EP0104434A2 - Liquid washing and cleaning composition virtually devoid of inorganic builder salts - Google Patents
Liquid washing and cleaning composition virtually devoid of inorganic builder salts Download PDFInfo
- Publication number
- EP0104434A2 EP0104434A2 EP83108321A EP83108321A EP0104434A2 EP 0104434 A2 EP0104434 A2 EP 0104434A2 EP 83108321 A EP83108321 A EP 83108321A EP 83108321 A EP83108321 A EP 83108321A EP 0104434 A2 EP0104434 A2 EP 0104434A2
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- European Patent Office
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- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 239000007788 liquid Substances 0.000 title claims abstract description 15
- 150000003839 salts Chemical class 0.000 title claims abstract description 8
- 238000005406 washing Methods 0.000 title description 11
- 238000004140 cleaning Methods 0.000 title description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 17
- 239000000194 fatty acid Substances 0.000 claims abstract description 17
- 229930195729 fatty acid Natural products 0.000 claims abstract description 17
- 239000000344 soap Substances 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000003599 detergent Substances 0.000 claims abstract description 13
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 11
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- 102000035195 Peptidases Human genes 0.000 claims abstract description 6
- 108091005804 Peptidases Proteins 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 239000011591 potassium Substances 0.000 claims abstract description 4
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 16
- 102000004190 Enzymes Human genes 0.000 claims description 15
- 108090000790 Enzymes Proteins 0.000 claims description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 150000005846 sugar alcohols Polymers 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 5
- 239000012459 cleaning agent Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 235000021281 monounsaturated fatty acids Nutrition 0.000 claims description 2
- 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 claims description 2
- 235000003441 saturated fatty acids Nutrition 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- 239000011877 solvent mixture Substances 0.000 claims description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 abstract description 6
- 239000000470 constituent Substances 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 229940088598 enzyme Drugs 0.000 description 14
- 150000002191 fatty alcohols Chemical class 0.000 description 14
- BXWNKGSJHAJOGX-UHFFFAOYSA-N n-hexadecyl alcohol Natural products CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 10
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- -1 ether radical Chemical class 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 4
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N 1-Tetradecanol Natural products CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 4
- 244000060011 Cocos nucifera Species 0.000 description 4
- 235000013162 Cocos nucifera Nutrition 0.000 description 4
- 229940120146 EDTMP Drugs 0.000 description 4
- 229960000541 cetyl alcohol Drugs 0.000 description 4
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 229940055577 oleyl alcohol Drugs 0.000 description 4
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004365 Protease Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 244000269722 Thea sinensis Species 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 239000004435 Oxo alcohol Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 235000014666 liquid concentrate Nutrition 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- AOHAPDDBNAPPIN-UHFFFAOYSA-N myristicinic acid Natural products COC1=CC(C(O)=O)=CC2=C1OCO2 AOHAPDDBNAPPIN-UHFFFAOYSA-N 0.000 description 2
- 229940043348 myristyl alcohol Drugs 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N n-hexadecanoic acid Natural products CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- XLIREHXMRXKQIV-UHFFFAOYSA-N (1-amino-1-phosphonobutyl)phosphonic acid Chemical compound CCCC(N)(P(O)(O)=O)P(O)(O)=O XLIREHXMRXKQIV-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- DJYWKXYRGAMLRE-QXMHVHEDSA-N (z)-icos-9-en-1-ol Chemical compound CCCCCCCCCC\C=C/CCCCCCCCO DJYWKXYRGAMLRE-QXMHVHEDSA-N 0.000 description 1
- VWFBLSZIALSICG-UHFFFAOYSA-N 1,2-dimethyl-1-phosphonobutane-1,2,3-tricarboxylic acid Chemical compound OC(=O)C(C)C(C)(C(O)=O)C(C)(C(O)=O)P(O)(O)=O VWFBLSZIALSICG-UHFFFAOYSA-N 0.000 description 1
- SLSIAHSHYAMVPP-UHFFFAOYSA-N 1-methyl-1-phosphonobutane-1,2,3-tricarboxylic acid Chemical compound OC(=O)C(C)C(C(O)=O)C(C)(C(O)=O)P(O)(O)=O SLSIAHSHYAMVPP-UHFFFAOYSA-N 0.000 description 1
- PHCGWDSPSARICX-UHFFFAOYSA-N 1-phosphonobutane-1,2,3-tricarboxylic acid Chemical compound OC(=O)C(C)C(C(O)=O)C(C(O)=O)P(O)(O)=O PHCGWDSPSARICX-UHFFFAOYSA-N 0.000 description 1
- COKIOUWMXONTKQ-UHFFFAOYSA-N 1-phosphonopropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(C(O)=O)P(O)(O)=O COKIOUWMXONTKQ-UHFFFAOYSA-N 0.000 description 1
- NUZPBDSCFJGAEJ-UHFFFAOYSA-N 2-(1,1-diphosphonoethyl)-2-methylbutanedioic acid Chemical compound OC(=O)CC(C)(C(O)=O)C(C)(P(O)(O)=O)P(O)(O)=O NUZPBDSCFJGAEJ-UHFFFAOYSA-N 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 238000009896 oxidative bleaching Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000002797 proteolythic effect Effects 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000004753 textile 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38618—Protease or amylase in liquid compositions only
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
- C11D10/045—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38663—Stabilised liquid enzyme compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- the agents are essentially free of inorganic skeletal salts, such as condensed alkali metal phosphates, silicates and carbonates. In many cases they contain enzymes and suitable stabilizing agents, furthermore alkanolamines, in particular triethanolamine, and small amounts of polyacids, such as citric acid and polyphosphonic acids.
- the nonionic surfactants are generally derived from alkylphenols or fatty alcohols or oxoalcohols with different chain lengths and, depending on the intended effect, have different degrees of alkoxylation. Basically, however, only those alkoxylation products are disclosed whose polyglycol ether radical - regardless of the degree of alkoxylation - is composed of ethylene glycol radicals. In contrast to these, it is known that polypropylene glycol ether groups have no hydrophilizing properties, which is why propoxylated fatty alcohols or Alkylphenols are not considered suitable for use in concentrated, aqueous liquid detergents.
- DE-OS 28 10 703 relates to nonionic surfactants which are contained by simultaneous or alternate addition of ethylene oxide and propylene oxide to higher alcohols.
- the ethylene and propylene glycol residues are present in statistical distribution or in repeated alternation.
- DE-OS 27 24 349 describes spray-dried detergents which are prepared using alkoxylates of the above formula R - 0 - Y - X.
- a teaching on the production of liquid detergents can not be found in this publication.
- DE-OS 29 18 826 in which the use of such alkoxylation products as low-foaming, biodegradable surfactants in detergents and cleaning agents is proposed.
- US-PS 2174761 from 1939 only in the alkoxylates of the type concerned times described, there are no indications of liquid detergents that would meet the current requirements regarding stability and washing ability, which are much higher than in the year of issue.
- the liquid detergents based on ethoxylated fatty alcohols cited in the first section have a sufficient detergent capacity against mineral and fatty soiling and - if they contain proteases and suitable stabilizing agents - also against protein-containing stains.
- the washability compared to bleachable ones is not entirely satisfactory. Soiling, especially stubborn tea stains. Since oxidizing bleaching agents are not suitable as components of the mixture in view of their inadequate resistance in aqueous preparations and in particular their destructive influence on enzymes, the task was therefore to develop a suitable composition which is more effective against the colored stains without affecting the detergency the other impurities.
- the compounds are derived from saturated and / or monounsaturated fatty alcohols of natural origin, such as lauryl, myristyl, cetyl, palmitoleyl, stearyl, oleyl, elaidyl, arachyl and gadoleyl alcohol, or from synthetic alcohols, for example oxo alcohols, the latter being usually consist of a mixture of linear and methyl-branched alcohols in the 2-position.
- the radicals R are preferably 25 to 100% by weight monounsaturated and 0 to 75% by weight saturated and have 12 to 18 carbon atoms.
- suitable starting alcohols are mixtures of 30 to 100% by weight, in particular 40 to 80% by weight of oleyl alcohol and 0 to 70% by weight, in particular 20 to 60% by weight of lauryl, Myristyl, cetyl and stearyl alcohol, such as are obtainable for example from coconut and tallow fatty acids or other natural fatty acid mixtures by hydrogenation.
