EP0201016B1 - Builder-free liquid detergents with softening properties - Google Patents
Builder-free liquid detergents with softening properties Download PDFInfo
- Publication number
- EP0201016B1 EP0201016B1 EP86105800A EP86105800A EP0201016B1 EP 0201016 B1 EP0201016 B1 EP 0201016B1 EP 86105800 A EP86105800 A EP 86105800A EP 86105800 A EP86105800 A EP 86105800A EP 0201016 B1 EP0201016 B1 EP 0201016B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- component
- acid
- detergent
- fatty acids
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003599 detergent Substances 0.000 title claims abstract description 22
- 239000007788 liquid Substances 0.000 title claims abstract description 7
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 35
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 34
- 239000000194 fatty acid Substances 0.000 claims abstract description 34
- 229930195729 fatty acid Natural products 0.000 claims abstract description 34
- 239000000344 soap Substances 0.000 claims abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 150000001298 alcohols Chemical class 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 9
- 239000011734 sodium Substances 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000021281 monounsaturated fatty acids Nutrition 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 4
- 239000003352 sequestering agent Substances 0.000 claims abstract description 4
- 150000004996 alkyl benzenes Chemical class 0.000 claims abstract 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 7
- 102000004190 Enzymes Human genes 0.000 claims description 7
- 108090000790 Enzymes Proteins 0.000 claims description 7
- 239000005642 Oleic acid Substances 0.000 claims description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 7
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical class OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004435 Oxo alcohol Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical class OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims 1
- 235000003441 saturated fatty acids Nutrition 0.000 abstract description 4
- 239000012141 concentrate Substances 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract description 2
- 125000003158 alcohol group Chemical group 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 15
- -1 ether alcohols Chemical class 0.000 description 10
- 150000007513 acids Chemical class 0.000 description 9
- 238000005406 washing Methods 0.000 description 7
- 229940088598 enzyme Drugs 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 235000013772 propylene glycol Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 229940079919 digestives enzyme preparation Drugs 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- LPMBTLLQQJBUOO-KTKRTIGZSA-N (z)-n,n-bis(2-hydroxyethyl)octadec-9-enamide Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)N(CCO)CCO LPMBTLLQQJBUOO-KTKRTIGZSA-N 0.000 description 1
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- 241000194108 Bacillus licheniformis Species 0.000 description 1
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 240000001238 Gaultheria procumbens Species 0.000 description 1
- 235000007297 Gaultheria procumbens Nutrition 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 235000021319 Palmitoleic acid Nutrition 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 235000003095 Vaccinium corymbosum Nutrition 0.000 description 1
- 240000000851 Vaccinium corymbosum Species 0.000 description 1
- 235000017537 Vaccinium myrtillus Nutrition 0.000 description 1
- 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 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000012962 antiaging additive Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000021014 blueberries Nutrition 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N n-hexadecyl alcohol Natural products CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 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 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 235000020095 red wine Nutrition 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 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
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
- C11D3/0015—Softening compositions liquid
-
- 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
- C11D1/38—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
-
- 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 present invention relates to a skeletal salt-free, liquid detergent concentrate which, due to its surfactant composition in combination with specially selected fatty acid diethanolamides, has textile-softening and grip-improving properties, so that the textiles washed therewith do not require any aftertreatment with a special softening agent.
- conditioning agents which, in addition to quaternary ammonium salts with 2 long-chain alkyl radicals, additionally contain fatty acid monoethanolamides and their mixtures with fatty acid diethanolamides in which the fatty acids have 12 to 18 carbon atoms and are preferably derived from tallow fatty acids, which are known to have high proportions contain stearic acid.
- the problem of how such compounds behave or can be used in detergent-containing detergents is not addressed in these publications. Furthermore, it has been shown that the stearic acid derivatives cannot be used in an effective amount in storage-stable liquid detergents.
- liquid detergent formulations which have more or less large contents of fatty acid mono- or diethanolamides. These are always those alkanolamides which are derived from fatty acid mixtures with a high proportion of G2-COs fatty acids, for example coconut fatty acids. These alkanolamides are said to increase washing and foaming power or to improve skin tolerance. These remedies do not have an aviva effect.
- Such agents are those according to DE-A 1 047 973, DE-A 2 022 064, DE-A 2 703 998 (FR-A 2 378 852, US-A 4 153 570), DE-A 2 819 455 , DE-A 3 022 767, DE-A 3 161 222, EP-A 38 101, US-A 2 861 956, US-A 2 943 058.
- the agent according to the invention described below is suitable for avoiding the deficiencies mentioned.
- the invention relates to a liquid detergent containing (a) sodium alkylbenzenesulfonate with 10 to 14 carbon atoms in the linear alkyl group, (b) water-soluble, ethoxylated alcohols with 12 to 18 carbon atoms in the hydrocarbon radical and 5 to 10 glycol ether groups, (c ) a water-soluble soap derived from saturated and / or unsaturated fatty acids with 12 to 18 carbon atoms, (d) fatty acid diethanolamide, (e) sequestering agents from the class of polycarboxylic acids and polyphosphonic acids, (f) water-miscible organic solvents and water, thereby characterized in that the proportion of component (a) 5 to 15 wt .-%, component (b) 7 to 20 wt .-%, component (c), based on fatty acid, 6 to 16 wt .-%, the Component (d) is 7 to 15% by weight, component (e) is 0.2 to 3% by weight and component (f) is
- the proportion of the linear sodium alkylbenzenesulfonate (a) is 5 to 15% by weight, preferably 6 to 10% by weight. Dodecylbenzenesulfonate is preferably used.
- Suitable nonionic ethoxylated alcohols are fatty alcohols or oxo alcohols with 12 to 18, preferably 12 to 16, carbon atoms which are methyl-branched in the 2-position.
- the number of attached ethylene oxide groups (EO) is 5 to 10.
- Ethoxylated alcohols whose HLB value is 9 to 14, in particular 11 to 13.5, have proven to be very suitable. Examples of this are ethoxylated coconut fatty alcohols, from which the preliminary alcohols (10 and fewer carbon atoms) are separated and essentially consist of lauryl and myristyl alcohol in addition to small amounts of cetyl and stearyl alcohol.
- ethoxylated oxo alcohols or alcohols produced by ethylene polymerization which essentially consist of alcohol mixtures with 12 to 16 carbon atoms.
