, for example by applying them to a damp, absorbent cloth or a sponge and thus wiping the hard surfaces and thus cleaning them from dust, grease, dirt and stains, or by putting the objects to be cleaned into dilute aqueous solutions Immerse the cleaning agent solutions and work with a sponge, rag or brush. It is desired that the surface treatment does not leave any detergent stains or strips and does not require any post-treatment with clear water.
- the fatty acid cyanamides are advantageously in the form of their water-soluble salts, i.e. H. as an alkali metal salt, such as. B. the lithium, sodium, potassium salt or used as ammonium or alkanolammonium salt.
- the fatty acid cyanamides used according to the invention can also be represented by the following general formula represent, in which R the fatty alkyl / alkenyl radical and Me e mean the associated cation as defined above.
- the synthetic surfactants mentioned are generally used in amounts of 1 to 30% by weight (based on the cleaning agent in concentrated form) together with the fatty acid cyanamides.
- the water-soluble organic polymers which are used in small amounts, ie in amounts of 0.01 to 2 % By weight (based on the cleaning agent used in concentrated form) are used, the water-soluble polyethylene glycols having a molecular weight between 300,000 and 4,000,000; the water-soluble polyvinyl alcohols with molecular weights of about 13,400 to 250,000; the water-soluble polyvinylpyrrolidones with molecular weights in the range from 10,000 to 1,000,000 and the water-soluble cellulose ethers, polysaccharides, proteins and polyacrylamides, which have average molecular weights of 5,000 to 10,000,000, preferably 20,000 to 2,000,000, and also by a charge density of greater than 0 but not greater than 0.5 are marked.
- These water-soluble polymers which can be used according to the invention as cleaning-enhancing additives are also explained in more detail in the further course of the description.
- the salts of fatty acid cyanamides used according to the invention are colorless to slightly yellowish substances of brittle to waxy nature which are solid at room temperature. They soften at higher temperatures and melt above 100 to 150 ° C.
- the fatty acid cyanamide salts can be prepared from carboxylic acid derivatives and cyanamide with subsequent neutralization by means of suitable bases (see German Patent 708 428 or A. E. Kretov and A. P. Momsenko j. Of Org. Chem. Of the USSR 1 (1965), pages 1765-1767).
- a simple production process from salts of cyanamide and carboxylic acid esters is described in German patent application P 32 02 213.1. In this process, the fatty acid cyanamide salts are obtained in anhydrous form.
- the salts of fatty acid cyanamides also have the advantage that they can be produced from renewable raw materials, here fatty acid derivatives, and from cyanamide, which is easily accessible from calcium cyanamide. This reduces the dependency on petroleum-based raw materials when using these surfactants.
- B. is the case with alkylbenzenesulfonate.
- the fatty acid cyanamides are to be regarded as extremely environmentally friendly compounds because of their good biodegradability and their toxicological harmlessness.
- the sodium salts of the fatty acid cyanamides are preferably used, in particular those which are derived from C 12 to C 6 fatty acids. These compounds can easily be obtained from monosodium cyanamide and the methyl esters of natural fatty acids and fatty acid mixtures, such as. B. Coconut fatty acid methyl ester.
- the detergents used in accordance with the invention are also notable for good skin tolerance on account of their content of fatty acid cyanamides.
- the quantitative ratio of fatty acid cyanamide salt and the co-surfactant is in the range from 9: 1 to 1: 9.
- the agents used according to the invention generally contain the fatty acid cyanamide salt in amounts of 1 to 90% by weight.
- the water-soluble polymer based on the amount of fatty acid cyanamide salt, is always clearly used in deficit, the amount of water-soluble polymer preferably not more than 1/5 and in particular not more than 1 / 10 of the amount of the fatty acid cyanamide salt.
- the fatty acid cyanamide salt is used together with a further synthetic surfactant and an addition of the cleaning-enhancing polymer.
- the cleaning agents used according to the invention are generally neutral to slightly alkaline, i.e. H.
- Their aqueous working solutions should have a pH in the range from 7.0 to 10.5, in particular 7.5 to 9.5, at application concentrations of 2 to 20, in particular 5 to 15 g / 1 of water or aqueous solution.
- the cleaning agents can contain an acidic or alkaline substance, which is compatible with the other constituents, to regulate the pH value.
- Solid carrier substances are understood to mean neutral reacting organic or inorganic salts, finely dispersed silicas, layered silicates and aluminosilicates and similar substances compatible with the other constituents.
- Suitable synthetic anionic surfactants which can be used together with the fatty acid cyanamide salts are, in particular, those of the sulfonate and sulfate type.
- the surfactants of the sulfonate type are primarily the alkylbenzenesulfonates with C S. 15 alkyl: groups and the esters of a-sulfo fatty acids, e.g. B. a-sulfonated methyl or ethyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.
- alkanesulfonates which are obtainable from C 12 -C 18 -alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins
- olefinsulfonates which are mixtures of alkene and hydroxyalkanesulfonates and disulfonates as obtained for example from monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline and acidic hydrolysis of the sulfonation products.
- Particularly suitable surfactants of the sulfate type are the sulfuric acid monoesters of primary alcohols of natural and synthetic origin, ie of fatty alcohols such as. As coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, or the C 10 -C 20 oxo alcohols, and those of secondary alcohols of these chain lengths.
- the sulfuric acid monoesters of the aliphatic primary alcohols ethoxylated with 1 to 8 moles of ethylene oxide or ethoxylated secondary alcohols or alkylphenols are suitable.
- Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.
- anionic surfactants are preferably used in the form of the salts, in particular in the form of the sodium salts, but also as potassium or ammonium salts or as soluble salts of organic bases, such as mono-, di- or triethanolamine.
- Such cleaning agents which have 1 to 80% by weight of fatty acid cyanamide salt and 1 to 30% by weight of synthetic anionic surfactant from the group of alkylbenzenesulfonates, ester sulfonates, alcohol sulfates and mixtures thereof, in addition to other customary components of washing and cleaning agents, have particularly favorable application properties contain.
- Addition products of 1 to 40, preferably 2 to 20 moles of ethylene oxide with 1 mole of an aliphatic compound having essentially 10 to 20 carbon atoms from the group of alcohols, alkylphenols, carboxylic acids and carboxamides are suitable as nonionic surfactants.
- non-fully or not fully water-soluble polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants. Because of their good biodegradability, the ethoxylation products of primary aliphatic alkanols and alkenols are of particular practical interest.
- EO ethylene oxide
- tallow fatty alcohol 5-EO oleyl / cetyl alcohol 5-EO (iodine number 30 to 50 )
- Tallow fatty alcohol 7-EO synthetic C 12 -C 16 fatty alcohol 6-EO, C 11 -C 15 oxo alcohol 3-EO, C 14
- Exemplary representatives for the non-ionic surfactants with an average degree of ethoxylation of 8 to 20, in particular 9 to 15, are the compounds coconut fatty alcohol 12-EO, synthetic C 15 / C 18 fatty alcohol 9-EO, oleyl / Cetyl-alcohol-10-EO, tallow fatty alcohol-14-EO, C 1l -C 1S -Oxoalko-hol-13-EO, C 15 -C 18 -Oxoalcohol-15-EO, iC 15 -C 17 -alkane-diol- 9-EO, C 14 / C 15 -oxoalcohol-11-EO, sec.-C 11 -C 15 -alcohol-9-EO.
- nonionic surfactants are the water-soluble adducts of ethylene oxide with polypropylene glycol, which contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups, Alkylenediamine-polypropylene glycol and useful on alkylpolypropylene glycols with 1 to 10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic radical.
- Nonionic surfactants of the amine oxide or sulfoxide type can also be used, for example the compounds N-cocoalkyl-N, N-dimethylamine oxide, N-hexadecyl-N, N-bis- (2,3-diethylroxypropyl) amine oxide, N-tallow alkyl-N, N-dihydroxyethylamine oxide.
- Suitable amphoteric surfactants are those which contain both acidic groups such as. B. carboxvl, sulfonic acid, sulfuric acid half-ester, phosphonic acid and phosphoric acid partial ester groups, as well as basic groups, such as. 8. Contain primary, secondary, tertiary and quaternary ammonium groups.
- Amphoteric compounds with quaternary ammonium groups belong to the type of betaines or zwitterionic surfactants. These are, in particular, derivatives of aliphatic quaternary ammonium compounds in which one of the aliphatic radicals consists of a C 8 -C 18 radical and another contains an anionic water-solubilizing carboxy, sulfo or sulfato group.
- Typical representatives of such surface-active betaines are, for example, the compounds 3- (N-hexadecyl-N, N-dimethylammonio) propane sulfonate, 3- (N-tallowate-N, N-dimethylammonio) -2-hydroxypropane sulfonate, 3- (N- Hexadecyl-N, N-bis (2-hydroxyethyl) -ammonio) -2-hydroxypropyl sulfate, 3- (N-coco-alkyl-N, N-bis (2,3-dihydroxypropyl) -ammonio) propane sulfonate, N-tetradecyl-N , N-dimethyl-ammonioacetate, N-hexadecyl-N, N-bis (2,3-di-hydroxypropyl) ammonium acetate.
- the water-soluble organic polymers which can be used according to the invention include water-soluble polyethylene glycols with a molecular weight between 300,000 and 4,000,000, preferably between 500,000 and 1,000,000, which are prepared in a known manner by subjecting ethylene glycols to a polycondensation process. They can also be considered as condensation polymers of ethylene oxide with ethylene glycol or water. They have the general formula HO (-CH 2 -CH 2 -0) n H, where n can vary between 4,800 and 64,800 in the case of the polyethylene glycols used according to the invention. Such polymers are also commercially available and z. B. from Union Carbon Carbide Corporation (UCC) under the name "POLYOXm".
- UCC Union Carbon Carbide Corporation
- the water-soluble nonionic polymers also include the polyvinyl alcohols and the polyvinylpyrrolidones.
- Polyvinyl alcohols can be produced by hydrolysis of polyvinyl acetate. They have the general formula (-CH 2 -CH (OH) -) n and molecular weights of about 13,400 to 250,000, preferably 80,000 to 100,000. They can still contain small amounts of acetyl radicals from the hydrolysis reaction, but these should be less than 40, preferably less than 15 and in particular less than 2 and if possible 0 percent.
- Polyvinyl alcohols are sold, for example, by Wacker-Chemie under the name "POLYVIOL m " or by Nippon Gohsei under the name "GOHSENOLE®”.
- Polyvinylpyrrolidones are also commercially available polymers. They are marketed by the company BASF, among others, under the name "LUVISKOLE®". Their degree of polymerization for the use according to the invention is between 100 and 9,000, preferably between 350 and 7,500, the mol-060014 weights between approximately 10,000 and 1,000,000, preferably between approximately 30,000 and 850,000.
- cellulose ethers Depending on the degree of substitution or conversion, cellulose ethers, polysaccharides, proteins and polyacrylamides are water-soluble so-called weakly anionic polymers. These are understood to mean those polymers whose charge density is greater than 0 but not greater than 0.5, preferably greater than 0 but not greater than 0 , 2 and in particular greater than 0, but not greater than 0.01.