- Component B consists of fatty acids in the form of their alkali metal or alkanolamine soaps, which are saturated or monounsaturated and have 10 to 20, preferably 12 to 18, carbon atoms.
- Suitable starting fatty acids are, in particular, coconut and tallow fatty acids and mixtures thereof, which essentially contain lauric, myristic, palmitic, stearic and oleic acid. They are preferably in the form of sodium and / or triethanolamine soaps, mixtures of 1 to 9 parts by weight of sodium soaps and 9 to 1 part by weight of triethanolamine soaps being particularly preferred.
- the proportion of component B in the agents according to the invention, based on fatty acid is 2 to 25% by weight and preferably 5 to 20% by weight.
- the proportion of the agents in components A and B should total 30 to 50% by weight, preferably 35 to 45% by weight.
- Proteases obtained from bacterial strains and mixtures of proteases and amylases are particularly suitable as enzymes.
- B. the enzymes obtained from Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus.
- These enzymes usually contain water-soluble calcium salts as potentiating and stabilizing agents and can be adjusted using adjusting agents, e.g. B. New tral salts, set to a defined degree of activation.
- the proportion of the enzymes is preferably 0.01 to 1% by weight.
- the organic solvents (component C) containing 5 to 25% by weight of the compositions consist of mono- or polyhydric alcohols or ether alcohols, such as ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol, 1,2-propylene glycol and glycerin .
- Ethanol, isopropanol and propylene glycol are the preferred solvents and are preferably used in a mixture, the weight ratio of monoalcohol to propylene glycol being 5: 1 to 1: 5.
- the proportion of organic solvent is preferably 8 to 16% by weight.
- compositions are free alkanolamines, especially triethanolamine, which has a stabilizing influence on the liquid agents and especially on the enzymes and is used in such an amount that, in addition to the acidic ingredients present for neutralization, an excess of 0.5 to 10% by weight .-%, preferably from 1 to 5 wt .-% is present.
- Acidic substances within the meaning of this definition are free fatty acids, polyacids and sulfonic acids which are not bound as alkali salts, such as can be present, for example, as optical brighteners.
- polyacids such as citric acid and polyphosphonic acids.
- polyphosphonic acids come e.g. B. 1-hydroxyethane-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid and their higher homologs, such as diethylenetriamine-pentamethylenephosphonic acid and 1-amino-butane-1,1-diphosphonic acid.
- phosphonoalkane arbonic acids such as 1-phosphonoethane-1,2-dicarboxylic acid, 2-phosphonopropane-2,3-dicarboxylic acid, 1-phosphonopropane-1,2,3-tricarboxylic acid, 1-phosphonopropane-1,2-dicarboxylic acid , 1-phosphono-2-methylpropane-1,2,3-tricarboxylic acid, 2-phosphate p honobutan-dicarboxylic acid 2,3-, 2-phosphonobutane-2,3,4-tricarboxylic acid, 2-phosphonobutane-1,2, 4-tricarboxylic acid, 1-phosphonobutane-1,2,3-tricarboxylic acid, 1-phosphono-2-methylbutane-1,2,3-tricarboxylic acid, 2-phosphono-3-methylbutane-2,3,4-tricarboxylic acid, 2- Phosphonopentane-2,3,4-tricarboxylic acid
- a preferred polycarboxylic acid is citric acid, which is advantageously present in proportions of 0.5 to 3% by weight.
- Further preferred polyacids are aminotrimethylenephosphonic acid and ethylenediamine-tetramethylenephosphonic acid, which can be present in amounts of 0.1 to 3% by weight.
- optical brighteners for example those from the class of the substituted 4,4-bis-triazinyl-diaminostilbene-disulfonic acids or the diphenyldistyryl.
- the 4,4-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) - stilbenedisulfonic acid 2,2'- and diphenyldistyryl-disulfonic acid are preferred.
- the optical brighteners can be in the form of salts of sodium, potassium or alkanolamines, the sodium salt being the most common.
- the proportion of optical brighteners is generally 0.05 to 1% by weight. ;
- Suitable additives are lower monocarboxylic acids or their salts, which have an additional stabilizing effect on the liquid concentrates or enzymes.
- suitable additives include formic acid, acetic acid, glycolic acid and lactic acid.
- Their proportion based on free acid can be up to 2% by weight, preferably 0.001 to 1% by weight.
- foam inhibitors in particular defoamers from the group of silicones, dyes and fragrances, opacifiers, microbial agents and solubility-improving compounds from the class alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl chains.
- composition of all constituents is chosen so that the pH is 6.5 to 9, preferably 3 to 8.5 in 1% aqueous solution.
- the water content of the concentrates averages 35 to 60% by weight.
- the procedure is expediently such that the soap-forming fatty acids or their predominant proportion are dissolved in an aqueous solution of the alkali metal hydroxides or the alkanolamines at a temperature which is above their melting point, then the solution is brought to temperatures below 50 Cools down and adds the organic solvents. Then the remaining ingredients are stirred into the still warm solution. The enzymes are finally added to the mixture which has cooled to below 30 ° C., preferably below 25 ° C.
- the liquid detergents according to the invention are notable for a long shelf life even at low and elevated temperatures. Unless the storage temperature does not significantly exceed 35 ° C, the enzymes are stable for many months. Their cleaning ability against greasy, protein-containing and mineral stains is good and corresponds to the performance of known liquid detergents of comparable composition. Compared to these comparative products, however, the washability against colored stains, in particular against tea stains, is improved.
- the agent was in the form of a clear, slightly viscous solution which, when cooled to temperatures below 14 ° C., became cloudy without any signs of segregation. The turbidity disappeared again when it was warmed up to room temperature. Storage tests at 25 ° C did not show a decrease in the enzyme activity within an observation period of 2 months.
- the washing tests were carried out in a launderometer with the addition of 10 steel balls each.
- the washing temperature was 60 ° C, the dosage 10 g / l, the water hardness 16 ° dH, the weight ratio of textile to washing liquor 1:12 and the washing time 30 minutes.
- the tap was rinsed with tap water three times for 15 seconds.
- Table 1 The text fabrics soiled in standardized conditions listed in Table 1 below were used: In the majority of cases, the results demonstrate a clear superiority of the agent according to the invention over the comparison samples, in particular with regard to the washing ability against soiling by tea and protein substances.
- composition of the agents is shown in Table 3.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Die flüssigen, von anorganischen Buildersalzen freien Waschmittel enthalten 20 - 40 Gew.-% eines Gemisches nichtionischer Tenside der Formel I: RO-(CH2-CHCH3-O)m -(CH2-CH2-O)n - H (I) worin R einen aliphatischen C10-C20-Kohlenwasserstoffrest, m = 0,5 bis 5 und n = 3 bis 20 bedeuten, wobei n größer als m ist. Das Gemisch besteht aus 5 bis 9 Gewichtsteilen (I) mit n = 3 bis 9 und 1 bis 5 Gewichtsteilen (I) mit n = 10 bis 20. Die weiteren Bestandteile sind 2 bis 25 Gew.-% an Natrium-, Kalium- oder Alkanolaminseife, die sich von gesättigten oder einfach ungesättigten C10-C20-Fettsäuren ableitet, 0,001 bis 2 Gew.-% eines proteolytischen Enzyms und 5 bis 25 Gew.-% an einwertigen und/oder mehrwertigen C2-C4-Alkoholen. Der Anteil der nichtionischen Tenside und der Seife beträgt 30 bis 50 Gew;-% der flüssigen Mittel und der pH-Wert der 1%igen wäßrigen Lösung 6,5 bis 9.The liquid detergents free of inorganic builder salts contain 20-40% by weight of a mixture of nonionic surfactants of the formula I: RO- (CH2-CHCH3-O) m - (CH2-CH2-O) n - H (I) where R is an aliphatic C10-C20 hydrocarbon radical, m = 0.5 to 5 and n = 3 to 20, where n is greater than m. The mixture consists of 5 to 9 parts by weight (I) with n = 3 to 9 and 1 to 5 parts by weight (I) with n = 10 to 20. The other constituents are 2 to 25% by weight of sodium, potassium or Alkanolamine soap, which is derived from saturated or monounsaturated C10-C20 fatty acids, 0.001 to 2% by weight of a proteolytic enzyme and 5 to 25% by weight of monohydric and / or polyhydric C2-C4 alcohols. The proportion of nonionic surfactants and soap is 30 to 50% by weight of the liquid agent and the pH of the 1% aqueous solution is 6.5 to 9.