- the degree of ethoxylation of these preferred alcohols or alcohol mixtures is in particular 6 to 9.
- the proportion of component (b) is 7 to 20% by weight, preferably 8 to 15% by weight.
- Suitable soaps (c) are sodium and potassium soaps and soaps from alkanolamines, in particular triethanolamine, which are derived from saturated and monounsaturated fatty acids having 12 to 18 carbon atoms. Due to their low cloud point, soaps from coconut fatty acids (after separation of the fatty acids with less than 12 carbon atoms) and oleic acid or from oleic acid-rich fatty acid mixtures and combinations of these soaps are particularly suitable. These soap mixtures are preferably used in the form of sodium soaps or as mixtures of sodium soaps and triethanolamine soaps.
- the proportion of soaps (c) is 6 to 16% by weight, preferably 8 to 15% by weight, based in each case on the fatty acid content.
- Component (d) are fatty acid diethanolamides which are derived from monounsaturated fatty acids with 16 to 18 carbon atoms and their mixtures with saturated fatty acids of the same chain length, but the proportion of unsaturated compounds is at least 50% by weight, preferably is at least 65% by weight.
- Diethanolamides derived from oleic acid and palmitoleic acid and their mixtures with the corresponding palmitic acid and stearic acid derivatives as are obtainable from naturally occurring fatty acid mixtures rich in oleic acid, for example from tallow fatty acids or tall oil fatty acids, by isolating the unsaturated portions by known separation processes (network separation) are particularly suitable.
- Fatty acid fractions which can be used well contain, for example, 50 to 100% by weight, preferably 65 to 95% by weight of oleic acid and 0 to 50% by weight, preferably 5 to 35% by weight, of palmitic acid and stearic acid, and in industrial mixtures also small amounts, ie up to 5%, of myristic acid may be present.
- the ethanolamides which can be prepared from these fatty acids by reaction with diethanolamine are technical mixtures which usually contain 85 to 95% by weight of N-acyl compound and 2 to 10% by weight of O-acyl compound. In addition, small amounts, i.e. up to 5% by weight of unreacted starting material, mainly free diethanolamine and very small amounts of free fatty acid. These usual additions do not interfere in the present compositions, but can be regarded as functional constituents, especially since the compositions already contain soap and, in a preferred embodiment, also alkanolamines.
- the proportion of component (d) is 7 to 15% by weight, preferably 8 to 15% by weight and in particular 10 to 12% by weight.
- Suitable sequestering agents are polycarboxylic acids and polyphosphonic acids.
- Suitable polycarboxylic acids are citric acid, nitrilotriacetic acid, ethylenediaminoetetraacetic acid and their higher homologues.
- Suitable polyphosphonic acids are aminotri- (methylenephosphonic acid), ethylenediaminetetra- (methylenephosphonic acid), diethylenetriaminepenta- (methylenephosphonic acid) and their higher homologues. Said acids can be used as salts of sodium, potassium and alkanolamines, e.g. of triethanolamine.
- Citric acid ethylenediaminetetra- (methylenephosphonic acid) and diethylenetriaminepenta- (methylenephosphonic acid) and mixtures thereof are particularly suitable. They are present in the agents in proportions of 0.2 to 3% by weight, preferably 0.4 to 2% by weight.
- Water-miscible organic solvents which are present in the compositions in proportions of 5 to 15% by weight, preferably 7 to 13% by weight, are e.g. Alcohols, glycols, polyglycols and ether alcohols, such as methanol, ethanol, propanol, isopropanol, glycerin, glycol, diethylene glycol, triethylene glycol and low molecular weight polyethylene glycols, propylene glycol and oligomeric propylene glycol ethers, furthermore ether alcohols, such as methyl propyl glycol, methyl butyl glycol or methyl ethyl glycol. Mixtures of ethanol and propylene glycol in a ratio of 1: 4 to 4: 1 are preferably used as solvents.
- Alcohols, glycols, polyglycols and ether alcohols such as methanol, ethanol, propanol, isopropanol, glycerin, glycol, diethylene glycol, triethylene glycol and
- Additional ingredients which are advantageously added to the agents are enzymes, enzyme stabilizers, compounds for adjusting the pH, optical brighteners, hydrotropes, foam inhibitors, dyes or color pigments and agents which act as opacifiers or give the solutions a silky sheen.
- Suitable enzymes are proteases and amylases obtained from fungi or bacteria in a known manner and mixtures thereof, e.g. enzymes obtained from Bacillus subtilis or Bacillus licheniformis.
- the commercially available enzyme preparations usually also contain activators, such as calcium and magnesium salts, and extenders and binders. The content of the agents in these enzyme preparations is generally 0.1 to 1.5% by weight.
- the stability of the enzymes can be increased by adding alkanolamines, especially triethanolamine.
- the triethanolamine is expediently present in excess, as a result of which a desired weakly alkaline reaction of 7.2 to 9, preferably 7.5 to 8.5, can be set.
- Low molecular weight acids such as formic acid, acetic acid and lactic acid are suitable as further enzyme stabilizers, which, based on free acid, can be present in proportions of 0.1 to 2, preferably 0.2 to 1,% by weight. Due to the basic reaction of the agents, these acids are predominantly or completely in the form of their salts, e.g. as sodium, potassium or alkanolamine salts.
- Disulfonic acid or diphenyl-distyryl-disulfonic acid in the form of their water-soluble salts - as optical brighteners are those known derivatives of the bis-triazinyl-4,4 'diaminostilbene-2,2' are suitable.
- Examples of these are salts of 4,4-bis (-2 " -anilino-4" -morpholino-1,3,5-triazinyl-6 "-amino) -stilbene-2,2-disulfonic acid or of 4,4- Bis (2-sulfostyryl) diphenyl, 4,4-bis (4-chloro-3-sulfostyryl) diphenyl and 4- (4-chlorostyryl) -4- (2-sulfostyryl) diphenyl.
- Suitable foam inhibitors are water-dispersible silicones, e.g. Dimethylpolysiloxanes, which can optionally be modified with polyglycol ether groups, and mixtures of such compounds with polysiloxane resins or finely divided silica, which is preferably silanated.
- the content of optical brighteners and silicone defoamers in the agents can be in the order of 0.01 to 1% by weight.
- the water content of the agents should be adjusted so that a homogeneous, easily pourable solution that is not segregated by precipitation results.