- the definition for the charge density corresponds to the following formula:
- the cellulose ethers with a charge density greater than 0, but not greater than 0.5, preferably greater than 0, but not greater than 0.2 include, above all, those whose 2 percent aqueous solution has a viscosity of greater than 20 ° C. 50 m Pa. s, preferably greater than 100 m Pa. s. This includes, by Henkel under the type collective term "CULMINAL m" treated methylcellulose (MC), methylhydroxyethylcelluloses (MHEC), methyl hydroxypropyl cellulose (MHPC), carboxymethyl (CMMC) and hydroxyethyl cellulose (HEC), also methylhydroxybutyl (MHBC) and hydroxybutyl as by Dow Chemicals under the brand name Methocel®. These cellulose ethers are preferred from the class of anionic polymers.
- Polysaccharides are particularly suitable in derivative form, for example as starch ethers (for example Solvitose e from WA Scholtens, Holland), the charge density from 0.5 to less than 0.2 also being decisive here.
- Alginates (“ALGIPON®” from Henkel) also belong to this class of polymers.
- the proteins which can be used according to the invention are, for example, sodium caseinate and gelatin, both of which are sold, inter alia, by the company Milac, Hamburg.
- Polyacrylamides ie polymers and copolymers of acrylamide with the general formula (-CH 2 -CH (CONH 2 ) -) n with molecular weights of 300,000 to 8,000,000, preferably 500,000 to 2,000,000, are marketed by Schuchardt, among others and are also suitable for use in accordance with the invention.
- Suitable pH-regulating agents are conventional inorganic or organic acids or acid salts, such as hydrochloric acid, sulfuric acid, bisulfates of the alkalis, aminosulfonic acid, as acidic substances, Phosphoric acid or other acids of phosphorus, in particular the anhydrous acids of phosphorus or their salts or their acid-reacting solid compounds with urea or other lower carboxylic acid anides, partial amides of phosphoric acids or anhydrous phosphoric acid, citric acid, tartaric acid, lactic acid are unequal.
- Organic or inorganic compounds such as alkane mines, namely mono-, di- or triethanolamine or ammonia can also be added as basic substances.
- alkaline builder substances and washing alkalis such as sodium tripolyphosphate, sodium carbonate and sodium bicarbonate, potassium carbonate and bicarbonate, sodium silicate and the sodium aluminosilicates are suitable.
- solubilizers for the preparation of the cleaning agents in liquid form, known solubilizers can be incorporated, which in addition to the water-soluble organic solvents such as, in particular, low-molecular aliphatic alcohols having 1 to 4 carbon atoms, also include the so-called hydrotropic substances of the lower alkylarylsulfonate type, for example toluene, xylene or cumene sulfonate . They can also be in the form of their sodium and / or potassium and / or alkylamino salts. Water-soluble organic solvents can also be used as solubilizers, in particular those with boiling points above 75 ° C., for example the ethers from the same or different polyhydric alcohols or the partial ethers from polyhydric alcohols.
- These include, for example, di- or triethylene glycol polyglycerols and also the partial ethers of ethylene glycol, propylene glycol, butylene glycol or oleacerine with aliphatic monohydric alcohols containing 1 to 4 carbon atoms in the molecule.
- Suitable water-soluble or water-emulsifiable organic solvents are also ketones, such as acetone, methyl ethyl ketone and aliphatic, cycloaliphatic, aromatic and chlorinated hydrocarbons, and also the terpene alcohols.
- the cleaning agents can contain additives of colors and fragrances, preservatives and, if desired, antimicrobial agents of any kind.
- Formaldehyde-amino alcohol condensation products are preferably used as antimicrobial agents.
- the products are obtained by reacting an aqueous solution of formaldehyde with amino alcohols, e.g. B. 2-aminoethanol, 1-aminoethanol, 1-amino-2-propanol, 2-aminoiso-butanol, 2 (2'-aminoethyl) aminoethanol.
- the cleaning agents can contain any organic or inorganic abrasives.
- the powdery consistency of the fatty acid cyanamide salts is again of particular advantage for the production of scouring powders.
- Plates with a mixed contamination of protein, fat and carbohydrates were soiled and rinsed at 45 ° C.
- the test products were used with a dosage of 0.1 g / l for powdery products and 0.4 g / l for liquid products.
- the number of plates that are rinsed clean with 5 l of washing liquid number of plates serves as a measure of the washing effect.
- Example 2 If in Example 2 the fatty acid cyanamide salt is replaced by C 11 -C 13 alkylbenzenesulfonate, Na salt, the same test gives a plate number of 16.
- the cleaning agent to be tested is placed on an artificially soiled plastic surface.
- a mixture of carbon black, machine oil, triglyceride, saturated fatty acids and low-boiling aliphatic hydrocarbon is used as artificial soiling.
- the test area of 26 x 28 cm is evenly coated with 2 g of the artificial soiling with the help of a surface coater.
- a plastic sponge is soaked with 12 ml of the detergent solution to be tested and moved mechanically on the test surface. After 6 wiping movements, the cleaned test area is kept under running water and the loose dirt is removed.
- the cleaning effect, d. that is, the whiteness of the plastic surface cleaned in this way is measured using an LF 90 photoelectronic colorimeter (Dr. B. Lange).
- the clean white plastic surface serves as the white standard.
- the read values for the cleaned plastic areas are to be equated with the percentage cleaning capacity (% RV).
- % RV values given are the values determined by this method for the cleaning ability of the cleaning agents examined. They represent mean values from fourfold determinations.
- This method allows a reproducible comparison as long as similar test materials are used.
- the cleaning agent of Example 4 in 1% solution in tap water of 16 ° d at room temperature gives a value of 85% RV.
- Example 5a For further comparison in Example 5a) the fatty acid cyanamide salt was replaced by C 12 -C 18 alkanesulfonate. A value of 50% RV was then obtained.
- the example shows that fatty acid cyanamide salts experience a great increase in the cleaning action even through small additions of polymers, so that cleaning agents which contain them are superior to those of the prior art.
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Abstract
Description
Die Acylcyanamide, insbesondere die Fettsäurecyanamide und ihre Eigung als seifenähnliche Netz- und Dispergier-mittel sind bereits seit den dreißiger Jahre- bekannt. So beschreiben die deutsche Patentschrift 708 428 und die britische Patentschrift 428 091 di- "rsteltung der Acylcyanamide und ein Verfahren zur Behandlung von Textilien mit diesen Substanzen.The acyl cyanamides, in particular the fatty acid cyanamides and their properties as soap-like wetting and dispersing agents, have been known since the 1930s. So describe the German Patent 708,428 and British Patent 428,091 di- "rsteltung the acylcyanamides and a method for treating textiles with these substances.
Bei der Entwicklung der modernen Reinigungsmittel für harte Oberflächen macht man von der Wirkungssteigerung, die bestimmte Tensidgemische und Tensid/Polymeren-Gemische im Vergleich zu den jeweiligen Einzelwirkstoffen zeigen, Gebrauch. Auf diese Weise ist es möglich, hohe Reinigungsleistung mit schonender Oberflächenbehandlung und guter Hautverträglichkeit zu verbinden, da man den erwarteten Reinigungseffekt mit geringer Anwendungskonzentration und ohne Verwendung von stark alkalischen oder stark sauren Zusätzen erzielen kann. So verwendet man Gemische aus einem synthetischen anionischen Sulfonattensid, beispielsweise Alkylbenzolsulfonat, und einem synthetischen anionischen Sulfattensid, beispielsweise ein Fettalkoholpolyglykolethersulfat, als synergistisch wirksame Tensidkomponente in Geschirrspülmitteln. Auch Kombinationen von nichttionsichen Tensiden und synthetischen anionischen Tensiden sind als die wirksamen Bestandteile von Reinigungsmitteln beschrieben worden beispielsweise die Kombination aus ethoxylierten Diolen und Alkylbenzolsulfonat oder Alkansulfonat (deutsche Offenlegungsschrift 27 09 890). Eine weitere Wirkungssteigerung wird durch einen Zusatz von bestimmten wasserlöslichen Polymeren aus der Gruppe der Polyethylenglykole, Polyvinylalkohole, Polyvinylpyrrolidone, Celluloseether. Polysaccharide, Proteine und Polyacrylamide zu den Reinigungsmitteln auf Basis nichtionischer und/oder anionischer synthetischer Tenside erzielt, wobei bereits geringe Polymeren-Zusätze eine signifikante Wirkungssteigerung hervorrufen (deutsche Offenlegungsschriften 28 40 463 und 29 13 049).In the development of modern cleaning agents for hard surfaces, use is made of the increase in activity which certain surfactant mixtures and surfactant / polymer mixtures show in comparison to the respective individual active ingredients. In this way it is possible to combine high cleaning performance with gentle surface treatment and good skin tolerance, since the expected cleaning effect can be achieved with a low application concentration and without the use of strongly alkaline or strongly acidic additives. For example, mixtures of a synthetic anionic sulfonate surfactant, for example alkylbenzenesulfonate, and a synthetic anionic sulfate surfactant, for example a fatty alcohol polyglycol ether sulfate, are used as the synergistically active surfactant component in dishwashing detergents. Combinations of non-ionic surfactants and synthetic anionic surfactants have also been described as the active constituents of cleaning agents, for example the combination of ethoxylated diols and alkylbenzenesulfonate or alkanesulfonate (German Offenlegungsschrift 27 09 890). A further increase in activity is achieved by adding certain water-soluble polymers from the group of polyethylene glycols, polyvinyl alcohols, polyvinyl pyrrolidones and cellulose ethers. Polysaccharides, proteins and polyacrylamides for cleaning agents based on nonionic and / or anionic synthetic surfactants have been achieved, with even small additions of polymers causing a significant increase in activity (German Offenlegungsschriften 28 40 463 and 29 13 049).
Es wurde nun gefunden, daß sich die Fettsäurecyanamide, insbesondere solche mit 8 bis 18 Kohlenstoffatomen im Fettsäurerest, in Form ihrer wasserlöslichen Salze in hervorragender Weise als tensidischer Wirkstoff zum Reinigen von harten Oberflächen und als Bestandteil von Reinigungsmitteln für harte Oberflächen eignen. Überraschenderweise führt der Einsatz der Fettsäurecyanamide zusammen mit einem weiteren synthetischen Tensid zu einer stark ausgeprägten Wirkungssteigerung; eine derartige Wirkungssteigerung tritt auch auf, wenn die Fettsäurecyanamide zusammen mit geringen Mengen an wasserlöslichen polymeren Substanzen eingesetzt werden, selbst wenn keine weiteren Tenside zugegen sind.It has now been found that the fatty acid cyanamides, in particular those having 8 to 18 carbon atoms in the fatty acid residue, in the form of their water-soluble salts are outstandingly suitable as a surfactant for cleaning hard surfaces and as a component of cleaning agents for hard surfaces. Surprisingly, the use of the fatty acid cyanamides together with another synthetic surfactant leads to a pronounced increase in activity; Such an increase in activity also occurs when the fatty acid cyanamides are used together with small amounts of water-soluble polymeric substances, even if no further surfactants are present.
