EP1497402B1 - Compositions d'adoucissant textile contenant des derives d'ester de betaine et procede d'amelioration du pouvoir lavant de lessives - Google Patents
Compositions d'adoucissant textile contenant des derives d'ester de betaine et procede d'amelioration du pouvoir lavant de lessives Download PDFInfo
- Publication number
- EP1497402B1 EP1497402B1 EP03718759A EP03718759A EP1497402B1 EP 1497402 B1 EP1497402 B1 EP 1497402B1 EP 03718759 A EP03718759 A EP 03718759A EP 03718759 A EP03718759 A EP 03718759A EP 1497402 B1 EP1497402 B1 EP 1497402B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- radical
- fabric softener
- washing
- rinse cycle
- atoms
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 238000009472 formulation Methods 0.000 title claims abstract description 73
- -1 betaine ester Chemical class 0.000 title claims abstract description 39
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229960003237 betaine Drugs 0.000 title claims abstract description 31
- 238000005406 washing Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 7
- 239000002979 fabric softener Substances 0.000 claims description 47
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 239000003599 detergent Substances 0.000 claims description 18
- 229910052757 nitrogen Chemical class 0.000 claims description 16
- 125000004433 nitrogen atom Chemical class N* 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004437 phosphorous atom Chemical group 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 230000008030 elimination Effects 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 150000003017 phosphorus Chemical class 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 229910052717 sulfur Chemical class 0.000 claims description 2
- 125000004434 sulfur atom Chemical class 0.000 claims description 2
- 150000002829 nitrogen Chemical group 0.000 claims 2
- 239000004094 surface-active agent Substances 0.000 abstract description 16
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000013270 controlled release Methods 0.000 abstract description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 19
- 239000000194 fatty acid Substances 0.000 description 19
- 229930195729 fatty acid Natural products 0.000 description 19
- 150000004665 fatty acids Chemical class 0.000 description 17
- 239000003925 fat Substances 0.000 description 14
- 235000019197 fats Nutrition 0.000 description 14
- 244000025254 Cannabis sativa Species 0.000 description 12
- 241001122767 Theaceae Species 0.000 description 12
- OENHQHLEOONYIE-UKMVMLAPSA-N all-trans beta-carotene Natural products CC=1CCCC(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C OENHQHLEOONYIE-UKMVMLAPSA-N 0.000 description 12
- 235000008452 baby food Nutrition 0.000 description 12
- 239000011648 beta-carotene Substances 0.000 description 12
- TUPZEYHYWIEDIH-WAIFQNFQSA-N beta-carotene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CCCC1(C)C)C=CC=C(/C)C=CC2=CCCCC2(C)C TUPZEYHYWIEDIH-WAIFQNFQSA-N 0.000 description 12
- 235000013734 beta-carotene Nutrition 0.000 description 12
- 229960002747 betacarotene Drugs 0.000 description 12
- 235000014121 butter Nutrition 0.000 description 12
- 235000021438 curry Nutrition 0.000 description 12
- 235000021185 dessert Nutrition 0.000 description 12
- 239000000835 fiber Substances 0.000 description 12
- 239000010721 machine oil Substances 0.000 description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 12
- 239000003415 peat Substances 0.000 description 12
- 235000020095 red wine Nutrition 0.000 description 12
- 235000015067 sauces Nutrition 0.000 description 12
- OENHQHLEOONYIE-JLTXGRSLSA-N β-Carotene Chemical compound CC=1CCCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C OENHQHLEOONYIE-JLTXGRSLSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000004744 fabric Substances 0.000 description 9
- 239000002736 nonionic surfactant Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000004753 textile Substances 0.000 description 7
- 239000002689 soil Substances 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical class C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 5
- 239000003093 cationic surfactant Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- 235000019486 Sunflower oil Nutrition 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- UFZOPKFMKMAWLU-UHFFFAOYSA-N ethoxy(methyl)phosphinic acid Chemical compound CCOP(C)(O)=O UFZOPKFMKMAWLU-UHFFFAOYSA-N 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002600 sunflower oil Substances 0.000 description 2
- 239000003784 tall oil Substances 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-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
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- 0 C*(C)N(N*(*)(N)NNN(C)O*)OCC(C)=N Chemical compound C*(C)N(N*(*)(N)NNN(C)O*)OCC(C)=N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 108010081873 Persil Proteins 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LQJBNNIYVWPHFW-QXMHVHEDSA-N gadoleic acid Chemical compound CCCCCCCCCC\C=C/CCCCCCCC(O)=O LQJBNNIYVWPHFW-QXMHVHEDSA-N 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/90—Betaines
Definitions
- the invention relates to fabric softener formulations comprising hydrolyzable betaine ester derivatives in addition to liquid esterquat fabric softener formulations for the controlled release of surfactants and to a commercial process for improving the washing performance of detergents using the fabric softener formulations.