- the water content is generally between 25 and 45% by weight, preferably between 33 and 40% by weight.
- the agents according to the invention are notable for high washing and cleaning properties as well as favorable softening and grip-improving properties. They are suitable both for hand washing and due to their balanced foam behavior for use in washing machines.
- EO attached ethylene oxide
- the reflectance of the samples was determined photometrically and the handle (degree of softness) was assessed. The mean was formed from 9 measurements or samples.
- comparative samples were used which had been washed under similar conditions with a commercially available high-performance detergent (V2) without further textile aftertreatment.
- V3 commercially available high-performance detergent
- the grip properties were determined after 1 wash treatment and after 5 wash treatments.
- the handle assessments were carried out on terry towels washed once. The results are shown in the following tables. They demonstrate the superiority of the agents according to the invention.
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Abstract
Description
Die vorliegende Erfindung betrifft ein gerüstsalzfreies, flüssiges Waschmittelkonzentrat, das aufgrund seiner Tensidzusammensetzung in Verbindung mit speziell ausgewählten Fettsäurediethanolamiden textilweichmachende und griffverbessernde Eigenschaften besitzt, so daß die damit gewaschenen Textilien keiner Nachbehandlung mit einem speziellen Avivagemittel bedürfen.The present invention relates to a skeletal salt-free, liquid detergent concentrate which, due to its surfactant composition in combination with specially selected fatty acid diethanolamides, has textile-softening and grip-improving properties, so that the textiles washed therewith do not require any aftertreatment with a special softening agent.
Es ist aus der Zeitschrift "Soap and Chemical Specialities", November 1958, Seiten 48 bis 50; bekannt, daß gewisse Stearinsäurederivate von Alkylolaminen als weichmachendes Agens in Textilbehandlungsmitteln eingesetzt werden. Aus GB-A 1 104 441 sind Avivagemittel bekannt, die neben quartären Ammoniumsalzen mit 2 langkettigen Akylresten zusätzlich Fettsäuremonoethanolamide und deren Gemische mit Fettsäurediethanolamiden enthalten, in denen die Fettsäuren 12 bis 18 C-Atome aufweisen und sich bevorzugt von Talgfettsäuren ableiten, die bekanntlich hohe Anteile an Stearinsäure enthalten. Das Problem, wie sich derartige Verbindungen in tensidhaltigen Waschmitteln verhalten bzw. eingesetzt werden können, wird in diesen Publikationen nicht berührt. Im übrigen hat sich gezeigt, daß die Stearinsäurederivate sich nicht in wirksamer Menge in lagerstabile Flüssigwaschmittel einsetzen lassen.It is from the journal "Soap and Chemical Specialties", November 1958, pages 48 to 50; It is known that certain stearic acid derivatives of alkylolamines are used as softening agents in textile treatment agents. From GB-A 1 104 441, conditioning agents are known which, in addition to quaternary ammonium salts with 2 long-chain alkyl radicals, additionally contain fatty acid monoethanolamides and their mixtures with fatty acid diethanolamides in which the fatty acids have 12 to 18 carbon atoms and are preferably derived from tallow fatty acids, which are known to have high proportions contain stearic acid. The problem of how such compounds behave or can be used in detergent-containing detergents is not addressed in these publications. Furthermore, it has been shown that the stearic acid derivatives cannot be used in an effective amount in storage-stable liquid detergents.
Ferner sind zahlreiche Flüssigwaschmittel-Rezepturen bekannt, die mehr oder weniger große Gehalte an Fettsäuremono- bzw. diethanolamiden aufweisen. Stets handelt es sich dabei um solche Alkanolamide, die sich von Fettsäuregemischen mit hohem Anteil an G2-COs-Fettsäuren, beispielsweise Cocosfettsäuren, ableiten. Diese Alkanolamide sollen die Wasch- und Schaumkraft steigern bzw. die Hautverträglichkeit verbessern. Eine Avivagewirkung kommt diesen Mitteln nicht zu. Als Beispiele für derartige Mittel seien die gemäß DE-A 1 047 973, DE-A 2 022 064, DE-A 2 703 998 (FR-A 2 378 852, US-A 4 153 570), DE-A 2 819 455, DE-A 3 022 767, DE-A 3 161 222, EP-A 38 101, US-A 2 861 956, US-A 2 943 058 aufgeführt.Furthermore, numerous liquid detergent formulations are known which have more or less large contents of fatty acid mono- or diethanolamides. These are always those alkanolamides which are derived from fatty acid mixtures with a high proportion of G2-COs fatty acids, for example coconut fatty acids. These alkanolamides are said to increase washing and foaming power or to improve skin tolerance. These remedies do not have an aviva effect. Examples of such agents are those according to DE-A 1 047 973, DE-A 2 022 064, DE-A 2 703 998 (FR-A 2 378 852, US-A 4 153 570), DE-A 2 819 455 , DE-A 3 022 767, DE-A 3 161 222, EP-A 38 101, US-A 2 861 956, US-A 2 943 058.
Weiterhin wurde bereits vorgeschlagen, Waschmitteln mit einem Gehalt an Aniontensiden avivierend wirkende Quartärsalze zuzusetzen, wobei die Quartärsalze längerkettige Fettsäurereste bzw. Fettalkylreste aufweisen. Da jedoch Aniontenside mit derartigen Quartärsalzen im allgemeinen unverträglich sind bzw. unter Bildung inaktiver Elektroneutralsalze reagieren, wird die erwünschte Wirkung in der Regel nicht erzielt.Furthermore, it has already been proposed to add detergents containing quaternary salts with an anionic surfactant effect, the quaternary salts having longer-chain fatty acid residues or fatty alkyl residues. However, since anionic surfactants are generally incompatible with quaternary salts of this type or react to form inactive electroneutral salts, the desired effect is generally not achieved.
Das nachfolgend beschriebene erfindungsgemäße Mittel ist geeignet, die genannten Mängel zu vermeiden.The agent according to the invention described below is suitable for avoiding the deficiencies mentioned.