Unter Mitteln für das Reinigen von harten Oberflächen werden feste, pulverförmige, pastenförmige und flüssige Mittel verstanden, die im Haushalt, in der Industrie und von gewerblichen Reinigungsbetrieben zur schonenden Reinigung verschmutzter Oberflächen verwendet werden. Neben den sogenannten Geschirrspülmitteln für die manuelle Reinigung von Geschirr werden somit Reinigungsmittel für harte Oberflächen aus Metall lackiertem Holz, Kunststoff keramischen Erzeugnissen wie Porzellan, Fliesen, Kacheln, Glas und dergleichen verstanden. Diese Reinigungsmittel lassen sich unverdünnt oder verdünnt anwenden, beispielsweise indem man sie auf ein feuchtes saugfähiges Tuch oder einen Schwamm aufbringt und damit die harten Oberflächen wischt und somit von Staub, Fett, Schmutz und Flecken reinigt, oder daß man die zu reinigenden Gegenstände in verdünnte wäßrige Lösungen der Reinigungsmittel eintaucht und mit einem Schwamm, einem Lappen oder einer Bürste bearbeitet. Dabei wird gewünscht, daß die Oberflächenbehandlung keine Reinigungsmittelflecken oder -streifen zurückläßt und keine Nachbehandlung mit klarem Wasser erfordert.Agents for cleaning hard surfaces are understood to mean solid, powder, paste and liquid agents which are used in the household, in industry and by commercial cleaning companies for the gentle cleaning of contaminated surfaces. In addition to the so-called dishwashing agents for manual cleaning of dishes, cleaning agents for hard surfaces made of metal-lacquered wood, plastic, ceramic products such as porcelain, tiles, tiles, glass and the like are understood. These cleaning agents can be used undiluted or diluted, for example by applying them to a damp, absorbent cloth or a sponge and thus wiping the hard surfaces and thus cleaning them from dust, grease, dirt and stains, or by putting the objects to be cleaned into dilute aqueous solutions Immerse the cleaning agent solutions and work with a sponge, rag or brush. It is desired that the surface treatment does not leave any detergent stains or strips and does not require any post-treatment with clear water.
Die Fettsäurecyanamide werden zweckmäßigerweise in Form ihrer wasserlöslichen Salze, d. h. als Alkalimetallsalz, wie z. B. das Lithium-, Natrium-, Kaliumsalz oder als Ammonium- oder Alkanolammoniumsalz verwendet.The fatty acid cyanamides are advantageously in the form of their water-soluble salts, i.e. H. as an alkali metal salt, such as. B. the lithium, sodium, potassium salt or used as ammonium or alkanolammonium salt.
Die erfindungsgemäß verwendeten Fettsäurecyanamide lassen sich auch durch die folgende allgemeine Formel
Als weitere synthetische Tenside, die mit den Fettsäurecyanamiden eine unerwartete Wirkungssteigerung ergeben, eignen sich übliche synthetische Tenside vom Typ der anionischen, nichtionischen und amphoteren Tenside; diese werden im weiteren Verlauf der Beschreibung ausführlicher erläutert. Neben den synthetischen Tensiden können auch übliche Seifen, d. h. die oberflächenaktiven Alkali- und Alkanolaminsalze von Fettsäuren eingesetzt werden. Besonders bevorzugt sind Tensidkombinationen mit synthetischen anionischen Tensiden vom Typ der Sulfonat- und Sulfattenside.Conventional synthetic surfactants of the anionic, nonionic and amphoteric surfactant type are suitable as further synthetic surfactants, which give the fatty acid cyanamides an unexpected increase in activity; these will be explained in more detail later in the description. In addition to the synthetic surfactants, conventional soaps, e.g. H. the surface-active alkali and alkanolamine salts of fatty acids are used. Surfactant combinations with synthetic anionic surfactants of the sulfonate and sulfate surfactant type are particularly preferred.
Die genannten synthetischen Tenside werden im allgemeinen in Mengen von 1 bis 30 Gew.-% (bezogen auf das Reinigungsmittel in konzentrierter Form) zusammen mit den Fettsäurecyanamiden eingesetzt.The synthetic surfactants mentioned are generally used in amounts of 1 to 30% by weight (based on the cleaning agent in concentrated form) together with the fatty acid cyanamides.
Zu den wasserlöslichen organischen Polymeren, die in geringen Mengen, d. h. in Mengen von 0,01 bis 2 Gew.-% (bezogen auf das verwendete Reinigungsmittel in konzentrierter Form), eingesetzt werden, gehören die wasserlöslichen Polyethylenglykole mit einem Molgewicht zwischen 300 000 und 4 000 000; die wasserlöslichen Polyvinylalkohole mit Molgewichten von etwa 13 400 bis 250 000; die wasserlöslichen Polyvinylpyrrolidone mit Molgewichten im Bereich Von 10 000 bis 1 000 000 sowie die wasserlöslichen Celluloseether, Polysaccharide, Proteine und Polyacrylamide, die mittlere Molekulargewichte von 5 000 bis 10 000 000, vorzugsweise 20 000 bis 2 000 000, aufweisen und außerdem durch eine Ladungsdichte von größer als 0 aber nicht größer als 0,5 gekennzeichnet sind. Diese erfindungsgemäß als reinigungsverstärkende Zusätze brauchbaren wasserlöslichen Polymeren werden ebenfalls im weiteren Verlauf der Beschreibung näher erläutert.The water-soluble organic polymers which are used in small amounts, ie in amounts of 0.01 to 2 % By weight (based on the cleaning agent used in concentrated form) are used, the water-soluble polyethylene glycols having a molecular weight between 300,000 and 4,000,000; the water-soluble polyvinyl alcohols with molecular weights of about 13,400 to 250,000; the water-soluble polyvinylpyrrolidones with molecular weights in the range from 10,000 to 1,000,000 and the water-soluble cellulose ethers, polysaccharides, proteins and polyacrylamides, which have average molecular weights of 5,000 to 10,000,000, preferably 20,000 to 2,000,000, and also by a charge density of greater than 0 but not greater than 0.5 are marked. These water-soluble polymers which can be used according to the invention as cleaning-enhancing additives are also explained in more detail in the further course of the description.
Bei den erfindungsgemäß verwendeten Salzen der Fettsäurecyanamide handelt es sich um bei Raumtemperatur feste, farblose bis leicht gelbliche Substanzen von spröder bis wachsartiger Beschaffenheit. Sie erweichen bei höheren Temperaturen und schmelzen oberhalb 100 bis 150 °C. Die Fettsäurecyanamidsalze können aus Carbonsäurederivaten und Cyanamid mit nachfolgender Neutralisation durch geeignete Basen hergestellt werden (siehe deutsche Patentschrift 708 428 oder A. E. Kretov und A. P. Momsenko j. of Org. Chem. of the USSR 1 (1965), Seiten 1765 - 1767). Ein einfaches Herstellungsverfahren aus Salzen des Cyanamids und Carbonsäureestern ist in der deutschen Patentanmeldung P 32 02 213.1 beschrieben. Bei diesem Verfahren fallen die Fettsäurecyanamidsalze in wasserfreier Form an. Dies ist ein gegenüber herkömmlichen Tensiden bemerkenswerter Vorteil, der es möglich macht, auch pulverförmige Reinigungsmittel mit hohem Tensidgehalt zu formulieren. Neben der leichten Herstellbarkeit besitzen die Salze der Fettsäurecyanamide noch den Vorzug, daß ihre Herstellung aus nachwachsenden Rohstoffen, hier Fettsäurederivaten, und dem aus Kalkstickstoff leicht zugänglichen Cyanamid möglich ist. Damit verringert sich beim Einsatz dieser Tenside die Abhängigkeit von Rohstoffen auf Erdölbasis, wie dies z. B. beim Alkylbenzolsulfonat der Fall ist. Im übrigen sind die Fettsäurecyanamide wegen ihrer guten biologischen Abbaubarkeit und ihrer toxikologischen Unbedenklichkeit als ausgesprochen umweltfreundliche Verbindungen anzusehen.The salts of fatty acid cyanamides used according to the invention are colorless to slightly yellowish substances of brittle to waxy nature which are solid at room temperature. They soften at higher temperatures and melt above 100 to 150 ° C. The fatty acid cyanamide salts can be prepared from carboxylic acid derivatives and cyanamide with subsequent neutralization by means of suitable bases (see German Patent 708 428 or A. E. Kretov and A. P. Momsenko j. Of Org. Chem. Of the USSR 1 (1965), pages 1765-1767). A simple production process from salts of cyanamide and carboxylic acid esters is described in German patent application P 32 02 213.1. In this process, the fatty acid cyanamide salts are obtained in anhydrous form. This is a remarkable advantage over conventional surfactants, which makes it possible to formulate powdered cleaning agents with a high surfactant content. In addition to being easy to produce, the salts of fatty acid cyanamides also have the advantage that they can be produced from renewable raw materials, here fatty acid derivatives, and from cyanamide, which is easily accessible from calcium cyanamide. This reduces the dependency on petroleum-based raw materials when using these surfactants. B. is the case with alkylbenzenesulfonate. Moreover, the fatty acid cyanamides are to be regarded as extremely environmentally friendly compounds because of their good biodegradability and their toxicological harmlessness.
Bevorzugt verwendet werden die Natriumsalze der Fettsäurecyanamide, insbesondere diejenigen, die sich von C12 - bis C,6-Fettsäuren ableiten. Diese Verbindungen können leicht aus Mononatriumcyanamid und den Methylestern natürlichen Fettsäuren und Fettsäuregemischen, wie z. B. Cocosfettsäuremethylester hergestellt werden.The sodium salts of the fatty acid cyanamides are preferably used, in particular those which are derived from C 12 to C 6 fatty acids. These compounds can easily be obtained from monosodium cyanamide and the methyl esters of natural fatty acids and fatty acid mixtures, such as. B. Coconut fatty acid methyl ester.
Die erfindungsgemäß verwendeten Reinigungsmittel zeichnen sich aufgrund ihres Gehaltes an Fettsäurecyanamiden außerdem durch eine gute Hautverträglichkeit aus.The detergents used in accordance with the invention are also notable for good skin tolerance on account of their content of fatty acid cyanamides.
Bei der bevorzugten Verwendung der Fettsäurecyanamidsalze zusammen mit einem Tensid aus der Gruppe der synthetischen anionischen, nichtionischen und amphoteren Tenside liegt das Mengenverhältnis von Fettsäurecyanamidsalz und dem Co-Tensid im Bereich von 9: 1 bis 1: 9. Dabei enthalten die erfindungsgemäß eingesetzten Mittel im allgemeinen das Fettsäurecyanamidsalz in Mengen von 1 bis 90 Gew.-%.In the preferred use of the fatty acid cyanamide salts together with a surfactant from the group of synthetic anionic, nonionic and amphoteric surfactants, the quantitative ratio of fatty acid cyanamide salt and the co-surfactant is in the range from 9: 1 to 1: 9. The agents used according to the invention generally contain the fatty acid cyanamide salt in amounts of 1 to 90% by weight.
Bei der gemeinsamen Verwendumg von Fettsäurecyanamidsalz und wasserlöslicher polymerer Substanz nach der obigen Definition wird das wasserlöslishe Polymere bezogen auf die Menge an Fettsäurecyanamidsalz immer eindeutig im Unterschuß eingesetzt, wobei die Menge des wasserlöslichen Polymeren vorzugsweise nicht mehr als 1/5 und insbesondere nicht mehr als 1/10 der Menge des Fettsäurecyanamidsalzes beträgt.When fatty acid cyanamide salt and water-soluble polymer substance are used together as defined above, the water-soluble polymer, based on the amount of fatty acid cyanamide salt, is always clearly used in deficit, the amount of water-soluble polymer preferably not more than 1/5 and in particular not more than 1 / 10 of the amount of the fatty acid cyanamide salt.