- wetting of the material to be cleaned with the wash liquor and the wetting of the solid or oily particle dirt are required for a cleaning.
- Wetting and wetting are effected by surfactants, surfactants.
- the electrochemical double layer formed between fiber, debris and surfactant is substantially increased by anionic surfactants and builders, thereby enhancing the repellency between soil and fiber.
- the detached liquid oil and grease dirt is solubilized by the micelles formed by the surfactants and thus kept in the wash liquor.
- Particle dirt is electrically charged by adsorption of surfactants and dispersed as a result of the repulsion of the individual particles in the wash liquor, so that a redeposition on the fabric is omitted.
- Nonionic surfactants are generally used in detergent formulations because of their ability to remove greasy and oily soils.
- Prior art cationic surfactants used in detergent formulations especially because of their attributed additional textilnostinden effects and not exclusively as a cleaning agent.
- Such additional effects to be observed depending on the structure of the cationic surfactants are, for example, the softening (U.S. 3,607,763), the antistatic (U.S. 3,951,879, U.S. 3,959,157), the bacteriocides (U.S. 2,742,434 US 3 539 520, US 3 965 026) and the color-protecting effect or also the improvement of the water-absorption capacity of the fabrics treated with them.
- basic detergent formulations are known in which selected nonionic and cationic surfactants are combined to achieve improved soil removal, as described in US Pat. Nos. 4,239,660 and 4,260,529.
- US Pat. No. 4,260,529 describes laundry detergent formulations containing betaine ester derivatives in the form of cationic ammonium salts in addition to a biodegradable nonionic surfactant.
- These laundry detergent formulations for the main wash cycle are said to have a high washing effect if they are used in the alkaline wash temperature range of specifically below 11 in the main wash cycle, so that hydrolysis of the surfactants used is prevented.
- Cationic surfactants of different structure are used as raw materials for laundry softeners. Particularly widespread are Estertagen based on triethanolamine such as N-methyl, N, N-bis (beta-C 14-18 -acyloxyethyl) -, N-beta-hydroxyethylammoniummethosulfat that (under trade names such Tetranyl ® AT 75 trademarks of KAO Corp. .), Stepanex ® VRH 90 (trademark of Stepan Corp.) or Rewoquat ® WE 18 (trademark of Goldschmidt Rewo GmbH & Co. KG) are distributed.
- Estertagen based on triethanolamine such as N-methyl, N, N-bis (beta-C 14-18 -acyloxyethyl) -, N-beta-hydroxyethylammoniummethosulfat that (under trade names such Tetranyl ® AT 75 trademarks of KAO Corp. .), Stepanex ® VRH 90 (trademark of Step
- U.S. 4,370,272 discloses alkoxylated quaternary ammonium betaine ester surfactants and their use as hair conditioners or fabric softeners. As advantages, their self-emulsifying action in water and the possibility to dispense with additional nonionic surfactants to obtain a stable emulsion are called. However, the softness of laundry treated with such fabric softeners does not meet the standards achieved by modern esterquat fabric softeners.
- a disadvantage of the prior art is further that the previously available surfactant molecules have no or no sufficient substantivity to raise from the aqueous liquor onto the fibers, which applies in particular to nonionic surfactant molecules.
- the object of the present invention was therefore to provide fabric softener formulations which show a significant detergency enhancing effect in the next wash and at the same time meet the standards of modern esterquat softener formulations, in particular with respect to the softening effect, the antistatic effect or the water absorbency of the fabrics treated therewith.
- the components of the laundry softener formulations must be applied to the textiles (substantivity).
- the radical R a of the betaine ester derivatives preferably comprises a long-chain alkyl radical having 9 to 17 C atoms.
- Y according to the formula (II) is a substituted nitrogen atom or phosphorus atom, and the radicals R b and R c are simultaneously -CH 3 .
- radicals R d and R e may be H at the same time.
- X is -C (O) -NH- or C (O) -N (CH 3 ) -.