Gegenstand der Erfindung ist ein Flüssigwaschmittel mit einem Gehalt an (a) Natriumalkylbenzolsulfonat mit 10 bis 14 C-Atomen in der linearen Alkylgruppe, (b) wasserlöslichen, ethoxylierten Alkoholen mit 12 bis 18 C-Atomen im Kohlenwasserstoffrest und 5 bis 10 Glykolethergruppen, (c) einer wasserlöslichen Seife, abgeleitet von gesättigten und/oder ungesättigten Fettsäuren mit 12 bis 18 C-Atomen, (d) Fettsäurediethanolamid, (e) Sequestrierungsmitteln aus der Klasse der Polycarbonsäuren und Polyphosphonsäuren, (f) mit Wasser mischbaren organischen Lösungsmitteln und Wasser, dadurch gekennzeichnet, daß der Anteil der Komponente (a) 5 bis 15 Gew.-%, der Komponente (b) 7 bis 20 Gew.-%, der Komponente (c), auf Fettsäure bezogen, 6 bis 16 Gew.-%, der Komponente (d) 7 bis 15 Gew.-%, der Komponente (e) 0,2 bis 3 Gew.-% und der Komponente (f) 5 bis 15 Gew.-% beträgt, mit der Maßgabe, daß das Verhältnis von (a):(b):(c):(d) = 1:(1-2):(1-2):(1,5-2,5) beträgt und die Komponente (d) sich von Fettsäuren mit 16 bis 18 Kohlenstoffatomen mit mehr als 50% an einfach ungesättigten Fettsäuren ableitet.The invention relates to a liquid detergent containing (a) sodium alkylbenzenesulfonate with 10 to 14 carbon atoms in the linear alkyl group, (b) water-soluble, ethoxylated alcohols with 12 to 18 carbon atoms in the hydrocarbon radical and 5 to 10 glycol ether groups, (c ) a water-soluble soap derived from saturated and / or unsaturated fatty acids with 12 to 18 carbon atoms, (d) fatty acid diethanolamide, (e) sequestering agents from the class of polycarboxylic acids and polyphosphonic acids, (f) water-miscible organic solvents and water, thereby characterized in that the proportion of component (a) 5 to 15 wt .-%, component (b) 7 to 20 wt .-%, component (c), based on fatty acid, 6 to 16 wt .-%, the Component (d) is 7 to 15% by weight, component (e) is 0.2 to 3% by weight and component (f) is 5 to 15% by weight, with the proviso that the ratio of ( a) :( b) :( c) :( d) = 1: (1-2) :( 1-2) :( 1.5-2.5) and component (d) is derived from fatty acids with 16 to 18 carbon atoms with more than 50% of monounsaturated fatty acids.
Der Anteil des linearen Natrium-alkylbenzolsulfonats (a) beträgt 5 bis 15 Gew.-%, vorzugsweise 6 bis 10 Gew.-%. Vorzugsweise wird Dodecylbenzolsulfonat eingesetzt.The proportion of the linear sodium alkylbenzenesulfonate (a) is 5 to 15% by weight, preferably 6 to 10% by weight. Dodecylbenzenesulfonate is preferably used.
Als nichtionische ethoxylierte Alkohole (b) kommen Fettalkohole bzw. in 2-Stellung methylverzweigte Oxo-Alkohole mit 12 bis 18, vorzugsweise 12 bis 16 C-Atomen infrage. Die Anzahl der angelagerten Ethylenoxidgruppen (EO) beträgt 5 bis 10. Als gut geeignet haben sich solche ethoxylierten Alkohole erwiesen, deren HLB-Wert 9 bis 14, insbesondere 11 bis 13,5 beträgt. Beispiele hierfür sind ethoxylierte Cocosfettalkohole, von denen die Vorlaufalkohole (10 und weniger C-Atome) abgetrennt sind und im wesentlichen aus Lauryl- und Myristylalkohol neben geringen Anteilen an Cetyl- und Stearylalkohol bestehen. Besonders geeignet sind ferner ethoxylierte Oxoalkohole bzw. durch Ethylenpolymerisation hergestellte Alkohole, die im wesentlichen aus Alkoholgemischen mit 12 bis 16 C-Atomen bestehen. Der Ethoxylierungsgrad dieser bevorzugten Alkohole bzw. Alkoholgemische beträgt insbesondere 6 bis 9. Der Anteil der Komponente (b) beträgt 7 bis 20 Gew.-%, vorzugsweise 8 bis 15 Gew.-%.Suitable nonionic ethoxylated alcohols (b) are fatty alcohols or oxo alcohols with 12 to 18, preferably 12 to 16, carbon atoms which are methyl-branched in the 2-position. The number of attached ethylene oxide groups (EO) is 5 to 10. Ethoxylated alcohols whose HLB value is 9 to 14, in particular 11 to 13.5, have proven to be very suitable. Examples of this are ethoxylated coconut fatty alcohols, from which the preliminary alcohols (10 and fewer carbon atoms) are separated and essentially consist of lauryl and myristyl alcohol in addition to small amounts of cetyl and stearyl alcohol. Also particularly suitable are ethoxylated oxo alcohols or alcohols produced by ethylene polymerization, which essentially consist of alcohol mixtures with 12 to 16 carbon atoms. The degree of ethoxylation of these preferred alcohols or alcohol mixtures is in particular 6 to 9. The proportion of component (b) is 7 to 20% by weight, preferably 8 to 15% by weight.
Als Seifen (c) kommen Natrium- und Kaliumseifen sowie Seifen von Alkanolaminen, insbesondere Triethanolamin, infrage, die sich von gesättigten und einfach ungesättigten Fettsäuren mit 12 bis 18 C-Atomen ableiten. Aufgrund ihres niedrig liegenden Trübungspunktes eignen sich insbesondere Seifen von Cocosfettsäuren (nach Abtrennung der Fettsäuren mit weniger als 12 C-Atomen) sowie der Ölsäure bzw. von ölsäurereichen Fettsäuregemischen sowie Kombinationen dieser Seifen. Diese Seifengemische werden vorzugsweise in Form der Natriumseifen bzw. als Gemische von Natriumseifen und Triethanolaminseifen eingesetzt.Suitable soaps (c) are sodium and potassium soaps and soaps from alkanolamines, in particular triethanolamine, which are derived from saturated and monounsaturated fatty acids having 12 to 18 carbon atoms. Due to their low cloud point, soaps from coconut fatty acids (after separation of the fatty acids with less than 12 carbon atoms) and oleic acid or from oleic acid-rich fatty acid mixtures and combinations of these soaps are particularly suitable. These soap mixtures are preferably used in the form of sodium soaps or as mixtures of sodium soaps and triethanolamine soaps.