Nach einer besonders bevorzugten Ausführungsform wird das Fettsäurecyanamidsalz zusammen mit einem weiteren synthetischen Tensid sowie einem Zusatz des reinigungsverstärkenden Polymeren verwendet.According to a particularly preferred embodiment, the fatty acid cyanamide salt is used together with a further synthetic surfactant and an addition of the cleaning-enhancing polymer.
Die konfektionierten pulverförmigen, pastenförmigen und flüssigen Reinigungsmittel, die erfindungsgemäß verwendet werden, enthalten vorzugsweise
- a) 1 bis 90 Gew.-% der oben definierten Fettsäurecyanamidsalze; daneben sind
- b) 0 bis 90 Gew.-% eines synthetischen Tensids aus der Gruppe der anionischen, nichtionischen und amphoteren Tenside und deren Mischungen, sowie
- c) 0 bis 2 Gew.-% eines wasserlöslichen organischen Polymeren vorhanden; wobei der Rest bis 100 Gew.-%, d. h.
- d) 10 bis 99 Gew.-% aus sonstigen in Mitteln zum Reinigen von harten Oberflächen üblichen Bestandteilen bestehen.
- a) 1 to 90% by weight of the fatty acid cyanamide salts defined above; are next to it
- b) 0 to 90 wt .-% of a synthetic surfactant from the group of anionic, nonionic and amphoteric surfactants and mixtures thereof, and
- c) 0 to 2% by weight of a water-soluble organic polymer is present; the rest up to 100 wt .-%, ie
- d) 10 to 99 wt .-% consist of other components common in agents for cleaning hard surfaces.
Die erfindungsgemäß verwendeten Reinigungsmittel sind im allgemeinen neutral bis schwach alkalisch eingestellt, d. h. ihre wäßrigen Gebrauchslösungen sollen bei Anwendungskonzentrationen von 2 bis 20, insbesondere 5 bis 15 g/1 Wasser bzw. wäßriger Lösung einen pH-Wert im Bereich von 7,0 bis 10,5, insbesondere 7,5 bis 9,5 besitzen. Aus diesem Grunde können die Reinigungsmittel unter den üblichen Bestandteilen eine sauer oder alkalisch reagierende Substanz, die mit den übrigen Bestandteilen verträglich ist, zur Regulierung des pH-Werts enthalten.The cleaning agents used according to the invention are generally neutral to slightly alkaline, i.e. H. Their aqueous working solutions should have a pH in the range from 7.0 to 10.5, in particular 7.5 to 9.5, at application concentrations of 2 to 20, in particular 5 to 15 g / 1 of water or aqueous solution. For this reason, the cleaning agents can contain an acidic or alkaline substance, which is compatible with the other constituents, to regulate the pH value.
Ein neutral reagierendes Reinigungsmittel entspricht allgemein der folgenden Rahmenrezeptur:
- a) 1 bis 90 Gew.-% des oben definierten Fettsäurecyanamidsalzes, vorzugsweise des C12- bis C16-Fettsäure- cyanamidnatriumsalzes,
- b) 0,5 bis 90 Gew.-% eines Tensids aus der Gruppe der synthetischen anionischen, nichtionischen und amphoteren Tenside, vorzugsweise aus der Gruppe der synthetischen Aniontenside, wobei das Verhältnis von a: b zwischen 9: 1 bis 1: 9 liegt,
- c) 0 bis 1 Gew.-% eines wasserlöslichen organischen Polymeren gemäß obiger Definition,
- d) 1 bis 15 Gew.-% in Reinigungsmitteln üblichen Bestandteilen aus der Gruppe der pH-regulierenden Puffersysteme, Lösungsmittel, Hydrotrope, Viskositätsregler, antimikrobielle Substanzen, Farb- und Duftstoffe, sowie
- e) 8,0 bis 97,5 Gew.-% Wasser oder feste Trägersubstanzen.
- a) 1 to 90% by weight of the fatty acid cyanamide salt defined above, preferably the C 12 to C 16 fatty acid cyanamide sodium salt,
- b) 0.5 to 90% by weight of a surfactant from the group of synthetic anionic, nonionic and amphoteric surfactants, preferably from the group of synthetic anionic surfactants, the ratio of a: b being between 9: 1 to 1: 9,
- c) 0 to 1% by weight of a water-soluble organic polymer as defined above,
- d) 1 to 15% by weight of components from the group of pH regulators customary in cleaning agents Buffer systems, solvents, hydrotropes, viscosity regulators, antimicrobial substances, colors and fragrances, as well
- e) 8.0 to 97.5% by weight of water or solid carrier substances.
Ein schwach alkalisch reagierendes Relgungsmittel hat allgemein die folgende Rahmenrezeptur:
- a) 1 bis 90 Gew.-% des Fettsäurecyn' lidsatzes nach obiger Definition, vorzugsweise des C12- bis C16-Fett- säurecyanamidnatriumsalzes,
- b) 0 bis 90 Gew.-% eines Temsids aus der Gruppe der synthetischen anionischen, nichtionischen und amphoteren Tenside, vorzugsweise aus der Gruppe der synthetischen anionischen Tenside, wobei das Verhältnis von a: b zwischen 1: 1 und 1: 9 liegt,
- c) 0 bis 1 Gew.-% eines wasserlöslichen organischen Polymeren gemäß obiger Definition, wobei wenigstens eine der Komponenten b oder c zugegen ist,
- d) 1 bis 90 Gew.-% an sonstigen, im Spül- und Reinigungsmitteln üblichen Bestandteilen aus der Gruppe der Builder-Substanzen, Lösungsmittel, Hydrotrope, Viskositätsregler, antimikrobielle Substanzen, Abrasivstoffe, Farb- und Duftstoffe, sowie
- e) 9 bis 98 Gew.-% Wasser oder inerte feste Trägersubstanzen.
- a) 1 to 90% by weight of the fatty acid cyanide set as defined above, preferably the C 12 to C 16 fatty acid cyanamide sodium salt,
- b) 0 to 90% by weight of a surfactant from the group of synthetic anionic, nonionic and amphoteric surfactants, preferably from the group of synthetic anionic surfactants, the ratio of a: b being between 1: 1 and 1: 9,
- c) 0 to 1% by weight of a water-soluble organic polymer as defined above, at least one of components b or c being present,
- d) 1 to 90% by weight of other constituents customary in dishwashing detergents and cleaning agents from the group of builder substances, solvents, hydrotropes, viscosity regulators, antimicrobial substances, abrasives, colors and fragrances, and
- e) 9 to 98% by weight of water or inert solid carrier substances.
Unter festen Trägersubstanzen werden neutral reagierende organische oder anorganische Salze, feindisperse Kieselsäuren, Schichtsilikate und Alumosilikate und ähnliche mit den übrigen Bestandteilen verträgliche Substanzen verstanden.Solid carrier substances are understood to mean neutral reacting organic or inorganic salts, finely dispersed silicas, layered silicates and aluminosilicates and similar substances compatible with the other constituents.
Es folgen nun Erläuterungen zu den wesentlichen gemeinsam mit den Fettsäurecyanamidsalzen verwendeten Reinigungsmittelbestandteilen.There now follows explanations of the essential detergent components used together with the fatty acid cyanamide salts.
Als synthetische Aniontenside, die zusammen mit den Fettsäurecyanamidsalzen verwendet werden können, eignen sich insbesondere solche vom Typ der Sulfonate und Sulfate.Suitable synthetic anionic surfactants which can be used together with the fatty acid cyanamide salts are, in particular, those of the sulfonate and sulfate type.
Bei den Tensiden vom Sulfonattyp handelt es sich in erster Linie um die Alkylbenzolsulfonate mit C S.15-Alkyl: gruppen und die Ester von a-Sulfofettsäuren, z. B. a-sulfonierten Methyl- oder Ethylester der hydrierten Kokos-, Palmkern- oder Talgfettsäuren. Weitere brauchbare Tenside vom Sulfonattyp sind die Alkansulfonate, die aus C12-C18-Alkanen durch Sulfochlorierung oder Sulfoxidation und anschließende Hydrolyse bzw. Neutralisation oder durch Bisulfitaddition an Olefine erhältlich sind, sowie die Olefinsulfonate, das sind Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließender alkalischer und saurer Hydrolyse der Sulfonierungsprodukte erhält.The surfactants of the sulfonate type are primarily the alkylbenzenesulfonates with C S. 15 alkyl: groups and the esters of a-sulfo fatty acids, e.g. B. a-sulfonated methyl or ethyl ester of hydrogenated coconut, palm kernel or tallow fatty acids. Other useful surfactants of the sulfonate type are the alkanesulfonates which are obtainable from C 12 -C 18 -alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and the olefinsulfonates, which are mixtures of alkene and hydroxyalkanesulfonates and disulfonates as obtained for example from monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline and acidic hydrolysis of the sulfonation products.
Besonders geeignete Tenside vom Sulfattyp sind die Schwefelsäuremonoester von primären Alkoholen natürlichen und synthetischen Ursprungs, d. h. von Fettalkoholen, wie z. B. Kokosfettalkoholen, Talgfettalkoholen, Oleylalkohol, oder den C10-C20-Oxoalkoholen, und solche von sekundären Alkoholen dieser Kettenlängen. Daneben kommen die Schwefelsäuremonoester der mit 1 bis 8 Mol Ethylenoxid ethoxylierten aliphatischen primären Alkohole bzw. ethoxylierten sekundären Alkohole bzw. Alkylphenole in Betracht. Ferner eignen sich sulfatierte Fettsäurealkanolamide und sulfatierte Fettsäuremonoglyceride.Particularly suitable surfactants of the sulfate type are the sulfuric acid monoesters of primary alcohols of natural and synthetic origin, ie of fatty alcohols such as. As coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, or the C 10 -C 20 oxo alcohols, and those of secondary alcohols of these chain lengths. In addition, the sulfuric acid monoesters of the aliphatic primary alcohols ethoxylated with 1 to 8 moles of ethylene oxide or ethoxylated secondary alcohols or alkylphenols are suitable. Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.
Alle diese anionischen Tenside werden bevorzugt in Form der Salze eingesetzt, insbesondere in Form der Natriumsalze, aber auch als Kalium- oder Ammoniumsalze oder als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin.All of these anionic surfactants are preferably used in the form of the salts, in particular in the form of the sodium salts, but also as potassium or ammonium salts or as soluble salts of organic bases, such as mono-, di- or triethanolamine.
Besonders günstige anwendungstechnische Eigenschaften weisen solche Reinigungsmittel auf, die 1 bis 80 Gew.-% Fettsäurecyanamidsalz und 1 bis 30 Gew.-% synthetisches anionisches Tensid aus der Gruppe der Alkylbenzolsulfonate, Estersulfonate, Alkoholsulfate und deren Mischungen neben anderen üblichen Bestandteilen von Wasch- und Reinigungsmitteln enthalten.Such cleaning agents which have 1 to 80% by weight of fatty acid cyanamide salt and 1 to 30% by weight of synthetic anionic surfactant from the group of alkylbenzenesulfonates, ester sulfonates, alcohol sulfates and mixtures thereof, in addition to other customary components of washing and cleaning agents, have particularly favorable application properties contain.