- R f is preferably an ethylene radical or a propylene radical.
- Y should preferably be a substituted nitrogen atom according to formula (II).
- R g is the residue of a fatty alcohol based on natural fatty acids which can be prepared by known processes.
- fatty acids for the preparation of fatty alcohols are - individually or in mixtures - fatty acids such as caproic, caprylic, capric, 2-ethylhexanoic, lauric, myristic, palmitic, palmitoleic, isostearic, stearic, hydroxystearic (ricinoleic), dihydroxystearic, oleic, linoleic, petroleum , Elaidic acid, arachidic acid, behenic acid and erucic acid, gadoleic acid and the technical mixtures obtained in the pressure splitting of natural fats and oils such as oleic acid, linoleic acid, linolenic acid, and especially coconut oil fatty acid, rapeseed oil fatty acid, soybean oil fatty acid, sunflower oil fatty acid, tall oil fatty acid. In principle, all fatty acids with a similar chain distribution are suitable.
- the iodine number is the amount of iodine absorbed by 100 g of the compound to saturate the double bonds.
- the laundry softener formulations mentioned are particularly suitable for achieving the effect according to the invention if they are further characterized in that the betaine ester derivative is stable to hydrolysis at pH values below 3.5 (at temperatures up to 70 ° C.) and in the aqueous alkaline range from pH 8 to 14, in particular 9 to 11 spontaneously to form cationic, anionic, zwitterionic and / or nonionic surfactants to form at least one good fat-soluble surfactant having an HLB value of ⁇ 10, and at least one readily water-soluble surfactant having an HLB value of> 10 is hydrolyzed.
- the fabric softener formulations have a content of at least 1% by weight, especially 1 to 10, especially 2 to 5, of at least one of the said betaine ester derivatives, together 5 to 20% by weight, especially 13 to 20, of one or more esterquaternary ester derivatives.
- Softeners, and the rest up to 100 wt .-% of conventional auxiliaries or additives and optionally water.
- the auxiliaries and additives are preferably selected from nonionic and ionic dispersants, (C 1 to C 5 ) -alkanols, ethylene glycol, propylene glycol, polyglycol, and derivatives thereof, ethoxylated or propoxylated phenol, benzyl alcohol, isopropanol, isobutanol having a mean degree of alkoxylation of> 2.5 to 3.5 and dyes and perfume oils and in particular in a proportion of together up to 5 wt .-%, especially 1 to 3 included.
- nonionic and ionic dispersants C 1 to C 5 ) -alkanols, ethylene glycol, propylene glycol, polyglycol, and derivatives thereof, ethoxylated or propoxylated phenol, benzyl alcohol, isopropanol, isobutanol having a mean degree of alkoxylation of> 2.5 to 3.5 and dyes and perfume oils and in particular in a proportion of together up
- the fabric softener formulations of the present invention contain betaine ester derivatives having excellent substantivity, and thus, once grown on the fiber, can be considered to carry an ionic and nonionic surfactant which controls them, that is, releases them at the next wash cycle. In this way, for the first time nonionic surfactants for the subsequent wash cycle by the temporary incorporation into a cationic compound can be fixed on textile fibers.
- one or more further quaternary ammonium compounds may be present in the laundry softeners according to the invention.
- a post-treatment of the clean laundry according to step (B) a post-treatment can be carried out exclusively with Betainesterformultechniken alone.
- the subsequent washing process is carried out analogously (C).
- the adjustment of the required pH values is carried out by a neutralization step with sufficient amounts of inorganic, but preferably conventional organic mono- or polybasic acids. It is also advantageous Applications of fabric softener formulations the use of corresponding buffer substances instead of acids.
- a wash usually involves placing the dry or wet soiled laundry in the washing machine and cleaning it with the added detergent and washing mechanics.
- the usual state-of-the-art detergents wet the dirt located on the textile fibers exclusively from the outside. There are initially no surfactant molecules between the textile fibers and the dirt particles.
- the soft touch was checked on commercial cotton terry fabric.
- aqueous fabric softener strength prepared with the additives according to the formulas 2 to 11 is generally in the amount of 2 wt .-% based on the finished fabric softener, in the case of the formulations 3 and 6 in the amount of 5%, were included in the case of the formulations 4 and 7 in the amount of 9 wt .-%.
- formulations according to the invention with the additions of the betaine ester derivatives Ia-f should ideally have a neutral behavior with respect to the softness of the treated tissue. A negative effect on the softness led to a devaluation in the overall assessment.