Der Anteil der Seifen (c) beträgt 6 bis 16 Gew.-%, vorzugsweise 8 bis 15 Gew.-%, jeweils bezogen auf den Gehalt an Fettsäure.The proportion of soaps (c) is 6 to 16% by weight, preferably 8 to 15% by weight, based in each case on the fatty acid content.
Als Komponente (d) kommen Fettsäurediethanolamide infrage, die sich von einfach ungesättigten Fettsäuren mit 16 bis 18 C-Atomen sowie deren Gemischen mit gesättigten Fettsäuren gleicher Kettenlänge ableiten, wobei jedoch der Anteil der ungesättigten Verbindungen mindestens 50 Gew.-%, vorzugsweise mindestens 65 Gew.-% beträgt. Geeignet sind insbesondere von Ölsäure und Palmitoleinsäure abgeleitete Diethanolamide sowie deren Gemische mit den entsprechenden Palmitinsäure- und Stearinsäurederivaten, so wie sie aus natürlich vorkommenden ölsäurereichen Fettsäuregemischen, z.B. aus Taigfettsäuren oder Tallölfettsäuren, durch Isolierung der ungesättigten Anteile nach bekannten Trennverfahren (Umnetztrennung) zugänglich sind. Gut brauchbare Fettsäurefraktionen enthalten z.B. 50 bis 100 Gew.-%, vorzugsweise 65 bis 95 Gew.-% Ölsäure und 0 bis 50 Gew.-%, vorzugsweise 5 bis 35 Gew.-%, Palmitinsäure und Stearinsäure, wobei in technischen Gemischen auch noch geringe Mengen, d.h. bis zu 5%, an Myristinsäure vorliegen können.Component (d) are fatty acid diethanolamides which are derived from monounsaturated fatty acids with 16 to 18 carbon atoms and their mixtures with saturated fatty acids of the same chain length, but the proportion of unsaturated compounds is at least 50% by weight, preferably is at least 65% by weight. Diethanolamides derived from oleic acid and palmitoleic acid and their mixtures with the corresponding palmitic acid and stearic acid derivatives, as are obtainable from naturally occurring fatty acid mixtures rich in oleic acid, for example from tallow fatty acids or tall oil fatty acids, by isolating the unsaturated portions by known separation processes (network separation) are particularly suitable. Fatty acid fractions which can be used well contain, for example, 50 to 100% by weight, preferably 65 to 95% by weight of oleic acid and 0 to 50% by weight, preferably 5 to 35% by weight, of palmitic acid and stearic acid, and in industrial mixtures also small amounts, ie up to 5%, of myristic acid may be present.
Die aus diesen Fettsäuren durch Umsetzung mit Diethanolamin herstellbaren Ethanolamide stellen technische Gemische dar, die üblicherweise 85 bis 95 Gew.-% N-Acylverbindung und 2 bis 10 Gew.-% O-Acylverbindung enthalten. Darüber hinaus können geringe Mengen, d.h. bis zu 5 Gew.-%, an nicht umgesetztem Ausgangsmaterial, hauptsächlich freies Diethanolamin sowie sehr geringe Mengen an freier Fettsäure anwesend sein. Diese üblichen Beimengungen stören in den vorliegenden Mitteln nicht, sondern können als funktionelle Bestandteile betrachtet werden, zumal die Mittel ohnehin Seife und in einer bevorzugten Ausführungsform auch Alkanolamine enthalten.The ethanolamides which can be prepared from these fatty acids by reaction with diethanolamine are technical mixtures which usually contain 85 to 95% by weight of N-acyl compound and 2 to 10% by weight of O-acyl compound. In addition, small amounts, i.e. up to 5% by weight of unreacted starting material, mainly free diethanolamine and very small amounts of free fatty acid. These usual additions do not interfere in the present compositions, but can be regarded as functional constituents, especially since the compositions already contain soap and, in a preferred embodiment, also alkanolamines.
Der Anteil der Komponente (d) beträgt 7 bis 15 Gew.-%, vorzugsweise 8 bis 15 Gew.-% und insbesondere 10 bis 12 Gew.-%.The proportion of component (d) is 7 to 15% by weight, preferably 8 to 15% by weight and in particular 10 to 12% by weight.
Als Sequestrierungsmittel (e) kommen Polycarbonsäuren und Polyphosphonsäuren infrage. Geeignete Polycarbonsäuren sind Citronensäure, Nitrilotriessigsäure, Ethylendiaminoetetraessigsäure und deren höhere Homologen. Geeignete Polyphosphonsäuren sind Aminotri-(methylenphosphonsäure), Ethy- lendiamintetra-(methylenphosphonsäure), Diethylentriaminpenta-(methylenphosphonsäure) sowie deren höhere Homologen. Die genannten Säuren können als Salze des Natriums, Kaliums und von Alkanolaminen, z.B. des Triethanolamins, vorliegen. Besonders geeignet sind Citronensäure, Ethylendiamintetra-(methylenphosphonsäure) und Diethylentriaminpenta-(methylenphosphonsäure) sowie deren Gemische. Sie sind in den Mitteln in Anteilen von 0,2 bis 3 Gew.-%, vorzugsweise 0,4 bis 2 Gew.-% anwesend.Suitable sequestering agents (e) are polycarboxylic acids and polyphosphonic acids. Suitable polycarboxylic acids are citric acid, nitrilotriacetic acid, ethylenediaminoetetraacetic acid and their higher homologues. Suitable polyphosphonic acids are aminotri- (methylenephosphonic acid), ethylenediaminetetra- (methylenephosphonic acid), diethylenetriaminepenta- (methylenephosphonic acid) and their higher homologues. Said acids can be used as salts of sodium, potassium and alkanolamines, e.g. of triethanolamine. Citric acid, ethylenediaminetetra- (methylenephosphonic acid) and diethylenetriaminepenta- (methylenephosphonic acid) and mixtures thereof are particularly suitable. They are present in the agents in proportions of 0.2 to 3% by weight, preferably 0.4 to 2% by weight.