Als nichtionische Tenside eignen sich Anlagerungsprodukte von 1 bis 40, vorzugsweise 2 bis 20 Mol Ethylenoxid an 1 Mol einer aliphatischen Verbindung mit im wesentlichen 10 bis 20 Kohlenstoffatomen aus der Gruppe der Alkohole, Alkylphenole, Carbonsäuren und Carbonsäureamide. Besonders wichtig sind die Anlagerungsprodukte von 8 bis 20 Mol Ethylenoxid an primäre Alkohole, wie zum Beispiel Kokos- oder Talgfettalkohole, an Oleylalkohol, an Oxoalkohole der entsprechenden Kettenlängen, oder an entsprechende sekundäre Alkohole, sowie an Mono- oder Dialkylphenole mit 8 bis 14 C-Atomen in den Alkylresten. Neben diesen wasserlöslichen Nonionics sind aber auch nicht bzw. nicht vollständig wasserlösliche Polyglykolether mit 2 bis 7 Ethylenglykoletherresten im Molekül von Interesse, insbesondere, wenn sie zusammen mit wasserlöslichen nichtionischen oder anionischen Tensiden eingesetzt werden. Von besonderem praktischem Interesse sind wegen ihrer guten biologischen Abbaubarkeit vor allem die Ethoxylierungsprodukte von primären aliphatischen Alkanolen und Alkenolen.Addition products of 1 to 40, preferably 2 to 20 moles of ethylene oxide with 1 mole of an aliphatic compound having essentially 10 to 20 carbon atoms from the group of alcohols, alkylphenols, carboxylic acids and carboxamides are suitable as nonionic surfactants. The addition products of 8 to 20 mol of ethylene oxide with primary alcohols, for example coconut oil or tallow fatty alcohols, with oleyl alcohol, with oxo alcohols of the corresponding chain lengths, or with corresponding secondary alcohols, and with mono- or dialkylphenols with 8 to 14 C- Atoms in the alkyl radicals. In addition to these water-soluble nonionics, non-fully or not fully water-soluble polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants. Because of their good biodegradability, the ethoxylation products of primary aliphatic alkanols and alkenols are of particular practical interest.
Typische Vertreter für die erfindungsgemäß verwendbaren nichtionischen Tenside mit einem mittleren Ethoxylierungsgrad von 2 bis 7 sind beispielsweise die Verbindungen Kokosfettalkohol-3-EO (EO = Ethylenoxid), Talgfettalkohol-5-EO, Oleyl-/Cetylalkohol-5-EO (Jodzahl 30 bis 50), Talgfettalkohol-7-EO, synth.-C 12-C16-Fett-alkohol-6-EO, C11-C15-Oxoalkohol-3-EO, C14/C15 -Oxoal-kohol-7-EO, i-C15-C17-Alkandiol-5-EO (i = innenständig); sek.-C11-C15-Alkohol-4-EO.Typical representatives of the nonionic surfactants which can be used according to the invention and have an average degree of ethoxylation of 2 to 7 are, for example, the compounds coconut fatty alcohol 3-EO (EO = ethylene oxide), tallow fatty alcohol 5-EO, oleyl / cetyl alcohol 5-EO (iodine number 30 to 50 ), Tallow fatty alcohol 7-EO, synthetic C 12 -C 16 fatty alcohol 6-EO, C 11 -C 15 oxo alcohol 3-EO, C 14 / C 15 oxo alcohol 7-EO , iC 15 -C 17 alkanediol-5-EO (i = internal); sec-C 11 -C 15 alcohol-4-EO.
Beispielhafte Vertreter für die nicht ionischen Tenside mit einem mittleren Ethoxylierungsgrad von 8 bis 20, insbesondere 9 bis 15, sind die Verbindungen Kokosfettalko-hol-12-EO, synth.-C15/C18-Fettalkohof-9-EO, Oleyl- /Cetyl-alkohol-10-EO, Talgfettalkohol-14-EO, C1l-C1S-Oxoalko-hol-13-EO, C15-C18-Oxoalkohol-15-EO, i-C15-C17-Alkan-diol-9-EO, C14/C15-Oxoalkohol-11-EO, sek.-C11-C15-Alko-hol-9-EO.Exemplary representatives for the non-ionic surfactants with an average degree of ethoxylation of 8 to 20, in particular 9 to 15, are the compounds coconut fatty alcohol 12-EO, synthetic C 15 / C 18 fatty alcohol 9-EO, oleyl / Cetyl-alcohol-10-EO, tallow fatty alcohol-14-EO, C 1l -C 1S -Oxoalko-hol-13-EO, C 15 -C 18 -Oxoalcohol-15-EO, iC 15 -C 17 -alkane-diol- 9-EO, C 14 / C 15 -oxoalcohol-11-EO, sec.-C 11 -C 15 -alcohol-9-EO.
Ferner sind als nichtionische Tenside die wasserlöslichen, 20 bis 250 Ethylenglykolethergruppen und 10 bis 100 Propylenglykolethergruppen enthaltenden Anlagerungsprodukte von Ethylenoxid an Polypropylenglykol, Alkylendiamin-poly-propylenglykol und an Alkylpolypropylenglykole mit 1 bis 10 Kohlenstoffatomen in der Alkylkette brauchbar, in denen die Polypropylenglykolkette als hydrophober Rest fungiert. Auch nichtionische Tenside vom Typ der Aminoxide oder Sulfoxide sind verwendbar, beispielsweise die Verbindungen N-Kokosalkyl-N,N-dimethylaminoxid, N-Hexadecyl-N,N-bis- (2,3-dihylroxypropyl) aminoxid, N-Talgalkyl-N,N-dihydroxyethylaminoxid.Also suitable as nonionic surfactants are the water-soluble adducts of ethylene oxide with polypropylene glycol, which contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups, Alkylenediamine-polypropylene glycol and useful on alkylpolypropylene glycols with 1 to 10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic radical. Nonionic surfactants of the amine oxide or sulfoxide type can also be used, for example the compounds N-cocoalkyl-N, N-dimethylamine oxide, N-hexadecyl-N, N-bis- (2,3-diethylroxypropyl) amine oxide, N-tallow alkyl-N, N-dihydroxyethylamine oxide.
Geeignete amphotere Tenside sind solche, die im Molekül sowohl saure Gruppen, wie z. B. Carboxvl-, Sulfonsäure-, Schwefelsäurehalbester-, Phosphonsäure- und Phosphorsäureteilestergruppen, als auch basische Gruppen, wie z. 8. primäre, sekundäre, tertiäre und quartäre Ammoniumgruppen enthalten. Amphotere Verbindungen mit quartären Ammoniumgruppen gehören zum Typ der Betaine oder zwitterionischen Tenside. Hierbei handelt es sich insbesondere um Derivate aliphatischer quartärer Ammoniumverbindungen, in denen einer der aliphatischen Reste aus einen C8 -C18-Rest besteht und ein weiterer eine anionische wasserlöslich machende Carboxy-, Sulfo- oder Sulfato-Gruppe enthält. Typische Vertreter derartiger oberflächenaktiver Betaine sind beispielsweise die Verbindungen 3-(N-Hexadecyl-N,N-dimethylammonio)-propansulfonat, 3-(N-Talgatkyl-N,N-dimethylammonio)-2-hydroxypropansulfo-nat, 3-(N-Hexadecyl-N,N-bis(2-hydroxyethyl)-ammonio)-2-hydroxypropylsulfat, 3-(N-Kokosatkyl-N,N-bis(2,3-dihydroxypropyl)-ammonio)-propansulfonat, N-Tetradecyl-N,N-dimethyl-ammonioacetat, N-Hexadecyl-N,N-bis(2,3-di-hydroxypropyl)-ammonioacetat.Suitable amphoteric surfactants are those which contain both acidic groups such as. B. carboxvl, sulfonic acid, sulfuric acid half-ester, phosphonic acid and phosphoric acid partial ester groups, as well as basic groups, such as. 8. Contain primary, secondary, tertiary and quaternary ammonium groups. Amphoteric compounds with quaternary ammonium groups belong to the type of betaines or zwitterionic surfactants. These are, in particular, derivatives of aliphatic quaternary ammonium compounds in which one of the aliphatic radicals consists of a C 8 -C 18 radical and another contains an anionic water-solubilizing carboxy, sulfo or sulfato group. Typical representatives of such surface-active betaines are, for example, the compounds 3- (N-hexadecyl-N, N-dimethylammonio) propane sulfonate, 3- (N-tallowate-N, N-dimethylammonio) -2-hydroxypropane sulfonate, 3- (N- Hexadecyl-N, N-bis (2-hydroxyethyl) -ammonio) -2-hydroxypropyl sulfate, 3- (N-coco-alkyl-N, N-bis (2,3-dihydroxypropyl) -ammonio) propane sulfonate, N-tetradecyl-N , N-dimethyl-ammonioacetate, N-hexadecyl-N, N-bis (2,3-di-hydroxypropyl) ammonium acetate.
Zu den erfindungsgemäß verwendbaren wasserlöslichen organischen Polymeren gehören wasserlösliche Polyethylenglykole mit einem Molgewicht zwischen 300 000 und 4 000 000, vorzugsweise zwischen 500 000 und 1 000 000, die in bekannter Weise dadurch hergestellt werden, daß man Ethylenglykole einem Polykondensationsprozeß unterwirft. Man kann sie auch als Kondensationspolymere des Ethylenoxids mit Ethylenglykol oder Wasser auffassen. Sie besitzen die allgemeine Formel HO(-CH2-CH2-0)n H, wobei n im Falle der erfindungsgemäß eingesetzten Polyethylenglykole zwischen 4 800 und 64 800 variieren kann. Derartige Polymere sind auch im Handel erhältlich und werden z. B. von der Firma Union Carbon Carbide Corporation (UCC) unter dem Namen "POLYOXm"vertrieben.The water-soluble organic polymers which can be used according to the invention include water-soluble polyethylene glycols with a molecular weight between 300,000 and 4,000,000, preferably between 500,000 and 1,000,000, which are prepared in a known manner by subjecting ethylene glycols to a polycondensation process. They can also be considered as condensation polymers of ethylene oxide with ethylene glycol or water. They have the general formula HO (-CH 2 -CH 2 -0) n H, where n can vary between 4,800 and 64,800 in the case of the polyethylene glycols used according to the invention. Such polymers are also commercially available and z. B. from Union Carbon Carbide Corporation (UCC) under the name "POLYOXm".