Description
Aus den deutschen Offenlegungsschriften 19 75 010, 20 22 064, 21 36 340, 21 52 141, 23 01 728, 23 04 060,. 23 04 098, 23 09 463, 23 63 730,24 31 718, 25 12 616, 25 12 616, 25 27 793, 25 59 224, 25 59 225, 26 09 752, 26 46 057, 26 35 913, 26 58 073, 27 09 463, 27 09 476, 29 48 921, und den europäischen Offenlegungsschriften 8142, 19315, 28865 und 28866, der französischen Patentschrift 1397399 und der amerikanischen Patentschrift 3860536 sind flüssige Waschmittel mit wechselnden Mengen an nichtionischen Tensiden bekannt, die vielfach im Gemisch mit Seifen und Aniontensiden vom Sulfonat- bzw. Sulfat-Typ vorliegen. Die Mittel sind im wesentlichen frei von anorganischen Gerüstsalzen, wie kondensierten Alkalimetallphosphaten, -silikaten und carbonaten. Vielfach enthalten sie Enzyme und dafür geeignete Stabilisierungsmittel, ferner Alkanolamine, insbesondere Triethanolamin sowie geringe Mengen an Polysäuren, wie Citronensäure und Polyphosphonsäuren. Die nichtionischen Tenside leiten sich in der Regel von Alkylphenolen oder Fettalkoholen bzw. Oxoalkoholen mit unterschiedlicher Kettenlänge ab und weisen, je nach beabsichtigter Wirkung, unterschiedliche Alkoxylierungsgrade auf. Grundsätzlich sind jedoch nur solche Alkoxylierungsprodukte offenbart, deren Polyglykoletherrest - unabhängig vom Alkoxylierungsgrad - aus Ethylenglykolresten aufgebaut ist. Im Gegensatz zu diesen, besitzen bekanntlich Polypropylenglykolethergruppen keine hydrophilierenden Eigenschaften, weshalb propoxylierte Fettalkohole oder Alkylphenole für den Einsatz in konzentrierten, wäßrigen Flüssigwaschmitteln als nicht geeignet angesehen werden.From German Offenlegungsschriften 19 75 010, 2 0 22 064, 21 36 340, 21 52 141, 23 01 728, 23 04 060 ,. 23 04 098, 23 09 463, 23 63 730.24 31 718, 25 12 616, 25 12 616, 25 27 793, 25 59 224, 25 59 225, 26 09 752, 26 46 057 , 2 6 35 913, 26 58 073, 27 09 463, 27 09 476, 29 48 921, and European patent applications 8142, 19315, 28865 and 28866, French patent specification 1397399 and American patent specification 3860536, liquid detergents with varying amounts of nonionic surfactants are known, which are widely used in Mix with soaps and anionic surfactants of the sulfonate or sulfate type. The agents are essentially free of inorganic skeletal salts, such as condensed alkali metal phosphates, silicates and carbonates. In many cases they contain enzymes and suitable stabilizing agents, furthermore alkanolamines, in particular triethanolamine, and small amounts of polyacids, such as citric acid and polyphosphonic acids. The nonionic surfactants are generally derived from alkylphenols or fatty alcohols or oxoalcohols with different chain lengths and, depending on the intended effect, have different degrees of alkoxylation. Basically, however, only those alkoxylation products are disclosed whose polyglycol ether radical - regardless of the degree of alkoxylation - is composed of ethylene glycol radicals. In contrast to these, it is known that polypropylene glycol ether groups have no hydrophilizing properties, which is why propoxylated fatty alcohols or Alkylphenols are not considered suitable for use in concentrated, aqueous liquid detergents.
Gegenstand der DE-OS 28 10 703 sind nichtionische Tenside, die durch gleichzeitige oder wechselweise Anlagerung von Ethylenoxid und Propylenoxid an höhere Alkohole enthalten werden. In den Glykoletherresten liegen die Ethylen- und Propylenglykolreste in statistischer Verteilung oder im wiederholten Wechsel vor. Diese Verbindungen weisen gegenüber vergleichbaren Alkoxylaten der allgemeinen Formeln
Weiterhin sind aus der DE-OS 27 24 349 sprühgetrocknete Waschmittel;beschrieben, die unter Verwendung von Alkoxylaten der vorstehenden Formel R - 0 - Y - X hergestellt werden. Eine Lehre zur Herstellung von Flüssigwaschmitteln läßt sich dieser Veröffentlichung nicht entnehmen. Gleiches gilt für die DE-OS 29 18 826, in der die Verwendung derartiger Alkoxylierungsprodukte als schaumarme, biologisch abbaufähige Tenside in Wasch- und Reinigungsmitteln vorgeschlagen wird. Auch die US-PS 2174761 aus dem Jahre 1939, in der Alkoxylate des betroffenden Typs erstmalig beschrieben werden, gibt keine Hinweise über Flüssigwaschmittel, die den derzeitigen, gegenüber dem Ausgabejahr sehr viel höher geschraubten Anforderungen hinsichtlich Stabilität und Waschvermögen genügen würden.Furthermore, DE-OS 27 24 349 describes spray-dried detergents which are prepared using alkoxylates of the above formula R - 0 - Y - X. A teaching on the production of liquid detergents can not be found in this publication. The same applies to DE-OS 29 18 826, in which the use of such alkoxylation products as low-foaming, biodegradable surfactants in detergents and cleaning agents is proposed. Also the US-PS 2174761 from 1939, only in the alkoxylates of the type concerned times described, there are no indications of liquid detergents that would meet the current requirements regarding stability and washing ability, which are much higher than in the year of issue.
Die im ersten Abschnitt zitierten Flüssigwaschmittel auf Basis ethoxylierter Fettalkohole besitzen ein ausreichendes Waschveτmögen gegenüber mineralischen und fetthaltigen Anschmutzungen und - sofern sie Proteasen und dafür geeignete Stabilisierungsmittel enthalten - auch gegenüber eiweißhaltigen Flecken. Nicht voll zu befriedigen vermag hingegen das Waschvermögen gegenüber bleichbaren. Anschmutzungen, insbesondere hartnäckigen Teeflecken. Da oxidierende Bleichmittel mit Rücksicht auf ihre mangelnde Beständigkeit in wäßrigen Zubereitungen und insbesondere ihren zerstörenden Einfluß auf Enzyme als Mischungsbestandteile nicht geeignet sind, bestand daher die Aufgabe, eine geeignete Zusammensetzung zu entwickeln, die gegenüber den farbigen Anschmutzungen besser wirksam ist, ohne daß die Waschkraft gegenüber den übrigen Verunreinigungen absinkt. Von den Verbindungen der Formel R - 0 - Y - X war dies nicht zu erwarten, da die zitierte DE-OS 28 10 703 lehrt, daß derartige Tenside ein vermindertes Waschvermögen aufweisen und für Flüssigkonzentrate aufgrund ihres hohen Erstarrungspunktes wenig geeignet sind.The liquid detergents based on ethoxylated fatty alcohols cited in the first section have a sufficient detergent capacity against mineral and fatty soiling and - if they contain proteases and suitable stabilizing agents - also against protein-containing stains. On the other hand, the washability compared to bleachable ones is not entirely satisfactory. Soiling, especially stubborn tea stains. Since oxidizing bleaching agents are not suitable as components of the mixture in view of their inadequate resistance in aqueous preparations and in particular their destructive influence on enzymes, the task was therefore to develop a suitable composition which is more effective against the colored stains without affecting the detergency the other impurities. This was not to be expected from the compounds of the formula R - 0 - Y - X, since the cited DE-OS 28 10 703 teaches that such surfactants have a reduced washing power and are not very suitable for liquid concentrates because of their high solidification point.