Mit Wasser mischbare organische Lösungsmittel, die in den Mitteln in Anteilen von 5 bis 15 Gew.-%, vorzugsweise 7 bis 13 Gew.-% vorliegen, sind z.B. Alkohole, Glykole, Polyglykole und Etheralkohole, wie Methanol, Ethanol, Propanol, Isopropanol, Glycerin, Glykol, Diethylenglykol, Triethylenglykol und niedermolekulare Polyethylenglykole, Propylenglykol und oligomere Propylenglykolether, ferner Etheralkohole, wie Methylpropylglykol, Methylbutylglykol oder Methylethylglykol. Vorzugsweise werden Gemische aus Ethanol und Propylenglykol im Verhältnis 1:4 bis 4:1 als Lösungsmittel verwendet.Water-miscible organic solvents, which are present in the compositions in proportions of 5 to 15% by weight, preferably 7 to 13% by weight, are e.g. Alcohols, glycols, polyglycols and ether alcohols, such as methanol, ethanol, propanol, isopropanol, glycerin, glycol, diethylene glycol, triethylene glycol and low molecular weight polyethylene glycols, propylene glycol and oligomeric propylene glycol ethers, furthermore ether alcohols, such as methyl propyl glycol, methyl butyl glycol or methyl ethyl glycol. Mixtures of ethanol and propylene glycol in a ratio of 1: 4 to 4: 1 are preferably used as solvents.
Zusätzliche Bestandteile, die den Mitteln vorteilhaft zugesetzt werden, sind Enzyme, Enzymstabilisatoren, Verbindungen zur Einstellung des pH-Wertes, optische Aufheller, Hydrotrope, Schauminhibitoren, Farbstoffe bzw. Farbpigmente und Mittel, die als Trübungsstoffe wirken bzw. den Lösungen einen Seidenglanz verleihen.Additional ingredients which are advantageously added to the agents are enzymes, enzyme stabilizers, compounds for adjusting the pH, optical brighteners, hydrotropes, foam inhibitors, dyes or color pigments and agents which act as opacifiers or give the solutions a silky sheen.
Als Enzyme eignen sich aus Pilzen oder Bakterien in bekannter Weise gewonnene Proteasen und Amylasen sowie deren Gemische, z.B. aus Bacillus subtilis oder Bacillus licheniformis gewonnene Enzyme. Die handelsüblichen Enzymzubereitungen enthalten in der Regel noch Aktivatoren, wie Calcium- und Magnesiumsalze, sowie Streck- und Bindemittel. Der Gehalt der Mittel an diesen Enzymzubereitungen beträgt im allgemeinen 0,1 bis 1,5 Gew.-%.Suitable enzymes are proteases and amylases obtained from fungi or bacteria in a known manner and mixtures thereof, e.g. enzymes obtained from Bacillus subtilis or Bacillus licheniformis. The commercially available enzyme preparations usually also contain activators, such as calcium and magnesium salts, and extenders and binders. The content of the agents in these enzyme preparations is generally 0.1 to 1.5% by weight.
Die Stabilität der Enzyme kann durch Zusatz von Alkanolaminen, insbesondere Triethanolamin, erhöht werden. Das Triethanolamin ist zweckmäßigerweise im Überschuß vorhanden, wodurch sich eine gewünschte schwach alkalische Reaktion von 7,2 bis 9, vorzugsweise von 7,5 bis 8,5 einstellen läßt.The stability of the enzymes can be increased by adding alkanolamines, especially triethanolamine. The triethanolamine is expediently present in excess, as a result of which a desired weakly alkaline reaction of 7.2 to 9, preferably 7.5 to 8.5, can be set.
Als weitere Enzymstabilisatoren eignen sich niedermolekulare Säuren wie Ameisensäure, Essigsäure und Milchsäure, die, auf freie Säure bezogen, in Anteilen von 0,1 bis 2, vorzugsweise 0,2 bis 1 Gew.-% anwesend sein können. Aufgrund der basischen Reaktion der Mittel liegen diese Säuren überwiegend oder vollständig in Form ihrer Salze vor, z.B. als Natrium-, Kalium- oder Alkanolaminsalze.Low molecular weight acids such as formic acid, acetic acid and lactic acid are suitable as further enzyme stabilizers, which, based on free acid, can be present in proportions of 0.1 to 2, preferably 0.2 to 1,% by weight. Due to the basic reaction of the agents, these acids are predominantly or completely in the form of their salts, e.g. as sodium, potassium or alkanolamine salts.
Als optische Aufheller eignen sich die bekannten Derivate der Bis-triazinyl-4,4'-diaminostilben-2,2'- disulfonsäure bzw. der Diphenyl-distyryl-disulfonsäure in Form ihrer wasserlöslichen Salze. Beispiele hierfür sind Salze der 4,4-Bis(-2"-anilino-4"-morpholino-1,3,5-triazinyl-6"-amino)-stilben-2,2-disulfonsäure bzw. des 4,4-Bis-(2-sulfostyryl)-diphenyls, 4,4-Bis(4-chlor-3-sulfostyryl)-diphenyls und 4-(4-Chlorstyryl)-4-(2-sulfostyryl)-diphenyls.Disulfonic acid or diphenyl-distyryl-disulfonic acid in the form of their water-soluble salts - as optical brighteners are those known derivatives of the bis-triazinyl-4,4 'diaminostilbene-2,2' are suitable. Examples of these are salts of 4,4-bis (-2 " -anilino-4" -morpholino-1,3,5-triazinyl-6 "-amino) -stilbene-2,2-disulfonic acid or of 4,4- Bis (2-sulfostyryl) diphenyl, 4,4-bis (4-chloro-3-sulfostyryl) diphenyl and 4- (4-chlorostyryl) -4- (2-sulfostyryl) diphenyl.
Als Schauminhibitoreh eignen sich in Wasser dispergierbare Silikone, z.B. Dimethylpolysiloxane, die gegebenenfalls mit Polyglykolethergruppen modifiziert sein können, sowie Gemische derartiger Verbindungen mit Polysiloxanharzen bzw. feinteiliger Kieselsäure, die vorzugsweise silaniert ist. Der Gehalt der Mittel an optischen Aufhellern und Silikonentschäumern kann in der Größenordnung 0,01 bis 1 Gew.- % liegen.Suitable foam inhibitors are water-dispersible silicones, e.g. Dimethylpolysiloxanes, which can optionally be modified with polyglycol ether groups, and mixtures of such compounds with polysiloxane resins or finely divided silica, which is preferably silanated. The content of optical brighteners and silicone defoamers in the agents can be in the order of 0.01 to 1% by weight.