Zu den wasserlöslichen nichtionischen Polymeren gehören ferner die Polyvinylalkohole und die Polyvinylpyrrolidone. Polyvinylalkohole können durch Hydrolyse von Polyvinylacetat hergestellt werden. Sie besitzen die allgemeine Formel (-CH2-CH(OH)-)n und Molgewichte von etwa 13 400 bis 250 000, vorzugsweise 80 000 bis 100 000. Sie können von der Hydrolysereaktion noch geringe Anteile an Acetylresten enthalten, diese sollen jedoch weniger als 40, vorzugsweise weniger als 15 und insbesondere weniger als 2 und möglichst 0 Prozent betragen. Polyvinylalkohole werden beispielsweise von der Firma Wacker-Chemie unter der Bezeichnung "POLYVIOLm" oder von de Firma Nippon Gohsei unter der Bezeichnung "GOHSENOLE®" gehandelt.The water-soluble nonionic polymers also include the polyvinyl alcohols and the polyvinylpyrrolidones. Polyvinyl alcohols can be produced by hydrolysis of polyvinyl acetate. They have the general formula (-CH 2 -CH (OH) -) n and molecular weights of about 13,400 to 250,000, preferably 80,000 to 100,000. They can still contain small amounts of acetyl radicals from the hydrolysis reaction, but these should be less than 40, preferably less than 15 and in particular less than 2 and if possible 0 percent. Polyvinyl alcohols are sold, for example, by Wacker-Chemie under the name "POLYVIOL m " or by Nippon Gohsei under the name "GOHSENOLE®".
Polyvinylpyrrolidone sind ebenfalls handelsübliche Polymere. Sie werden unter anderem von der Firma BASF unter dem Namen "LUVISKOLE®" vertrieben. Ihr Polymerisationsgrad liegt für den erfindungsgemäßen Einsatz zwischen 100 und 9 000, vorzugsweise zwischen 350 und 7 500, die Mol-060014 gewichte zwischen etwa 10 000 und 1 000 000, vorzugsweise zwischen etwa 30 000 und 850 000.Polyvinylpyrrolidones are also commercially available polymers. They are marketed by the company BASF, among others, under the name "LUVISKOLE®". Their degree of polymerization for the use according to the invention is between 100 and 9,000, preferably between 350 and 7,500, the mol-060014 weights between approximately 10,000 and 1,000,000, preferably between approximately 30,000 and 850,000.
Celluloseether, Polysaccharide, Proteine und Polyacrylamide stellen je nach Substitutions- beziehungsweise Umsetzungsgrad wasserlösliche sogenannte schwachanionische Polymere dar. Darunter versteht man solche Polymere, deren Ladungsdichte größer als 0, aber nicht größer als 0,5, vorzugsweise größer als 0, aber nicht größer als 0,2 und insbesondere größer als 0, aber nicht größer als 0,01 ist. Die Definition für die Ladungsdichte entspricht dabei folaender Formel:
Zu den Celluloseethern mit einer Ladungsdichte größer als 0, aber nicht größer als 0,5, vorzugsweise größer als 0, aber nicht größer als 0,2 gehören vor allen solche, deren 2-prozentige wäßrige Lösung bei 20 °C eine Viskosität von größer als 50 m Pa. s, vorzugsweise von größer als 100 m Pa. s aufweist. Hierzu gehören die von der Firma Henkel unter der Typensammelbezeichnung "CULMINALm" Behandelten Methylcellulosen (MC), Methylhydroxyethylcellulosen (MHEC), Methylhydroxypropylcellulosen (MHPC), Carboxymethylmethylcellulose (CMMC) und Hydroxyethylcellulosen (HEC), außerdem Methylhydroxybutylcellulose (MHBC) und Hydroxybutylcellulose, wie sie von der Dow Chemicals unter dem Markennamen Methocel® gehandelt werden. Diese Celluloseether werden aus der Klasse der anionischen Polymeren bevorzugt.The cellulose ethers with a charge density greater than 0, but not greater than 0.5, preferably greater than 0, but not greater than 0.2 include, above all, those whose 2 percent aqueous solution has a viscosity of greater than 20 ° C. 50 m Pa. s, preferably greater than 100 m Pa. s. This includes, by Henkel under the type collective term "CULMINAL m" treated methylcellulose (MC), methylhydroxyethylcelluloses (MHEC), methyl hydroxypropyl cellulose (MHPC), carboxymethyl (CMMC) and hydroxyethyl cellulose (HEC), also methylhydroxybutyl (MHBC) and hydroxybutyl as by Dow Chemicals under the brand name Methocel®. These cellulose ethers are preferred from the class of anionic polymers.
Polysaccharide kommen insbesondere in Derivatform, zum Beispiel als Stärkeether (zum Beispiel Solvitosee der Firma W. A. Scholtens, Holland) in Betracht, wobei auch hier die Ladungsdichte von 0,5 bis kleiner als 0,2 ausschlaggebend ist. Ebenso gehören Alginate ("ALGIPON®" der Firma Henkel) zu dieser Polymerenklasse.Polysaccharides are particularly suitable in derivative form, for example as starch ethers (for example Solvitose e from WA Scholtens, Holland), the charge density from 0.5 to less than 0.2 also being decisive here. Alginates ("ALGIPON®" from Henkel) also belong to this class of polymers.
Bei den erfindungsgemäß einsetzbaren Proteinen handelt es sich beispielsweise um Natriumcaseinat und Gelatine, die beide unter anderem von der Firma Milac, Hamburg vertrieben werden.The proteins which can be used according to the invention are, for example, sodium caseinate and gelatin, both of which are sold, inter alia, by the company Milac, Hamburg.
Polyacrylamide, d. h. Polymere und Copolymere des Acrylamids mit der allgemeinen Formel (-CH2-CH(CONH2)-)n mit Molgewichten von 300 000 bis 8 000 000, vorzugsweise 500 000 bis 2 000 000 werden unter anderem von der Firma Schuchardt vertrieben und eignen sich ebenfalls für den erfindungsgemäßen Einsatz. Zur pH-Wert-Regulierung eignen sich als saure Substanzen übliche anorganische oder organische Säuren oder saure Salze, wie beispielsweise Salzsäure, Schwefelsäure, Bisulfate der Alkalien, Aminosulfonsäure, Phosphorsäure oder andere Säuren des Phosphors, insbesondere die anhydrischen Säuren des Phosphors bzw. deren Salze oder deren sauer reagierende feste Verbindungen mit Harnstoff oder anderen niederen Carbonsäureaniden, Teilamide der Phosphorsäuren oder der anhydrischen Phosphorsäure, Citronensäure, Weinsäure, Milchsäure unridergleichen. Als basische Substanzen können auch organische oder anorganische Verbindungen wie Alkancmine, nämlich Mono-, Di- oder Triethanolamin oder Ammoniak zugesetzt werden. Zur Einstellung eines schwach alkalischen pH-Wertes sind ferner alkalisch reagierende Builder-Substanzen und Waschalkalien, wie z. B. Natriumtripolyphosphat, Natriumcarbonat und Natriumbicarbonat, Kaliumcarbonat und -bicarbonat, Natriumsilikat sowie die Natriumalumosilikate geeignet.Polyacrylamides, ie polymers and copolymers of acrylamide with the general formula (-CH 2 -CH (CONH 2 ) -) n with molecular weights of 300,000 to 8,000,000, preferably 500,000 to 2,000,000, are marketed by Schuchardt, among others and are also suitable for use in accordance with the invention. Suitable pH-regulating agents are conventional inorganic or organic acids or acid salts, such as hydrochloric acid, sulfuric acid, bisulfates of the alkalis, aminosulfonic acid, as acidic substances, Phosphoric acid or other acids of phosphorus, in particular the anhydrous acids of phosphorus or their salts or their acid-reacting solid compounds with urea or other lower carboxylic acid anides, partial amides of phosphoric acids or anhydrous phosphoric acid, citric acid, tartaric acid, lactic acid are unequal. Organic or inorganic compounds such as alkane mines, namely mono-, di- or triethanolamine or ammonia can also be added as basic substances. To set a weakly alkaline pH, alkaline builder substances and washing alkalis, such as. As sodium tripolyphosphate, sodium carbonate and sodium bicarbonate, potassium carbonate and bicarbonate, sodium silicate and the sodium aluminosilicates are suitable.
Zur Herstellung der Reinigungsmittel in flüssiger Form kann man an sich bekannte Lösungsvermittler einarbeiten, wozu außer den wasserlöslichen organischen Lösungsmitteln wie insbesondere niedermolekularen aliphatischen Alkoholen mit 1 bis 4 Kohlenstoffatomen auch die sogenannten hydrotropen Stoffe vom Typ der niederen Alkylarylsulfonate beispielsweise Toluol-, Xylol- oder Cumolsulfonat gehören. Sie können auch in Form ihrer Natriun- und/oder Kalium- und/oder Alkylaminosalze vorliegen. Als Lösungsvermittler sind weiterhin wasserlösliche organische Lösungsmittel verwendbar, insbesondere solche mit Siedepunkten oberhalb von 75°C wie beispielsweise die Ether aus gleich- oder verschiedenenartigen mehrwertigen Alkoholen oder die Teilether aus mehrwertigen Alkoholen. Hierzu gehören beispielsweise Di- oder Triethylenglykolpolyglycerine sowie die Teilether aus Ethylenglykol, Propylenglykol, Butylenglykol oder Olycerin mit aliphatischen, 1 bis 4 Kohlenstoffatome im Molekül enthaltenden einwertigen Alkoholen.For the preparation of the cleaning agents in liquid form, known solubilizers can be incorporated, which in addition to the water-soluble organic solvents such as, in particular, low-molecular aliphatic alcohols having 1 to 4 carbon atoms, also include the so-called hydrotropic substances of the lower alkylarylsulfonate type, for example toluene, xylene or cumene sulfonate . They can also be in the form of their sodium and / or potassium and / or alkylamino salts. Water-soluble organic solvents can also be used as solubilizers, in particular those with boiling points above 75 ° C., for example the ethers from the same or different polyhydric alcohols or the partial ethers from polyhydric alcohols. These include, for example, di- or triethylene glycol polyglycerols and also the partial ethers of ethylene glycol, propylene glycol, butylene glycol or oleacerine with aliphatic monohydric alcohols containing 1 to 4 carbon atoms in the molecule.
Als wasserlösliche oder mit Wasser emulgierbare organische Lösungsmittel kommen auch Ketone, wie Aceton, Methylethylketon sowie aliphatische, cycloaliphatische, aromatische und chlorierte Kohlenwasserstoffe, ferner die Terpenalkohole in Betracht.Suitable water-soluble or water-emulsifiable organic solvents are also ketones, such as acetone, methyl ethyl ketone and aliphatic, cycloaliphatic, aromatic and chlorinated hydrocarbons, and also the terpene alcohols.
Zur Regulierung der Viskosität empfiehlt sich gegebenenfalls ein Zusatz von höheren Polyglykolethern mit Molgewichten bis etwa 600 oder Polyglycerin. Weiterhin empfiehlt sich zur Regulierung der Viskosität ein Zusatz an Natriumchlorid und/oder Harnstoff.To regulate the viscosity, it may be advisable to add higher polyglycol ethers with molecular weights up to about 600 or polyglycerol. It is also recommended to add sodium chloride and / or urea to regulate the viscosity.
Außerdem können die Reinigungsmittel Zusätze an Farb- und Duftstoffen, Konservierungsmitteln und gewünschtenfalls auch antimikrobiell wirksamen Mittel beliebiger Art enthalten.In addition, the cleaning agents can contain additives of colors and fragrances, preservatives and, if desired, antimicrobial agents of any kind.