Gegenstand der Erfindung, mit der diese Aufgabe gelöst wird, sind homogene, flüssige, von anorganischen Gerüstsalzen im wesentlichen freies Wasch- und Reinigungsmittel, enthaltend nichtionische Tenside, fettsaure Seifen, Enzyme und ein aus Wasser und ein- bzw. mehrwertigen Alkoholen bestehendes Lösungsmittelgemisch, gekennzeichnet durch einen Gehalt an
- A) 20 bis 40 Gew.-% eines Gemisches nichtionischer Tenside der Formel I:
- Al) 5 bis 9 Gewichtsteile einer Verbindung der Formel I mit n = 3 bis 9 und
- A2) 1 bis 5 Gewichtsteile einer Verbindung der Formel I mit n = 10 bis 20
- B) 2 bis 25 Gew.-% gesättigte und/oder einfach ungesättigte Fettsäure mit 10 bis 20 Kohlenstoffatomen, vorliegend als Seife des Natriums, Kaliums und/oder von Mono-, Di- oder Trialkanolaminen,
- C) 0,001 bis 2 Gew.-% eines proteolytischen Enzyms,
- D) 5 bis 25 Gew.-% minestens eines einwertigen und/oder
mehrwertigen Alkohols mit 2 bis 4 Kohlenstoffatomen, wobei der Anteil der Komponenten A und B 30 bis 50 Gew.-% des Mittels und der pH-Wert einer einprozentigen wäßrigen Lösung 6,5 bis 9 beträgt.The object of the invention with which this object is achieved are homogeneous, liquid washing and cleaning which is essentially free of inorganic skeletal salts medium, containing nonionic surfactants, fatty acid soaps, enzymes and a solvent mixture consisting of water and monohydric or polyhydric alcohols, characterized by a content of
- A) 20 to 40% by weight of a mixture of nonionic surfactants of the formula I:
- Al) 5 to 9 parts by weight of a compound of formula I with n = 3 to 9 and
- A2) 1 to 5 parts by weight of a compound of the formula I with n = 10 to 20
- B) 2 to 25% by weight of saturated and / or monounsaturated fatty acid with 10 to 20 carbon atoms, in the present case as a soap of sodium, potassium and / or of mono-, di- or trialkanolamines,
- C) 0.001 to 2% by weight of a proteolytic enzyme,
- D) 5 to 25% by weight of at least one monovalent and / or
polyhydric alcohol with 2 to 4 carbon atoms, the proportion of components A and B being 30 to 50% by weight of the composition and the pH of a one percent aqueous solution being 6.5 to 9.
Die Verbindungen der Formel I sind in bekannter Weise durch Propoxylierung von Alkoholen und anschließend Ethoxylierung enthältlich. Der Gehalt an Propylenglykolethergruppen (Index m) der beiden Mischungskomponenten Al und A2 kann gleich oder verschieden sein. Vorzugsweise ist das Gemisch der Verbindungen gemäß Formel I wie folgt zusammengesetzt:
- A1 mit m = 1 bis 3, n = 4 bis 8,
- A2 mit m = 1 bis 4, n = 12 bis 16,
wobei auf 6 bis 8 Gewichtsteile Al 2 bis 4 Gewichtsteile A2 entfallen.The compounds of the formula I are contained in a known manner by propoxylation of alcohols and then ethoxylation. The content of propylene glycol ether groups (index m) of the two mixture components Al and A2 can be the same or different. The mixture of the compounds of the formula I is preferably composed as follows:
- A1 with m = 1 to 3, n = 4 to 8,
- A2 with m = 1 to 4, n = 12 to 16,
6 to 8 parts by weight of Al make up 2 to 4 parts by weight of A2.
In einer weiteren bevorzugten Ausführungsform kann das Gemisch noch bis zu 6 Gewichtsteile einer Komponente A3 mit m = 1 bis 3 und n = 9 bis 11 enthalten.In a further preferred embodiment, the mixture can also contain up to 6 parts by weight of a component A3 with m = 1 to 3 and n = 9 to 11.
Die Verbindungen leiten sich von gesättigten und/oder einfach ungesättigten Fettalkoholen natürlichen Ursprungs, wie Lauryl-, Myristyl-, Cetyl-, Palmitoleyl, Stearyl-, Oleyl-, Elaidyl-, Arachyl und Gadoleylalkohol oder von synthetischen Alkoholen, beispielsweise Oxoalkoholen ab, wobei letztere meist aus einem Gemisch von linearen und in 2-Stellung methylverzweigten Alkoholen bestehen. Vorzugsweise sind die Reste R zu 25 bis 100 Gew.-% einfach ungesättigt und zu 0 - 75 Gew.-% gesättigt und weisen 12 bis 18 Kohlenstoffatome auf. Beispiele für geeignete Ausgangsalkohole sind Gemische aus 30 bis 100 Gew.-%, insbesondere 40 bis 80 Gew.-% Oleylalkohol und 0 bis 70 Gew.-%, insbesondere 20 bis 60 Gew.-% Lauryl-, Myristyl-, Cetyl- und Stearylalkohol, wie sie beispielsweise aus Cocos- und Talgfettsäuren oder anderen natürlichen Fettsäuregemischen durch Hydrierung erhältlich sind.The compounds are derived from saturated and / or monounsaturated fatty alcohols of natural origin, such as lauryl, myristyl, cetyl, palmitoleyl, stearyl, oleyl, elaidyl, arachyl and gadoleyl alcohol, or from synthetic alcohols, for example oxo alcohols, the latter being usually consist of a mixture of linear and methyl-branched alcohols in the 2-position. The radicals R are preferably 25 to 100% by weight monounsaturated and 0 to 75% by weight saturated and have 12 to 18 carbon atoms. Examples of suitable starting alcohols are mixtures of 30 to 100% by weight, in particular 40 to 80% by weight of oleyl alcohol and 0 to 70% by weight, in particular 20 to 60% by weight of lauryl, Myristyl, cetyl and stearyl alcohol, such as are obtainable for example from coconut and tallow fatty acids or other natural fatty acid mixtures by hydrogenation.
Die Komponente B besteht aus Fettsäuren in Form ihrer Alkalimetall- bzw. Alkanolaminseifen, die gesättigt oder einfach ungesättigt sind und 10 bis 20, vorzugsweise 12 bis 18 Kohlenstoffatomen aufweisen. Geeignete Ausgangsfettsäuren sind insbesondere Cocos- und Talgfettsäuren sowie deren Gemische, die im wesentlichen Laurin-, Myristin-, Palmitin-, Stearin- und Ölsäure enthalten. Sie liegen vorzugsweise als Natrium- und/oder Triethanolaminseifen vor, wobei Gemische aus der 1 bis 9 Gewichtsteilen Natriumseifen und 9 bis 1 Gewichtsteilen Triethanolaminseifen besonders bevorzugt sind. Der Anteil der Komponente B in den erfindungsgemäßen Mitteln beträgt, auf Fettsäure bezogen, 2 bis 25 Gew.-% und bevorzugt 5 bis 20 Gew.-%.Component B consists of fatty acids in the form of their alkali metal or alkanolamine soaps, which are saturated or monounsaturated and have 10 to 20, preferably 12 to 18, carbon atoms. Suitable starting fatty acids are, in particular, coconut and tallow fatty acids and mixtures thereof, which essentially contain lauric, myristic, palmitic, stearic and oleic acid. They are preferably in the form of sodium and / or triethanolamine soaps, mixtures of 1 to 9 parts by weight of sodium soaps and 9 to 1 part by weight of triethanolamine soaps being particularly preferred. The proportion of component B in the agents according to the invention, based on fatty acid, is 2 to 25% by weight and preferably 5 to 20% by weight.
Der Anteil der Mittel an den Komponenten A und B soll insgesamt 30 bis 50 Gew.-%, vorzugsweise 35 bis 45 Gew.-% betragen.The proportion of the agents in components A and B should total 30 to 50% by weight, preferably 35 to 45% by weight.
Als Enzyme kommen insbesondere aus Bacterienstämmen gewonnene Proteasen und Gemische aus Proteasen und Amylasen in Frage. Geeignet sind z. B. die aus Bacillus subtilis, Bacillus licheniformis und Streptomyces griseus gewonnenen Enzyme. Diese Enzyme enthalten in der Regel wasserlösliche Calciumsalze als Potenzierungs- und Stabilisierungsmittel und sind mittels Stellmitteln, z. B. Neutralsalzen, auf einen definierten Aktivierungsgrad eingestellt. Der Anteil der Enzyme beträgt vorzugsweise 0,01 bis 1 Gew.-%.Proteases obtained from bacterial strains and mixtures of proteases and amylases are particularly suitable as enzymes. Are suitable for. B. the enzymes obtained from Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus. These enzymes usually contain water-soluble calcium salts as potentiating and stabilizing agents and can be adjusted using adjusting agents, e.g. B. New tral salts, set to a defined degree of activation. The proportion of the enzymes is preferably 0.01 to 1% by weight.