Der Wassergehalt der Mittel soll so eingestellt sein, daß eine homogene, gut gießbare und nicht durch Ausfällungen entmischte Lösung entsteht. Der Wassergehalt liegt im allgemeinen zwischen 25 und 45 Gew.-%, vorzugsweise zwischen 33 und 40 Gew.-%.The water content of the agents should be adjusted so that a homogeneous, easily pourable solution that is not segregated by precipitation results. The water content is generally between 25 and 45% by weight, preferably between 33 and 40% by weight.
Die erfindungsgemäßen Mittel zeichnen sich durch ein hohes Wasch- und Reinigungsvermögen sowie günstige weichmachende und griffverbessernde Eigenschaften aus. Sie eignen sich sowohl für ein Waschen von Hand als auch aufgrund ihres ausgewogenen Schaumverhaltens zur Anwendung in Waschmaschinen.The agents according to the invention are notable for high washing and cleaning properties as well as favorable softening and grip-improving properties. They are suitable both for hand washing and due to their balanced foam behavior for use in washing machines.
Zur Herstellung eines Mittels gemäß nachstehender Zusammensetzung wurde eine 50% wäßrige Paste von Natrium-dodecylbenzolsulfonat mit dem nichtionischen Tensid (Abkürzung EO = angelagertes Ethylenoxid) vermischt, anschließend das Lösungsmittel, das Fettsäurediethanolamid und die zur Seifenbildung benötigte Fettsäure sowie die Phosphonsäure (Diethylentriamin-pentamethylenphosphonsäure) und die Citronensäure zugemischt. Nach der Neutralisation mit Natronlauge und Triethanolamin erfolgte der Zusatz der übrigen Stoffe (Angaben in Gew.-%, bezogen auf wasserfreie Substanz). In dem Vergleichsprodukt V1 wurde das Olsäurediethanolamid zu gleichen Teilen durch Alkylbenzolsulfonat und nichtionisches Tensid ersetzt.
Das Waschvermögen und die Avivagewirkung wurden unter praxisnahen Bedingungen getestet. Hierzu wurden Textilproben aus Baumwolle, die unter standardisierten Bedingungen mit Hautfett, Pigmentschmutz und Flecken von Rotwein, Tee und Blaubeeren angeschmutzt worden waren, zusammen mit 3 kg Ballastwäsche in einem Haushaltswaschautomaten (Kapazität 4 kg) bei 60°C und 90°C gewaschen. Die Waschdauer einschließlich Aufheizung betrug 20 Minuten, die Waschmittelkonzentration 7,5 g/Liter, das Verhältnis von Textilmenge (in kg) zu Waschlauge (in Liter) betrug 1:10, die Härte des Leitungswassers 16°dH (160 mg Ca0 pro Liter). Nach dreimaligem Nachspülen wurde geschleudert und getrocknet. Die Remission der Proben wurde photometrisch bestimmt und der Griff (Weichheitsgrad) beurteilt. Aus jeweils 9 Messungen bzw. Abmusterungen wurde der Mittelwert gebildet. Bei der Beurteilung der weichmachenden Eigenschaften wurden Vergleichsproben herangezogen, die unter gleichartigen Bedingungen mit einem handelsüblichen Hochleistungswaschmittel (V2) ohne weitere Textilnachbehandlung gewaschen worden waren. In einer dritten Versuchsreihe wurden Proben zum Vergleich herangezogen, die mit einem handelsüblichen Hochleistungswaschmittel (V3) gewaschen wurden, das einen avivierend wirkenden Zusatz auf Basis eines Cocosalkyl-trimethylammoniumsalzes enthielt. Die Bestimmung der Griffeigenschaften wurden nach 1 Waschbehandlung sowie nach 5 Waschbehandlungen vorgenommen. Zusätzlich wurden die Griffbeurteilungen an 1 mal gewaschener Frottierware vorgenommen. Die Ergebnisse sind den folgenden Tabellen zu entnehmen. Sie belegen die Überlegenheit der erfindungsgemäßen Mittel.
Griff (0 = niedrigste, 6 = höchste Bewertung; 6 entspricht der Wirkung eines im 4. Spülgang eingesetzten hochwirksamen Avivagemittels)Handle (0 = lowest, 6 = highest rating; 6 corresponds to the effect of a highly effective anti-aging agent used in the 4th rinse)
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT86105800T ATE49608T1 (en) | 1985-05-04 | 1986-04-26 | SALT-FREE LIQUID DETERGENT WITH TEXTILE SOFTENING PROPERTIES. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19853516091 DE3516091A1 (en) | 1985-05-04 | 1985-05-04 | NO-SALT-FREE LIQUID DETERGENT WITH TEXTILE SOFTENING PROPERTIES |
| DE3516091 | 1985-05-04 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0201016A2 EP0201016A2 (en) | 1986-11-12 |
| EP0201016A3 EP0201016A3 (en) | 1987-09-23 |
| EP0201016B1 true EP0201016B1 (en) | 1990-01-17 |
Family
ID=6269852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86105800A Expired - Lifetime EP0201016B1 (en) | 1985-05-04 | 1986-04-26 | Builder-free liquid detergents with softening properties |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4717507A (en) |
| EP (1) | EP0201016B1 (en) |
| JP (1) | JPS61255999A (en) |
| AT (1) | ATE49608T1 (en) |
| DE (1) | DE3668330D1 (en) |
| ES (1) | ES8900056A1 (en) |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3639322A1 (en) * | 1986-11-17 | 1988-05-26 | Henkel Kgaa | METHOD FOR CLEANING AND DISINFECTING ENDOSCOPES AND MEANS FOR IMPLEMENTING THE METHOD |
| JPS644226A (en) * | 1987-06-25 | 1989-01-09 | Kao Corp | Strong alkali aqueous solution of nonionic surfactant |
| GB8818215D0 (en) * | 1988-07-30 | 1988-09-01 | Flow Lab | Phosphate-free detergent |
| US5269960A (en) * | 1988-09-25 | 1993-12-14 | The Clorox Company | Stable liquid aqueous enzyme detergent |
| USRE35621E (en) * | 1989-05-30 | 1997-10-07 | Hercules Incorporated | Cardable hydrophobic polypropylene fiber, material and method for preparation thereof |