Als antimikrobielle Mittel kommen vorzugsweise Formaldehyd-Aminoalkohol-Kondensationsprodukte zum Einsatz. Die Produkte werden durch Umsetzung einer wäßrigen Lösung von Formaldehyd mit Aminoalkoholen, z. B. 2-Aninoethanol, 1-Aminoethanol, 1-Amino-2-propanol, 2-Aminoiso-butanol, 2(2'-Aminoethyl)-aminoethanol hergestellt.Formaldehyde-amino alcohol condensation products are preferably used as antimicrobial agents. The products are obtained by reacting an aqueous solution of formaldehyde with amino alcohols, e.g. B. 2-aminoethanol, 1-aminoethanol, 1-amino-2-propanol, 2-aminoiso-butanol, 2 (2'-aminoethyl) aminoethanol.
Weiterhin können die Reinigungsmittel beliebige organische oder anorganische Abrasivstoffe enthalten. Für die Herstellung von Scheuerpulvern ist die pulverförmige Konsistenz der Fettsäurecyanamidsalze wiederum von besonderem Vorteil.Furthermore, the cleaning agents can contain any organic or inorganic abrasives. The powdery consistency of the fatty acid cyanamide salts is again of particular advantage for the production of scouring powders.
Zum Nachweis des Reinigungseffektes der erfindungsgemäß eingesetzten Tensidkombination beim manuellen Geschirrspülen wurde der sogenannte Tellertest durchgeführt. Die Methodik ist in der Zeitschrift "Fette, Seifen, Anstrichmittel", 74 (1972), Seiten 183 bis 165 beschrieben.The so-called plate test was carried out to demonstrate the cleaning effect of the surfactant combination used according to the invention in manual dishwashing. The methodology is described in the journal "Fette, Seifen, Anstrichmittel", 74 (1972), pages 183 to 165.
Es wurden Teller mit einer Mischanschmutzung aus Eiweiß, Fett und Kohlenhydraten angeschmutzt und bei 45 °C gespült. Die Prüfprodukte wurden mit einer Dosierung von 0,1 g/I bei pulverförmigen und 0,4 g/1 bei flüssigen Produkten eingesetzt. Als Maß für die Spülwirkung dient die Anzahl an Tellern, die mit 5 1 Spülflotte sauber gespült werden = Tellerzahl.Plates with a mixed contamination of protein, fat and carbohydrates were soiled and rinsed at 45 ° C. The test products were used with a dosage of 0.1 g / l for powdery products and 0.4 g / l for liquid products. The number of plates that are rinsed clean with 5 l of washing liquid = number of plates serves as a measure of the washing effect.
Es wurden folgende Bestandteile in Gewichtsprozent gemischt:
- 54 % C12-C16-Fettsäurecyanamid-Na-Salz
- 18 % C11-C13-Alkylbenzolsulfonat, Na-Salz
- 13,5 % C12-C14-Fettalkohol-2E0-Sulfat, Na-Salz
- 4,5 % Kokosfettsäurediethanolamid
- 0,8 % Borax wasserfrei
- 1,0 % Borsäure
- Rest auf 100 % Na-Sulfat, Farb- und Duftstoffe
- Mit einem Mittel nach diesem Beispiel ließen sich 21 Teller reinigen.
- 54% C 12 -C 16 fatty acid cyanamide Na salt
- 18% C 11 -C 13 alkyl benzene sulfonate, Na salt
- 13.5% C 12 -C 14 fatty alcohol 2E0 sulfate, Na salt
- 4.5% coconut fatty acid diethanolamide
- 0.8% borax anhydrous
- 1.0% boric acid
- Rest on 100% Na sulfate, colors and fragrances
- With an agent according to this example, 21 plates could be cleaned.
Bei mengengleichem Austausch der Tensidkombination aus Beispiel 1 gegen folgende Einzeltenside ergeben sich unter gleichen Testbedingungen folgende Prüfwerte:
- Bei C12-C14-Fettalkohol-2E0-Sulfat, Na-Salz: Tellerzahl = 15,
- bei C11-C13-Alkylbenzolsulfonat, Na-Salz: Tellerzahl = 11.
- Man erkennt die synergistische Wirkung der Tensidkombination mit einem Gehalt an C12 -C16
- -Fettsäurecyanamid-Na-Salz.
- For C 12 -C 14 fatty alcohol 2E0 sulfate, Na salt: number of plates = 15,
- for C 11 -C 13 alkylbenzenesulfonate, Na salt: number of plates = 11.
- The synergistic effect of the surfactant combination containing C 12 -C 16 can be seen
- -Fatty acid cyanamide sodium salt.
{Mengen in Gewichtsprozent)
- 16 % C14-Fettsäurecyanamid-Na-Salz
- 4% C12-C14-Fettalkohol-2E0-Sulfat, Na-Salz
- 5 % Ethanol
- 5 % Harnstoff
- 0,1 % 2-Hydroxy-2',4,4'-trichlordiphenylether als Antimikrobikum
- Rest auf 100 % Wasser, Farb- und Duftstoffe
- Tellerzahl = 22.
- 16% C14 fatty acid cyanamide Na salt
- 4% C 12 -C 14 fatty alcohol 2E0 sulfate, Na salt
- 5% ethanol
- 5% urea
- 0.1% 2-hydroxy-2 ', 4,4'-trichlorodiphenyl ether as an antimicrobial
- Rest on 100% water, colors and fragrances
- Number of plates = 22.
Ersetzt man in Beispiel 2 das Fettsäurecyanamidsalz gegen C11-C13-Alkylbenzolsulfonat, Na-Salz, so ergibt der gleiche Test eine Tellerzahl von 16.If in Example 2 the fatty acid cyanamide salt is replaced by C 11 -C 13 alkylbenzenesulfonate, Na salt, the same test gives a plate number of 16.
(Mengen in Gewichtsprozent)
- 12 % C12-C16-Fettsäurecyanamid-Na-Salz
- 12% C12-C14-Fettalkohol-2E0-Sulfat, Na-Salz
- 4% Ethanol
- 8 % Harnstoff
- Rest auf 100 % Wasser, Farb- und Duftstoffe.
- Tellerzahl = 23.
- 12% C 12 -C 16 fatty acid cyanamide Na salt
- 12% C 12 -C 14 fatty alcohol 2E0 sulfate, Na salt
- 4% ethanol
- 8% urea
- Rest on 100% water, colors and fragrances.
- Number of plates = 23.
Ersetzt man in diesem Beispiel das Fettsäurecyanamidsalz gegen das Alkylbenzolsulfonat, so ergibt sich eine Tellerzahl von 17.Replacing the fatty acid cyanamide salt with the alkylbenzenesulfonate in this example results in a plate number of 17.
Die folgenden Beispiele betreffen flüssige Allzweckreinigungsmittel. Das Reinigungsvermögen der Rezepturen mit der Kombination Fettsäurecyanamidsalz plus weiteres Tensid bzw. polymere Substanz wurde nach der folgenden Methode ermittelt:The following examples are for all-purpose liquid detergents. The cleaning ability of the recipes with the combination of fatty acid cyanamide salt plus additional surfactant or polymeric substance was determined using the following method:
Das zu prüfende Reinigungsmittel wird auf eine künstlich angeschmutzte Kunststoffoberfläche gegeben. Als künstliche Anschmutzung wird ein Gemisch aus Ruß, Maschinenöl, Triglycerid gesättigter Fettsäuren und niedersiedendem aliphatischen Kohlenwasserstoff verwendet. Die Testfläche von 26 x 28 cm wird mit Hilfe eines Flächenstreichers gleichmäßig mit 2 g der künstlichen Anschmutzung beschichtet.The cleaning agent to be tested is placed on an artificially soiled plastic surface. A mixture of carbon black, machine oil, triglyceride, saturated fatty acids and low-boiling aliphatic hydrocarbon is used as artificial soiling. The test area of 26 x 28 cm is evenly coated with 2 g of the artificial soiling with the help of a surface coater.
Ein Kunststoffschwamm wird jeweils mit 12 ml der zu prüfenden Reinigungsmittellösung getränkt und maschinell auf der Testfläche bewegt. Nach 6 Wischbewegungen wird die gereinigte Testfläche unter fließendes Wasser gehalten und der lose sitzende Schmutz entfernt. Die Reinigungswirkung, d. h., der Weißgrad der so gereinigten Kunststoffoberfläche wird mit einem photoelektronischen Farbmeßgerät LF 90 (Dr. B. Lange) gemessen. Als Weiß-Standard dient die saubere weiße Kunststoffoberfläche.A plastic sponge is soaked with 12 ml of the detergent solution to be tested and moved mechanically on the test surface. After 6 wiping movements, the cleaned test area is kept under running water and the loose dirt is removed. The cleaning effect, d. that is, the whiteness of the plastic surface cleaned in this way is measured using an LF 90 photoelectronic colorimeter (Dr. B. Lange). The clean white plastic surface serves as the white standard.
Da bei der Messung der sauberen Oberfläche auf 100 % eingestellt und die angeschmutzte Fläche mit 0 angezeigt wird, sind die abgelesenen Werte bei den gereinigten Kunststoff-Flächen mit dem Prozentgehalt Reinigungsvermögen (% RV) gleichzusetzen. Bei den nachstehenden Versuchen sind die angegebenen % RV-Werte die nach dieser Methode ermittelten Werte für das Reinigungsvermögen der untersuchten Reinigungsmittet. Sie stellen jeweils Mittelwerte aus 4fachen Bestimmungen dar.Since the measurement of the clean surface is set to 100% and the soiled area is displayed with 0, the read values for the cleaned plastic areas are to be equated with the percentage cleaning capacity (% RV). In the experiments below, the% RV values given are the values determined by this method for the cleaning ability of the cleaning agents examined. They represent mean values from fourfold determinations.
Diese Methode gestattet einen gut reproduzierbaren Vergleich, solange gleichartige Testmaterialien verwendet werden.This method allows a reproducible comparison as long as similar test materials are used.
- 2 % Laurinsäurecyanamid-Na-Salz2% lauric acid cyanamide sodium salt
- 8 % C11-C13-Alkylbenzolsulfonat, Na-Salz8% C 11 -C 13 alkyl benzene sulfonate, Na salt
- 3 % Pentanatriumtripolyphosphat3% pentasodium tripolyphosphate
- 2 % Na-Cumolsulfonat2% Na cumene sulfonate
- Rest auf 100 % Wasser, Farb- und DuftstoffeRest on 100% water, colors and fragrances
Nach der vorstehend angegebenen Testmethode ergibt das Reinigungsmittel des Beispiels 4 in 1%iger Lösung in Leitungswasser von 16 °d bei Raumtemperatur einen Wert von 85 % RV.According to the test method given above, the cleaning agent of Example 4 in 1% solution in tap water of 16 ° d at room temperature gives a value of 85% RV.
Setzt madiagegen anstelle der Tensidkombination mengengleich jeweils das angegebene Einzeltensid ein, so erhält man unter gleichen Testbedingungen folgende Werte:
- Gesamttensidmenge als Alkylbenzolsulfonat vorliegend:
- 80 % RV,
- Total amount of surfactant present as alkylbenzenesulfonate:
- 80% RV,
Gesamttensidmenge als Laurinsäurecyanamidsalz: 52 % RV.Total amount of surfactant as lauric acid cyanamide salt: 52% RV.
Man erkennt den Synergismus, der sich hier durch Kombination beider Tenside im Verhältnis 1: 4 ergibt.You can see the synergism that results from the combination of both surfactants in a ratio of 1: 4.