Die in den Mitteln mit einem Anteil von 5 bis 25 Gew.-% enthaltenden organischen Lösungsmittel (Komponente C) bestehen aus ein- oder mehrwertigen Alkoholen oder Etheralkoholen, wie Ethanol, Propanol, Isopropanol, Ethylenglykol, Diethylenglykol, 1,2-Propylenglykol and Glycerin. Ethanol, Isopropanol und Propylenglykol stellen die bevorzugt verwendeten Lösungsmittel dar und werden vorzugsweise im Gemisch verwendet, wobei das Gewichtsverhältnis von Monoalkohol zu Propylenglykol 5 : 1 bis 1 : 5 betragen kann. Vorzugsweise beträgt der Anteil an organischem Lösungsmittel 8 bis 16 Gew.-%.The organic solvents (component C) containing 5 to 25% by weight of the compositions consist of mono- or polyhydric alcohols or ether alcohols, such as ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol, 1,2-propylene glycol and glycerin . Ethanol, isopropanol and propylene glycol are the preferred solvents and are preferably used in a mixture, the weight ratio of monoalcohol to propylene glycol being 5: 1 to 1: 5. The proportion of organic solvent is preferably 8 to 16% by weight.
Weitere vorteilhafte Bestandteile sind freie Alkanolamine, insbesondere Triethanolamin, das auf die flüssigen Mittel und speziell auf die Enzyme einen stabilisierenden Einfluß ausübt und in solcher Menge eingesetzt wird, daß über die zur Neutralisation anwesender saurer Bestandteile hinaus noch ein Überschuß von 0,5 bis 10 Gew.-%, vorzugsweise von 1 bis 5 Gew.-% vorhanden ist. Als saure Stoffe im Sinne dieser Definition sind freie, nicht als Alkalisalze gebundene Fettsäuren, Polysäuren und Sulfonsäuren, wie sie beispielsweise als optische Aufheller vorliegen können.Other advantageous ingredients are free alkanolamines, especially triethanolamine, which has a stabilizing influence on the liquid agents and especially on the enzymes and is used in such an amount that, in addition to the acidic ingredients present for neutralization, an excess of 0.5 to 10% by weight .-%, preferably from 1 to 5 wt .-% is present. Acidic substances within the meaning of this definition are free fatty acids, polyacids and sulfonic acids which are not bound as alkali salts, such as can be present, for example, as optical brighteners.
Weitere vorteilhafte Mischungsbestandteile sind Polysäuren, wie Citronensäure und Polyphosphonsäuren. Als Polyphosphonsäuren kommen z. B. 1-Hydroxyethan-1,1-diphosphonsäure, Aminotrimethylenphosphonsäure, Ethylendiamintetramethylenphosphonsäure und deren höhere Homologe, wie Diethylentriamin-pentamethylenphosphonsäure und 1-Amino- butan-1,1-diphosphonsäure.Other advantageous components of the mixture are polyacids, such as citric acid and polyphosphonic acids. As a poly phosphonic acids come e.g. B. 1-hydroxyethane-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid and their higher homologs, such as diethylenetriamine-pentamethylenephosphonic acid and 1-amino-butane-1,1-diphosphonic acid.
Weitere brauchbare Polysäuren sind Phosphonoalkanearbonsäuren, wie 1-Phosphonoäthan-1,2-dicarbonsäure, 2-Phos- phonopropan-2,3-dicarbonsäure, 1-Phosphonopropan-1,2,3-tricarbonsäure, 1-Phosphonopropan-1,2-dicarbonsäure, 1-Phosphono-2-methylpropan-1,2,3-tricarbonsäure, 2-Phos- phonobutan-2,3-dicarbonsäure, 2-Phosphonobutan-2,3,4-tricarbonsäure, 2-Phosphonobutan-1,2,4-tricarbonsäure, 1-Phosphonobutan-1,2,3-tricarbonsäure, 1-Phosphono-2-methylbutan-1,2,3-tricarbonsäure, 2-Phosphono-3-methylbutan-2,3,4-tricarbonsäure, 2-Phosphonopentan-2,3,4-tricarbonsäure, 2-Phosphono-3-methylpentan-2,3,4-tricarbonsäure, 1,1-Diphosphonopropan-2,3-dicarbonsäure, 1,1-Diphos- phono-2-methylpropan-2,3-dicarbonsäure, 2,2-Diphosphono- butan-3,4-dicarbonsäure, 1,1-Diphosphonbutan-2,3-dicarbonsäure, 2,2-Diphosphono-3-methylbutan-3,4-dicarbonsäure, 2,2-Diphosphonopentan-3,4-dicarbonsäure, 1,1-Diphos- phono-2-methylbutan-2,3-dicarbonsäure, 2,2-Diphosphono-3-methylpentan-3,4-d1carbonsäure.Other useful polyacids are phosphonoalkane arbonic acids, such as 1-phosphonoethane-1,2-dicarboxylic acid, 2-phosphonopropane-2,3-dicarboxylic acid, 1-phosphonopropane-1,2,3-tricarboxylic acid, 1-phosphonopropane-1,2-dicarboxylic acid , 1-phosphono-2-methylpropane-1,2,3-tricarboxylic acid, 2-phosphate p honobutan-dicarboxylic acid 2,3-, 2-phosphonobutane-2,3,4-tricarboxylic acid, 2-phosphonobutane-1,2, 4-tricarboxylic acid, 1-phosphonobutane-1,2,3-tricarboxylic acid, 1-phosphono-2-methylbutane-1,2,3-tricarboxylic acid, 2-phosphono-3-methylbutane-2,3,4-tricarboxylic acid, 2- Phosphonopentane-2,3,4-tricarboxylic acid, 2-phosphono-3-methylpentane-2,3,4-tricarboxylic acid, 1,1-diphosphonopropane-2,3-dicarboxylic acid, 1,1-diphosphonophono-2-methylpropane 2,3-dicarboxylic acid, 2,2-diphosphonobutane-3,4-dicarboxylic acid, 1,1-diphosphonobutane-2,3-dicarboxylic acid, 2,2-diphosphono-3-methylbutane-3,4-dicarboxylic acid, 2, 2-diphosphonopentane-3,4-dicarboxylic acid, 1,1-diphosphono-2-methylbutane-2,3-dicarboxylic acid, 2,2-diphosphono-3-methylpentane-3,4-d1carboxylic acid.
Eine bevorzugte Polycarbonsäure ist die Citronensäure, die zweckmäßigerweise in Anteilen von 0,5 bis 3 Gew.-% anwesend ist. Weitere bevorzugte Polysäuren sind Aminotrimethylenphosphonsäure und Ethylendiamin-tetra- methylenphosphonsäure, die in Mengen von 0,1 bis 3 Gew.-% anwesend sein können.A preferred polycarboxylic acid is citric acid, which is advantageously present in proportions of 0.5 to 3% by weight. Further preferred polyacids are aminotrimethylenephosphonic acid and ethylenediamine-tetramethylenephosphonic acid, which can be present in amounts of 0.1 to 3% by weight.