- the use concentration of all fabric softening formulations was 0.025% by weight for softness evaluation.
- Table 1 formulation softness Recipe 1 4 Recipe 2 3.9 Recipe 3 3.2 Recipe 4 2.7 Recipe 5 3.9 Recipe 6 3.3 Recipe 7 2.6 Recipe 8 3.8 Recipe 9 3.7 Recipe 10 3.8 Recipe 11 3.7 3% recipe 4 1.4 5% recipe 4 1.6
- the fabric softeners were dosed both with the usual concentration of 0.025 wt .-% active content as well as with an excessive concentration of 0.075 wt .-%.
- Stainmonitors contain on a piece of fabric 16 different types of dirt, so that a fairly comprehensive evaluation of the washing performance, or stain removal is possible.
- the washing tests were carried out in Miele W 715 and W 918 washing machines.
- Table 2 Powder detergent (batch 1) pollution no fabric softener * Formulation 1 * 0.025% by weight Formulation 2 ++ 0.025% by weight Formulation 2 ++ 0.075 wt .-% Make up 59.3 58.0 62.5 57.2 curry 81.7 84.3 89.8 92.0 red wine 63.9 61.4 66.9 61.8 Spaghetti sauce 87.9 84.8 91.9 96.5 dessert 74.7 75.6 75.8 80.0 peat 61.0 58.4 65.4 61.2 tea 56.8 54.8 62.2 66.9 Beta-carotene 72.1 77.6 75.0 90.0 grass 89.0 60.1 91.7 95.1 animal.
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)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Claims (11)
- Formulations assouplissantes pour le linge contenant des dérivés d'ester de bétaïne de formule générale (I) suivante :
Y représente selon la formule (II)Ra est un radical alkyle à longue chaîne ayant de 7 à 21 atomes de C,X est un radical issu des groupes -O-C(O)-, -(O)C-O-, -NH-C(O)-, -(O)C-NH-, -(CH3)N-C(O)-, -(O)C-N(CH3)-, -S(O2)-O-, -0-S(02)-, -S(O2)-NH-, -NH-S(02)-, -S(02)-N(CH3)-, -N(CH3)-S(02)-,Rb, Rc sont des radicaux alkyle ayant 1 à 4 atomes de C, indépendants l'un de l'autre et le cas échéant ramifiés, ceux-ci pouvant contenir le cas échéant des substituants d'hétéroatome;les radicauxRd Re sont choisis indépendamment l'un de l'autre parmi l'hydrogène (H), des radicaux alkyle ayant de 1 à 4 atomes de C, le cas échéant ramifiés, des radicaux aryle ou benzyle, le cas échéant substitués, ainsi que du CH2COOH, CH2COOR, CH2CH2COOH, CH2CH2COOR,Rf est un radical hydrocarbure ramifié et/ou substitué et/ou cyclique ayant de 1 à 10, de manière préférée 2 ou 3 atomes de carbon, et contenant le cas échéant des liaisons multiples, ou un radical styrène ou est constitué exclusivement de radicaux éthylène, propylène, butylène ou styrène ou est un polymère statistique ou un copolymère en bloc contenant les radicaux cités,Rg est un radical hydrocarbure ayant de 1 à 30 atomes de C, le cas échant ramifié, contenant le cas échéant des liaisons doubles, le cas échant cyclique,Z est un radical issu des groupes atome d'azote, atome d'oxygène, -0-C(0)-, -NH-C(0)-, - (CH3)N-C (0) -,
n = 1, quand Z n'est pas un atome d'azote et o = 1;
n = 2, quand Z est un atome d'azote et o = 1;
n = 1, quand Z n'est pas un atome d'azote et o = 2,k et l valent de 1 à 4 indépendamment l'un de l'autre,
k valant de manière préférée 2 ou 3, et
l valant de manière préférée 1,m possède une valeur de 0 à 30, de manière préférée de 1 à 10, en particulier de 3 à 7 etA- est un anion etun assouplissant d'esterquat liquide du commerce. - Formulations assouplissantes pour le linge selon la revendication 1, caractérisées en ce que le radical Ra des dérivés d'ester de bétaïne comporte un radical alkyle à longue chaîne ayant de 9 à 17 atomes de C.