| ATE139276T1 (en) * | 1990-11-15 | 1996-06-15 | Hercules Inc | CARDABLE HYDROPHOBIC POLYOLEFIN FIBER, MATERIAL AND METHOD FOR PRODUCING SAME |
| ES2080241T3 (en) * | 1991-09-27 | 1996-02-01 | Procter & Gamble | SOFTENING COMPOSITIONS OF CONCENTRATED FABRICS. |
| US5545481A (en) * | 1992-02-14 | 1996-08-13 | Hercules Incorporated | Polyolefin fiber |
| US5298195A (en) * | 1992-03-09 | 1994-03-29 | Amway Corporation | Liquid dishwashing detergent |
| EP0592947A1 (en) * | 1992-10-12 | 1994-04-20 | ALBRIGHT & WILSON UK LIMITED | Cleaning preparations |
| WO1999000479A1 (en) * | 1997-06-27 | 1999-01-07 | The Procter & Gamble Company | Non-aqueous, fatty acid-containing structured liquid detergent compositions |
| US6395693B1 (en) * | 1999-09-27 | 2002-05-28 | Cabot Microelectronics Corporation | Cleaning solution for semiconductor surfaces following chemical-mechanical polishing |
| US6534462B1 (en) | 2000-07-10 | 2003-03-18 | Access Business Group International Llc | Liquid laundry detergent and pretreatment composition |
| GB2371307B (en) * | 2001-01-19 | 2003-10-15 | Reckitt Benckiser Nv | Packaged detergent compositions |
| WO2002086041A1 (en) * | 2001-04-19 | 2002-10-31 | Lataniotis Christos Of Lazaros | General purpose liquid cleaning composition and method for the preparation thereof |
| US20040077519A1 (en) * | 2002-06-28 | 2004-04-22 | The Procter & Gamble Co. | Ionic liquid based products and method of using the same |
| BRPI0416944A (en) * | 2003-12-05 | 2007-02-13 | Unilever Nv | liquid laundry detergent composition and method for cleaning a fabric substrate |
| US20050176617A1 (en) * | 2004-02-10 | 2005-08-11 | Daniel Wood | High efficiency laundry detergent |
| US20060090271A1 (en) * | 2004-11-01 | 2006-05-04 | Price Kenneth N | Processes for modifying textiles using ionic liquids |
| US20060090777A1 (en) * | 2004-11-01 | 2006-05-04 | Hecht Stacie E | Multiphase cleaning compositions having ionic liquid phase |
| US7776810B2 (en) * | 2004-11-01 | 2010-08-17 | The Procter & Gamble Company | Compositions containing ionic liquid actives |
| US20060094616A1 (en) * | 2004-11-01 | 2006-05-04 | Hecht Stacie E | Ionic liquids derived from surfactants |
| US7737102B2 (en) * | 2004-11-01 | 2010-06-15 | The Procter & Gamble Company | Ionic liquids derived from functionalized anionic surfactants |
| US7939485B2 (en) * | 2004-11-01 | 2011-05-10 | The Procter & Gamble Company | Benefit agent delivery system comprising ionic liquid |
| US20060094621A1 (en) * | 2004-11-01 | 2006-05-04 | Jordan Glenn T Iv | Process for improving processability of a concentrate and compositions made by the same |
| US7786065B2 (en) * | 2005-02-18 | 2010-08-31 | The Procter & Gamble Company | Ionic liquids derived from peracid anions |
| JP4749781B2 (en) * | 2005-07-07 | 2011-08-17 | 花王株式会社 | Method for activating α-amylase |
| US8889612B2 (en) * | 2010-04-19 | 2014-11-18 | The Procter & Gamble Company | Method of laundering fabric using a compacted liquid laundry detergent composition |
| JP5912812B2 (en) * | 2012-04-26 | 2016-04-27 | 花王株式会社 | Disinfectant composition for textile products |
| SE1750157A1 (en) * | 2014-07-18 | 2017-02-17 | Morgan Sophia | Stain remover kit |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1104441A (en) * | 1964-07-08 | 1968-02-28 | Unilever Ltd | Fabric conditioner |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2861956A (en) * | 1953-02-25 | 1958-11-25 | Monsanto Chemicals | Liquid detergent compositions |
| DE1047973B (en) * | 1956-09-21 | 1958-12-31 | Willi Maurer K G | Resistant detergent pastes |
| US2943058A (en) * | 1956-10-15 | 1960-06-28 | Diamond Alkali Co | Liquid detergent compositions |
| US3697451A (en) * | 1969-01-02 | 1972-10-10 | Witco Chemical Corp | Stable enzyme containing liquid detergent |
| DE2703998C3 (en) * | 1977-02-01 | 1981-10-01 | Henkel KGaA, 4000 Düsseldorf | Liquid detergent concentrate with low foaming power |
| GB1600018A (en) * | 1977-05-06 | 1981-10-14 | Unilever Ltd | Liquid detergent composition |
| FR2466501A1 (en) * | 1979-10-01 | 1981-04-10 | Unilever Nv | Stable liq. aq. soap compsn. - contg. ethanolamine soap and fatty acid or alkanol:amide as thickener |
| US4452717A (en) * | 1980-04-09 | 1984-06-05 | Lever Brothers Company | Built liquid detergent compositions and method of preparation |
| GR77642B (en) * | 1981-09-25 | 1984-09-25 | Procter & Gamble |
-
1986
- 1986-04-26 DE DE8686105800T patent/DE3668330D1/en not_active Expired - Fee Related
- 1986-04-26 EP EP86105800A patent/EP0201016B1/en not_active Expired - Lifetime
- 1986-04-26 AT AT86105800T patent/ATE49608T1/en not_active IP Right Cessation
- 1986-04-30 ES ES554587A patent/ES8900056A1/en not_active Expired
- 1986-05-01 JP JP61099515A patent/JPS61255999A/en active Pending
- 1986-05-05 US US06/860,275 patent/US4717507A/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1104441A (en) * | 1964-07-08 | 1968-02-28 | Unilever Ltd | Fabric conditioner |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0201016A3 (en) | 1987-09-23 |
| DE3668330D1 (en) | 1990-02-22 |
| JPS61255999A (en) | 1986-11-13 |
| ATE49608T1 (en) | 1990-02-15 |
| ES8900056A1 (en) | 1988-11-16 |
| ES554587A0 (en) | 1988-11-16 |
| EP0201016A2 (en) | 1986-11-12 |
| US4717507A (en) | 1988-01-05 |
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