Fakultative Bestandteile sind optische Aufheller, beispielsweise solche aus der Klasse der substituierten 4,4-Bis-triazinyl-diaminostilben-disulfonsäuren oder der Diphenyldistyryle. Bevorzugt sind die 4,4-Bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)- stilbendisufonsäu- re-2,2'und Diphenyldistyryl-disulfonsäure. Die optischen Aufheller können als Salze des Natriums, Kaliums oder von Alkanolaminen vorliegen, wobei das Natriumsalz das gebräuchlichste ist. Der Anteil der optischen Aufheller beträgt im allgemeinen 0,05 bis 1 Gew.-%. ; Optional components are optical brighteners, for example those from the class of the substituted 4,4-bis-triazinyl-diaminostilbene-disulfonic acids or the diphenyldistyryl. The 4,4-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) - stilbenedisulfonic acid 2,2'- and diphenyldistyryl-disulfonic acid are preferred. The optical brighteners can be in the form of salts of sodium, potassium or alkanolamines, the sodium salt being the most common. The proportion of optical brighteners is generally 0.05 to 1% by weight. ;
Weitere geeignete Zusätze sind niedere Monocarbonsäuren bzw. deren Salze, die eine zusätzliche stabilisierende Wirkung auf die Flüssigkonzentrate bzw. Enzyme ausüben. Beispiele hierfür sind-Ameisensäure, Essigsäure, Glykolsäure und Milchsäure. Ihr auf freie Säure bezogener An- : teil kann bis zu 2 Gew.-%, vorzugsweise 0,001 bis 1 Gew.-% betragen.Other suitable additives are lower monocarboxylic acids or their salts, which have an additional stabilizing effect on the liquid concentrates or enzymes. Examples include formic acid, acetic acid, glycolic acid and lactic acid. Their proportion based on free acid can be up to 2% by weight, preferably 0.001 to 1% by weight.
Weitere fakulatative Bestandteile sind Schauminhibitoren, insbesondere Entschäumer aus der Gruppe der Silikone, Farb- und Duftstoffe, Trübungsmittel, mikrobielle Mittel sowie löslichkeitsverbessernde Verbindungen aus der Klasse Alkylbenzolsulfonate mit 1 bis 3 Kohlenstoffatome in den Alkylketten.Other optional components are foam inhibitors, in particular defoamers from the group of silicones, dyes and fragrances, opacifiers, microbial agents and solubility-improving compounds from the class alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl chains.
Die Zusammensetzung aller Bestandteile, insbesondere der sauren und der alkalisierenden wird so gewählt, daß der pH-Wert 6,5 bis 9, vorzugsweise 3 bis 8,5 in 1-prozentiger wäßriger Lösung beträgt. Der Wassergehalt der Konzentrate beträgt im Durchschnitt 35 bis 60 Gew.-%.The composition of all constituents, in particular the acidic and the alkalizing, is chosen so that the pH is 6.5 to 9, preferably 3 to 8.5 in 1% aqueous solution. The water content of the concentrates averages 35 to 60% by weight.
Bei der Herstellung der Mittel geht man zweckmäßigerweise so vor, daß man die seifenbildenden Fettsäuren bzw. deren überwiegenden Anteil bei einer Temperatur, die oberhalb ihres Schmelzpunktes liegt, in einer wäßrigen Lösung der Alkalimetallhydroxide bzw. der Alkanolamine löst, darauf die Lösung auf Temperaturen unterhalb 50 °C abkühlt und die organischen Lösungsmittel hinzufügt. Anschließend werden die übrigen Bestandteile in die noch warme Lösung eingerührt werden. Die Zugabe der Enzyme erfolgt am Schluß in die auf unterhalb 30 °C, vorzugsweise unterhalb 25 °C abgekühlte Mischung.In the preparation of the agents, the procedure is expediently such that the soap-forming fatty acids or their predominant proportion are dissolved in an aqueous solution of the alkali metal hydroxides or the alkanolamines at a temperature which is above their melting point, then the solution is brought to temperatures below 50 Cools down and adds the organic solvents. Then the remaining ingredients are stirred into the still warm solution. The enzymes are finally added to the mixture which has cooled to below 30 ° C., preferably below 25 ° C.
Die erfindungsgemäßen Flüssigwaschmittel zeichnen sich durch eine hohe Lagerbeständigkeit auch bei niedrigen und erhöhten Temperaturen aus. Die Enzyme sind, sofern die Lagertemperatur nicht wesentlich über 35 °C hinausgeht, über viele Monate stabil. Ihr Reinigungsvermögen gegenüber fettigen, eiweißhaltigen und mineralischen Anschmutzungen ist gut und entspricht der Leistungsfähigkeit bekannter Flüssigwaschmittel vergleichbarer Zusammensetzung. Gegenüber diesen Vergleichsprodukten ist jedoch das Waschvermögen gegenüber farbigen Anschmutzungen, insbesondere gegenüber Teeflecken verbessert.The liquid detergents according to the invention are notable for a long shelf life even at low and elevated temperatures. Unless the storage temperature does not significantly exceed 35 ° C, the enzymes are stable for many months. Their cleaning ability against greasy, protein-containing and mineral stains is good and corresponds to the performance of known liquid detergents of comparable composition. Compared to these comparative products, however, the washability against colored stains, in particular against tea stains, is improved.
In einer auf 70 °C erwärmten Lösung von 1,2 Gewichtsteilen NaOH in 35 Gewichtsteilen Wasser wurden 10 Gewichtsteile einer hydrierten Palmkernfettsäure, bestehend aus einem Gemisch gesättigter Fettsäuren mit 12 bis 18 C-Atomen, dispergiert. Nach Zusatz von 5 Gewichtsteilen Triethanolamin wurde die Lösung auf 40 °C abgekühlt und mit 10 Gewichtsteilen Ethanol (96%ig) sowie 5 Gewichtsteilen 1,2-Propylenglykol versetzt. Anschließend wurden 30 Gewichtsteile eines Gemisches zugefügt, enthaltend 2,5 Gewichtsteile Kokosfettsäure, 2,5 Teile Wasser und
- Al) 17,4 Gewichtsteile eines alkoxylierten Fettalkohols der Formel I mit m = 1,2 und n = 6,3,
- A2) 7,6 Gewichtsteil eines alkoxylierten Fettalkohols der Formel I mit m = 2 und n = 14,
deren Fettalkoholrest sich zu 60 Gew.-% aus Oleylalkohol, zu 30 Gew.-% aus Cetylalkohol und zu 10 % aus Stearylalkohol zusammensetzte. Nach Zumischen von 0,06 Gewichtsteilen Milchsäure und 0,06 Gewichtsteilen eines optischen Aufhellers vom Bis-(triazinyl)-aminostilben-disulfonsäure-Typ wurde die Lösung auf 20 °C abgekühlt und mit 0,78 Teilen eines proteolytischen, aus Bacterium subtilis-Stämmen gewonnenen Enzyms versetzt. Das Mittel enthielt 38,9 Gew.-% Wasser und wies in l%iger wäßriger Verdünnung einen pH-Wert von 8,2 auf. Die in dem Mittel enthaltene Seife lag zu etwa 60 % als Natriumseife und zu etwa 40 % als Triethanolaminseife vor.10 parts by weight of a hydrogenated palm kernel fatty acid consisting of a mixture of saturated fatty acids with 12 to 18 carbon atoms were dispersed in a solution of 1.2 parts by weight of NaOH in 35 parts by weight of water heated to 70 ° C. After adding 5 parts by weight of triethanolamine, the solution was cooled to 40 ° C. and 10 parts by weight of ethanol (96%) and 5 parts by weight of 1,2-propylene glycol were added. Then 30 parts by weight of a mixture were added, containing 2.5 parts by weight of coconut fatty acid, 2.5 parts of water and
- Al) 17.4 parts by weight of an alkoxylated fatty alcohol of the formula I with m = 1.2 and n = 6.3,
- A2) 7.6 parts by weight of an alkoxylated fatty alcohol of the formula I with m = 2 and n = 14,
whose fatty alcohol residue was composed of 60% by weight of oleyl alcohol, 30% by weight of cetyl alcohol and 10% of stearyl alcohol. After admixing 0.06 part by weight of lactic acid and 0.06 part by weight of an optical brightener of the bis- (triazinyl) aminostilbene-disulfonic acid type, the solution was cooled to 20 ° C. and mixed with 0.78 part of a proteolytic strain from Bacterium subtilis obtained enzyme added. The composition contained 38.9% by weight of water and had a pH of 8.2 in 1% aqueous dilution. About 60% of the soap contained in the composition was sodium soap and about 40% was triethanolamine soap.
Das Mittel lag als klare, leicht viskose Lösung vor, die sich beim Abkühlen auf Temperaturen unterhalb 14 °C ohne Entmischungserscheinungen trübte. Bei Wiedererwärmung auf Raumtemperatur verschwand die Trübung wieder. Lagerversuche bei 25 °C ergaben innerhalb eines Beobachtungszeitraums von 2 Monaten keine Abnahme der Enzymaktivität.The agent was in the form of a clear, slightly viscous solution which, when cooled to temperatures below 14 ° C., became cloudy without any signs of segregation. The turbidity disappeared again when it was warmed up to room temperature. Storage tests at 25 ° C did not show a decrease in the enzyme activity within an observation period of 2 months.