(Mengen in Gewichtsprozent)
- 10% C12-C18-Fettsäurecyanamid a) = Na-Salz
- b) = Li-Salz
- 3 % Pentanatriumtripolyphosphat
- 0,2 % Polyethylenglykol mit einem Molgewicht von etwa 600.000 (Handelsprodukt "POLYOX WSR 205®" der Firma UCC)
- 5 % Harnstoff
- Rest auf 100 % Wasser, Farb- und Duftstoffe
- RV-Wert der 1 %igen Lösung in Leitungswasser a) = 74 % RV, b) = 75 %.
- 10% C 12 -C 18 fatty acid cyanamide a) = Na salt
- b) = Li salt
- 3% pentasodium tripolyphosphate
- 0.2% polyethylene glycol with a molecular weight of about 600,000 (commercial product "POLYOX WSR 205®" from UCC)
- 5% urea
- Rest on 100% water, colors and fragrances
- RV value of the 1% solution in tap water a) = 74% RV, b) = 75%.
Zum Vergleich wurde ein handelsüblicher Haushaltsreiniger, der 8.5 % C12-C18-Alkansulfonat + 2,8 % aliphatisches nichtionisches Tensid und ferner 4 % Pentanatriumtripolyphosphat enthielt, geprüft. Er zeigte als 1%ige Lösung einen Wert von 42 % RV.For comparison, a commercial household cleaner containing 8.5% C 12 -C 18 alkanesulfonate + 2.8% aliphatic nonionic surfactant and also 4% pentasodium tripolyphosphate was tested. It showed a value of 42% RV as a 1% solution.
Zum weiteren Vergleich wurde in Beispiel 5a) das Fettsäurecyanamidsalz mengengleich durch C12-C18-Alkansulfonat ersetzt. Man erhielt dann einen Wert von 50 % RV. Das Beispiel zeigt, daß Fettsäurecyanamidsalze auch durch geringe Zusätze an Polymeren eine große Steigerung der Reinigungswirkung erfahren, so daß Reinigungsmittel, die diese enthalten, denen des Standes der Technik überlegen sind.For further comparison in Example 5a) the fatty acid cyanamide salt was replaced by C 12 -C 18 alkanesulfonate. A value of 50% RV was then obtained. The example shows that fatty acid cyanamide salts experience a great increase in the cleaning action even through small additions of polymers, so that cleaning agents which contain them are superior to those of the prior art.
(Mengen in Gewichtsprozent)(Quantities in percent by weight)
2 % Fettsäurecyanamid-Na-Salz
- a) Fettsäurerest = C12-C16
- b) Fettsäurerest = C14-C18
- 8 % C11-C13-Alkylbenzolsulfonat, Na-Salz
- 3 % Pentanatriumtripolyphosphat
- 0,2 % Polyox WSR 205, wie in den Beispielen 5
- 5 % Harnstoff
- 2 % Butylglykol
- Rest auf 100 % Wasser, Farb- und Duftstoffe
- RV der 1%igen Lösung, Beispiel 6a): 85 %
- 6b): 75 %
- a) fatty acid residue = C 12 -C 16
- b) fatty acid residue = C 14 -C 18
- 8% C 11 -C 13 alkyl benzene sulfonate, Na salt
- 3% pentasodium tripolyphosphate
- 0.2% Polyox WSR 205 as in Examples 5
- 5% urea
- 2% butyl glycol
- Rest on 100% water, colors and fragrances
- RV of the 1% solution, example 6a): 85%
- 6b): 75%
Ersetzte man in diesen Beispielen die Fettsäurecyanamidsalze mengengleich durch ein C11-C14-Alkandiol + 10 EO, so erhielt man den Wert: 70 % RV. Das Beispiel zeigt, daß bei gleichzeitiger Verwendung einer synergistisch wirkenden Tensidkombination mit Fettsäurecyanamidsalzen und eines Polymeren eine höhere Wirkungssteigerung erzielt wird als mit bekannten und bereits als hochwirksam eingestuften Substanzen.If in these examples the fatty acid cyanamide salts were replaced by a C 11 -C 14 alkanediol + 10 EO, the value was: 70% RV. The example shows that when a synergistic surfactant combination with fatty acid cyanamide salts and a polymer is used at the same time, a greater increase in activity is achieved than with known substances which have already been classified as highly effective.
(Mengen in Gewichtsprozent)
- 6% Fettsäurecyanamid-Na-Salz
- Fettsäure = C12-C16 6 % C11-C13-Alkylbenzolsulfonat, Na-Salz
- 0,1 % bzw. 0,3 % Polymeres
- a) 0,1 % Polyox WSR 205 gemäß Beispiele 5
- b) 0,3 % Methylhydroxypropylcellulose 3 % Cumolsulfonat
- 15 % Anlagerungsprodukt von Formaldehyd an Monoethanolamin als Antimikrobikum
- Rest auf 100 % Wasser, Farb- und Duftstoffe
- RV der 1%igen Lösungen Beispiel 7a): 85 %
- 7b): 73 %
- 6% fatty acid cyanamide Na salt
- Fatty acid = C 12 -C 16 6% C11-C13 alkylbenzenesulfonate, Na salt
- 0.1% or 0.3% polymer
- a) 0.1% Polyox WSR 205 according to Example 5
- b) 0.3% methyl hydroxypropyl cellulose 3% cumene sulfonate
- 15% adduct of formaldehyde with monoethanolamine as an antimicrobial
- Rest on 100% water, colors and fragrances
- RV of the 1% solutions Example 7a): 85%
- 7b): 73%
Diese Beispiele zeigen, daß die Fettsäurecyanamidsalze auch in Abwesenheit von Gerüstsubstanzen hohe Reinigungsleistungen erbringen.These examples show that the fatty acid cyanamide salts provide high cleaning performance even in the absence of builders.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT84106289T ATE21924T1 (en) | 1983-06-09 | 1984-06-01 | USE OF FATTY ACID CYANAMIDE SALTS AS SURFACTANTS FOR CLEANING HARD SURFACES. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833320727 DE3320727A1 (en) | 1983-06-09 | 1983-06-09 | USE OF FATTY ACID CYANAMIDES AS A SURFACTANT FOR CLEANING HARD SURFACES |
| DE3320727 | 1983-06-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0131138A1 EP0131138A1 (en) | 1985-01-16 |
| EP0131138B1 true EP0131138B1 (en) | 1986-09-03 |
Family
ID=6200965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84106289A Expired EP0131138B1 (en) | 1983-06-09 | 1984-06-01 | Use of fatty acid cyanamides as surface-active agents in the cleaning of hard surfaces |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4569782A (en) |
| EP (1) | EP0131138B1 (en) |
| JP (1) | JPS606792A (en) |
| AT (1) | ATE21924T1 (en) |
| DE (2) | DE3320727A1 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3413292A1 (en) * | 1984-04-09 | 1985-10-17 | Henkel KGaA, 4000 Düsseldorf | TEXTILE DETERGENT FOR COLORED TEXTILES |
| US4954292A (en) * | 1986-10-01 | 1990-09-04 | Lever Brothers Co. | Detergent composition containing PVP and process of using same |
| GB8926904D0 (en) * | 1989-11-28 | 1990-01-17 | Unilever Plc | Thickening system |
| US5585340A (en) * | 1990-12-14 | 1996-12-17 | Henkel Corporation | Substantially phosphate free acidic cleaner for plastics |
| ES2089495T3 (en) * | 1990-12-14 | 1996-10-01 | Henkel Corp | CLEANER MODERALLY ACID AND PRACTICALLY FREE OF PHOSPHATES FOR PLASTIC MATERIALS. |
| US5480586A (en) * | 1991-04-15 | 1996-01-02 | Colgate-Palmolive Co. | Light duty liquid detergent compostion comprising a sulfosuccinamate-containing surfactant blend |
| DE4307473A1 (en) * | 1993-03-10 | 1994-09-15 | Henkel Ecolab Gmbh & Co Ohg | Mop care products |
| GB9310365D0 (en) † | 1993-05-18 | 1993-06-30 | Unilever Plc | Hard surface cleaning compositions comprising polymers |
| DE4319287A1 (en) * | 1993-06-11 | 1994-12-15 | Henkel Kgaa | Pourable liquid aqueous detergent concentrates |
| US6328816B1 (en) * | 1995-07-25 | 2001-12-11 | Henkel Corporation | Composition and method for degreasing metal surfaces |
| US20060040843A1 (en) * | 2004-08-19 | 2006-02-23 | Kinnaird Michael G | Sodium-free, lithium-containing concrete cleaning compositions and method for use thereof |
| GB0501831D0 (en) * | 2004-10-21 | 2005-03-09 | Unilever Plc | Improved detergent composition |
| GB0525566D0 (en) * | 2005-12-16 | 2006-01-25 | Pilkington Plc | Glass storage |
| JP6051111B2 (en) * | 2013-06-05 | 2016-12-27 | ライオン株式会社 | Liquid detergent for kitchen |
| DE102019130148A1 (en) * | 2019-11-08 | 2021-05-12 | Alzchem Trostberg Gmbh | Use of acyl cyanamides or their salts to regulate plant growth |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB428091A (en) * | 1932-12-14 | 1935-05-07 | Heinz Hunsdiecker | Improvements in or relating to the treatment of textile materials and the preparation of dispersions |
| DE708428C (en) * | 1932-12-15 | 1941-07-21 | Boehme Fettchemie Ges M B H | Process for the preparation of alkali salts of monoacylcyanamides |
| JPS5124569B2 (en) * | 1973-09-05 | 1976-07-24 | ||
| SE424740B (en) * | 1976-07-28 | 1982-08-09 | Stora Kopparbergs Bergslags Ab | MANUFACTURING THE RAJAR BY MELT REDUCTION |
| DE2709690B1 (en) * | 1977-03-05 | 1978-05-11 | Henkel Kgaa | Liquid detergent |
| DE2840463C2 (en) * | 1978-09-16 | 1983-12-22 | Henkel KGaA, 4000 Düsseldorf | Using a liquid agent to clean hard surfaces |
| DE2913049A1 (en) * | 1979-03-31 | 1980-10-16 | Henkel Kgaa | LIQUID DETERGENT |
| DE3202213A1 (en) * | 1982-01-25 | 1983-08-04 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR PRODUCING THE ALKALINE METAL SALTS OF ACYLCYANAMIDES |
-
1983
- 1983-06-09 DE DE19833320727 patent/DE3320727A1/en not_active Withdrawn
-
1984
- 1984-06-01 DE DE8484106289T patent/DE3460610D1/en not_active Expired
- 1984-06-01 AT AT84106289T patent/ATE21924T1/en not_active IP Right Cessation
- 1984-06-01 EP EP84106289A patent/EP0131138B1/en not_active Expired
- 1984-06-05 JP JP59114008A patent/JPS606792A/en active Pending
- 1984-06-08 US US06/618,794 patent/US4569782A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| ATE21924T1 (en) | 1986-09-15 |
| DE3320727A1 (en) | 1984-12-13 |
| US4569782A (en) | 1986-02-11 |
| EP0131138A1 (en) | 1985-01-16 |
| DE3460610D1 (en) | 1986-10-09 |
| JPS606792A (en) | 1985-01-14 |
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