In der Rezeptur nach Beispiel 1 wurden die unter A1 und A2 aufgeführten Alkoxylate durch die folgenden Verbindungen bzw. Gemische ersetzt:
- V1: 25 Gewichtsteile 5-fach ethoxylierter Fettalkohol (C12-C18, mittlere Kettenlänge C15.5).
- V2: 25 Gewichtsteile 12-fach ethoxylierter Fettalkohol (C12-C18, mittlere Kettenlänge C15.5).
- V3: 12,5 Gewichtsteile ethoxylierte Fettalkohol V1 12,5 Gewichtsteile ethoxylierte Fettalkohol V2
- V1: 25 parts by weight of 5-fold ethoxylated fatty alcohol (C 12 -C 18 , average chain length C 15.5 ).
- V2: 25 parts by weight of 12-fold ethoxylated fatty alcohol (C 12 -C 18 , average chain length C 15.5 ).
- V3: 12.5 parts by weight of ethoxylated fatty alcohol V1 12.5 parts by weight of ethoxylated fatty alcohol V2
Die Waschversuche.wurden im Launderometer unter Zusatz von jeweils 10 Stahlkugeln durchgeführt. Die Waschtemperatur betrug 60 °C, die Dosierung 10 g/l, die Wasserhärte 16 °dH, das Gewichtsverhältnis von Textilgut zur Waschlauge 1 : 12 und die Waschdauer 30 Minuten. Nach dem Waschen wurde 3mal je 15 Sekunden mit Leitungswasser nachgespült. Es wurden die in der folgenden Tabelle 1 aufgeführten, unter standardisierten Bedingungen angeschmutzten Textgewebe eingesetzt:
Die Zusammensetzung der Mittel, angegeben in Gew.-%, ist der Tabelle 3 zu entnehmen.The composition of the agents, given in% by weight, is shown in Table 3.
Die Abkürzungen haben die folgende Bedeutung:
- PO Propylenoxidgruppen,
- EO Ethylenoxidgruppen,
- FA1 Fettalkoholrest gemäß Beispiel 1,
- FA2 Fettalkoholrest aus 80 % Oleylalkohol, Rest Cetylalkohol,
- FA3 Fettalkoholrest aus 50 % Oleylalkohol, 1 % Laurylalkohol, 9 % Myristylalkohol, 30 % Cetylalkohol und 10 % Stearylalkohol,
- TAF Talgfettsäure,
- COF Cocosfettsäure,
- HPF hydrierte Palmkernfettsäure,
- TEA Triethanolamin,
- ATI4P Aminotrimethylenphosphonat (Na-Salz),
- EDTMP Ethylendiamintetramethylenphosphonat (Na-Salz),
- PO propylene oxide groups,
- EO ethylene oxide groups,
- FA 1 fatty alcohol residue according to Example 1,
- FA 2 fatty alcohol residue from 80% oleyl alcohol, residue cetyl alcohol,
- FA 3 fatty alcohol residue from 50% oleyl alcohol, 1% lauryl alcohol, 9% myristyl alcohol, 30% cetyl alcohol and 10% stearyl alcohol,
- TAF tallow fatty acid,
- COF coconut fatty acid,
- HPF hydrogenated palm kernel fatty acid,
- TEA triethanolamine,
- ATI4P aminotrimethylene phosphonate (Na salt),
- EDTMP ethylenediaminetetramethylenephosphonate (Na salt),
Lagerverhalten, Enzymstabilität und Waschvermögen der Mittel sind innerhalb der Fehlergrenzen die gleichen wie in Beispiel 1.
Claims (10)
. mehrwertigen Alkohols mit 2 bis 4 Kohlenstoffatomen, wobei der Anteil der Komponenten A und B 30 bis 50 Gew.-% des flüssigen Mittels und der pH-Wert einer einprozentigen wäßrigen Lösung 6,5 bis 9 beträgt.1. Homogeneous, liquid detergent and cleaning agent essentially free of inorganic skeletal salts, containing nonionic surfactants, fatty acid soaps, enzymes and a solvent mixture consisting of water and monohydric or polyhydric alcohols, characterized by a content of
. polyhydric alcohol with 2 to 4 carbon atoms, the proportion of components A and B being 30 to 50% by weight of the liquid agent and the pH of a one-percent aqueous solution being 6.5 to 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3232616 | 1982-09-02 | ||
| DE19823232616 DE3232616A1 (en) | 1982-09-02 | 1982-09-02 | LIQUID, INORGANIC FRUIT SALT, IN ESSENTIAL FREE DETERGENT AND CLEANING AGENT |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0104434A2 true EP0104434A2 (en) | 1984-04-04 |
| EP0104434A3 EP0104434A3 (en) | 1985-11-21 |
Family
ID=6172290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83108321A Withdrawn EP0104434A3 (en) | 1982-09-02 | 1983-08-24 | Liquid washing and cleaning composition virtually devoid of inorganic builder salts |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4608189A (en) |
| EP (1) | EP0104434A3 (en) |
| JP (1) | JPS5959799A (en) |
| DE (1) | DE3232616A1 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0272574A3 (en) * | 1986-12-22 | 1989-09-06 | Henkel Kommanditgesellschaft Auf Aktien | Mixtures of liquid non-ionic surfactants |
| EP0306843A3 (en) * | 1987-09-09 | 1989-11-29 | Henkel Kommanditgesellschaft auf Aktien | Thickened aqueous surfactant solutions, in particular for their use in the domain of cosmetic preparations |
| EP0235774A3 (en) * | 1986-03-05 | 1990-05-23 | Henkel Kommanditgesellschaft Auf Aktien | Liquid surface-active mixtures |
| EP0339994A3 (en) * | 1988-04-29 | 1991-05-29 | Unilever Plc | Detergent composition in gel form |
| EP0592947A1 (en) * | 1992-10-12 | 1994-04-20 | ALBRIGHT & WILSON UK LIMITED | Cleaning preparations |
| WO1995009229A1 (en) * | 1993-09-27 | 1995-04-06 | Henkel Kommanditgesellschaft Auf Aktien | Pasty washing agent |
| WO1996006910A3 (en) * | 1994-08-31 | 1996-03-21 | Ecolab Inc | Improved proteolytic enzyme cleaner |
| WO1997005227A1 (en) * | 1995-07-27 | 1997-02-13 | Unilever, N.V. | An anionic stabilized enzyme-based clean-in-place system |
| WO2018049036A1 (en) * | 2016-09-07 | 2018-03-15 | Ecolab Usa Inc. | Detergent compositions containing a stabilized enzyme by phosphonates |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4737314A (en) * | 1985-02-08 | 1988-04-12 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Stabilized alkylene oxide adduct containing lactic acid or a lactate |
| US4822514A (en) * | 1987-01-14 | 1989-04-18 | Murphy-Phoenix Company | Compositions and methods for cleaning surfaces while selectively imparting gloss or shine thereto |
| US5269960A (en) * | 1988-09-25 | 1993-12-14 | The Clorox Company | Stable liquid aqueous enzyme detergent |
| DE3936413A1 (en) * | 1988-12-27 | 1990-06-28 | Feinchemie Schwebda Gmbh | CLEANING AGENTS FOR CLEANING FIELD SPRAYERS FROM PLANT PROTECTION RESIDUES |
| JP3135066B2 (en) | 1991-05-14 | 2001-02-13 | エコラボ インコーポレイテッド | Two-part drug concentrate |
| US5789364A (en) * | 1993-02-17 | 1998-08-04 | The Clorox Company | High water liquid enzyme prewash composition |
| US5589448A (en) * | 1993-02-17 | 1996-12-31 | The Clorox Company | High water liquid enzyme prewash composition |
| EP0623671A1 (en) * | 1993-05-06 | 1994-11-09 | The Procter & Gamble Company | Mixing order to prepare aqueous clear detergent compositions |
| US6156715A (en) * | 1997-01-13 | 2000-12-05 | Ecolab Inc. | Stable solid block metal protecting warewashing detergent composition |
| US6177392B1 (en) * | 1997-01-13 | 2001-01-23 | Ecolab Inc. | Stable solid block detergent composition |
| US6258765B1 (en) | 1997-01-13 | 2001-07-10 | Ecolab Inc. | Binding agent for solid block functional material |
| US6150324A (en) | 1997-01-13 | 2000-11-21 | Ecolab, Inc. | Alkaline detergent containing mixed organic and inorganic sequestrants resulting in improved soil removal |
| US6063206A (en) * | 1998-05-04 | 2000-05-16 | C. J. Latta & Associates | De-oiling process using enzymes |
| US6376446B1 (en) | 1999-01-13 | 2002-04-23 | Melaleuca, Inc | Liquid detergent composition |
| US20050164902A1 (en) * | 2003-10-24 | 2005-07-28 | Ecolab Inc. | Stable compositions of spores, bacteria, and/or fungi |
| US7569532B2 (en) | 2000-06-29 | 2009-08-04 | Ecolab Inc. | Stable liquid enzyme compositions |
| US6624132B1 (en) * | 2000-06-29 | 2003-09-23 | Ecolab Inc. | Stable liquid enzyme compositions with enhanced activity |
| US7795199B2 (en) | 2000-06-29 | 2010-09-14 | Ecolab Inc. | Stable antimicrobial compositions including spore, bacteria, fungi, and/or enzyme |
| US6638902B2 (en) | 2001-02-01 | 2003-10-28 | Ecolab Inc. | Stable solid enzyme compositions and methods employing them |
| US6632291B2 (en) * | 2001-03-23 | 2003-10-14 | Ecolab Inc. | Methods and compositions for cleaning, rinsing, and antimicrobial treatment of medical equipment |
| MX2009007475A (en) * | 2007-01-11 | 2009-08-13 | Dow Global Technologies Inc | Alkoxylate blend surfactants. |
| EP2161327A1 (en) * | 2008-09-05 | 2010-03-10 | Cognis IP Management GmbH | Emulsifiers for metal working fluids |
| US7964548B2 (en) | 2009-01-20 | 2011-06-21 | Ecolab Usa Inc. | Stable aqueous antimicrobial enzyme compositions |
| US7723281B1 (en) | 2009-01-20 | 2010-05-25 | Ecolab Inc. | Stable aqueous antimicrobial enzyme compositions comprising a tertiary amine antimicrobial |
| JP5902622B2 (en) * | 2010-09-10 | 2016-04-13 | ライオン株式会社 | Liquid detergent composition |
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| US2174761A (en) * | 1935-04-13 | 1939-10-03 | Ig Farbenindustrie Ag | Condensation products derived from hydroxy compounds and method of producing them |
| US3022335A (en) * | 1955-03-30 | 1962-02-20 | Wyandotte Chemicals Corp | Surface active polyoxyalkylene compounds having a plurality of heteric polyoxypropylene-polyoxyethylene chains |
| FR1501661A (en) * | 1965-11-29 | 1967-11-10 | Witco Chemical Corp | Liquid detergent composition, stable, multi-functional, one hundred percent active, and its production process |
| US3860536A (en) * | 1970-01-02 | 1975-01-14 | Cpc International Inc | Enzyme-detergent combination |
| US3733281A (en) * | 1971-04-06 | 1973-05-15 | L Durfey | Method of cleaning carpets and fabrics |
| US4101457A (en) * | 1975-11-28 | 1978-07-18 | The Procter & Gamble Company | Enzyme-containing automatic dishwashing composition |
| IT1106254B (en) * | 1976-03-08 | 1985-11-11 | Procter & Gamble Europ | LIQUID DETERGENT COMPOSITION CONTAINING ENZYMES |
| DE2727463A1 (en) * | 1976-06-24 | 1978-01-05 | Procter & Gamble | DETERGENT PARTICULARLY SUITABLE FOR USE IN DISHWASHING MACHINES |
| US4115292A (en) * | 1977-04-20 | 1978-09-19 | The Procter & Gamble Company | Enzyme-containing detergent articles |
| US4176079A (en) * | 1977-04-20 | 1979-11-27 | The Procter & Gamble Company | Water-soluble enzyme-containing article |
| US4238345A (en) * | 1978-05-22 | 1980-12-09 | Economics Laboratory, Inc. | Stabilized liquid enzyme-containing detergent compositions |
| NL8000452A (en) * | 1979-02-07 | 1980-08-11 | Unilever Nv | PREPARATION FOR LAUNDRY. |
| DE2918826A1 (en) * | 1979-05-10 | 1980-11-27 | Basf Ag | USE OF ALCOXYLATED ALCOHOLS AS BIODEGRADABLE, LOW-FOAM SURFACES IN DETERGENTS AND CLEANERS |
| US4272394A (en) * | 1979-11-19 | 1981-06-09 | Basf Wyandotte Corporation | Machine dishwashing detergents containing low-foaming nonionic surfactants |
| US4316824A (en) * | 1980-06-26 | 1982-02-23 | The Procter & Gamble Company | Liquid detergent composition containing alkyl sulfate and alkyl ethoxylated sulfate |
-
1982
- 1982-09-02 DE DE19823232616 patent/DE3232616A1/en not_active Withdrawn
-
1983
- 1983-08-24 EP EP83108321A patent/EP0104434A3/en not_active Withdrawn
- 1983-08-30 JP JP58157273A patent/JPS5959799A/en active Pending
-
1985
- 1985-05-08 US US06/731,760 patent/US4608189A/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0235774A3 (en) * | 1986-03-05 | 1990-05-23 | Henkel Kommanditgesellschaft Auf Aktien | Liquid surface-active mixtures |
| EP0272574A3 (en) * | 1986-12-22 | 1989-09-06 | Henkel Kommanditgesellschaft Auf Aktien | Mixtures of liquid non-ionic surfactants |
| EP0306843A3 (en) * | 1987-09-09 | 1989-11-29 | Henkel Kommanditgesellschaft auf Aktien | Thickened aqueous surfactant solutions, in particular for their use in the domain of cosmetic preparations |
| US4992263A (en) * | 1987-09-09 | 1991-02-12 | Henkel Kommanditgesellschaft Auf Aktien | Thickended aqueous surfactant solutions and their use in cosmetic preparations |
| EP0339994A3 (en) * | 1988-04-29 | 1991-05-29 | Unilever Plc | Detergent composition in gel form |
| EP0592947A1 (en) * | 1992-10-12 | 1994-04-20 | ALBRIGHT & WILSON UK LIMITED | Cleaning preparations |
| US5929014A (en) * | 1993-09-27 | 1999-07-27 | Henkel-Ecolab Gmbh & Co. Ohg | Paste-form detergent |
| WO1995009229A1 (en) * | 1993-09-27 | 1995-04-06 | Henkel Kommanditgesellschaft Auf Aktien | Pasty washing agent |
| WO1996006910A3 (en) * | 1994-08-31 | 1996-03-21 | Ecolab Inc | Improved proteolytic enzyme cleaner |
| WO1997005227A1 (en) * | 1995-07-27 | 1997-02-13 | Unilever, N.V. | An anionic stabilized enzyme-based clean-in-place system |
| AU719399B2 (en) * | 1995-07-27 | 2000-05-11 | Diversey Ip International Bv | An anionic stabilized enzyme-based clean-in-place system |
| WO2018049036A1 (en) * | 2016-09-07 | 2018-03-15 | Ecolab Usa Inc. | Detergent compositions containing a stabilized enzyme by phosphonates |
| US11021680B2 (en) | 2016-09-07 | 2021-06-01 | Ecolab Usa Inc. | Detergent compositions containing a stabilized enzyme by phosphonates |
| US11807835B2 (en) | 2016-09-07 | 2023-11-07 | Ecolab Usa Inc. | Detergent compositions containing a stabilized enzyme by phosphonates |
| EP3510133B1 (en) * | 2016-09-07 | 2024-07-10 | Ecolab USA Inc. | Detergent compositions containing a stabilized enzyme by phosphonates |
| US12203055B2 (en) | 2016-09-07 | 2025-01-21 | Ecolab Usa Inc. | Detergent compositions containing a stabilized enzyme by phosphonates |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0104434A3 (en) | 1985-11-21 |
| US4608189A (en) | 1986-08-26 |
| DE3232616A1 (en) | 1984-03-08 |
| JPS5959799A (en) | 1984-04-05 |
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