- Formulations assouplissantes pour le linge selon la revendication 1 ou 2, caractérisées en ce que Y selon la formule (II) est un atome de phosphore ou un atome d'azote substitué et les radicaux Rb et Rc sont simultanément du -CH3.
- Formulations assouplissantes pour le linge selon l'une quelconque des revendications 1 à 3, caractérisées en ce que les radicaux Rd et Re sont simultanément de l'hydrogène.
- Formulations assouplissantes pour le linge selon l'une quelconque des revendications 1 à 4, caractérisées en ce que X = -C(O)-NH- ou C(O)-N(CH3)-.
- Formulations assouplissantes pour le linge selon l'une quelconque des revendications 1 à 5, caractérisées en ce que n = 1 et o = 1, ainsi que Z est un atome d'oxygène.
- Formulations assouplissantes pour le linge selon l'une quelconque des revendications 1 à 6, caractérisées en ce que k = 2 ou 3 et 1 = 1.
- Formulations assouplissantes pour le linge selon l'une quelconque des revendications 1 à 7, caractérisées en ce que Rf est un radical éthylène ou un radical propylène.
- Formulations assouplissantes pour le linge selon l'une quelconque des revendications 1 à 8, caractérisées en ce que m = 1 à 10 et Rg est un radical alkyle ayant de 1 à 30 atomes de C.
- Formulations assouplissantes pour le linge selon l'une quelconque des revendications 3 à 9, caractérisées en ce que Y selon la formule (II) est un atome de phosphore ou d'azote substitué, Ra est un radical alkyle ayant de 7 à 21 atomes de C, de manière préférée un radical alkyle à longue chaîne ayant de 9 à 17 atomes de C, X = -C(O)-NH-, Rb et Rc = -CH3, Rd et Re sont simultanément de l'hydrogène, Rf est un radical éthylène ou un radical propylène, de manière préférée un radical éthylène, n = 1, o = 1 et Z est un atome d'oxygène, ainsi que k = 3, 1 = 1, m = 2 et Rg est un radical alkyle ayant de 6 à 22, en particulier de 8 à 18 atomes de C.
- Procédé d'amélioration de la performance de lavage de lessives, comprenant les étapes :(A)élimination de l'alcalinité résultante du programme de lavage;(B)traitement secondaire du linge propre à des valeurs pH inférieures à 3,5 avec une formulation assouplissante pour le linge selon l'une quelconque des revendications 1 à 11 et(C)lavage du linge sali par l'usage ou d'autre manière avec une lessive en milieu aqueux alcalin.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10217705A DE10217705A1 (de) | 2002-04-20 | 2002-04-20 | Wäscheweichspülformulierungen enthaltend Betainesterderivate sowie Verfahren zur Verbesserung der Waschleistung von Waschmitteln |
DE10217705 | 2002-04-20 | ||
PCT/EP2003/003912 WO2003089558A1 (fr) | 2002-04-20 | 2003-04-15 | Compositions d'adoucissant textile contenant des derives d'ester de betaine et procede d'amelioration du pouvoir lavant de lessives |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1497402A1 EP1497402A1 (fr) | 2005-01-19 |
EP1497402B1 true EP1497402B1 (fr) | 2007-02-28 |
Family
ID=28798636
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03718759A Expired - Lifetime EP1497402B1 (fr) | 2002-04-20 | 2003-04-15 | Compositions d'adoucissant textile contenant des derives d'ester de betaine et procede d'amelioration du pouvoir lavant de lessives |
Country Status (7)
Country | Link |
---|---|
US (1) | US7056878B2 (fr) |
EP (1) | EP1497402B1 (fr) |
AT (1) | ATE355353T1 (fr) |
AU (1) | AU2003222815A1 (fr) |
CA (1) | CA2482998A1 (fr) |
DE (2) | DE10217705A1 (fr) |
WO (1) | WO2003089558A1 (fr) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10217705A1 (de) * | 2002-04-20 | 2003-11-06 | Goldschmidt Ag Th | Wäscheweichspülformulierungen enthaltend Betainesterderivate sowie Verfahren zur Verbesserung der Waschleistung von Waschmitteln |
US8791045B2 (en) | 2011-11-09 | 2014-07-29 | Kimberly-Clark Worldwide, Inc. | Non-tacky wetness indicator composition for application on a polymeric substrate |
US9889222B2 (en) | 2011-11-09 | 2018-02-13 | Kimberly-Clark Worldwide, Inc. | Aqueous medium-sensitive coating compositions for triggered release of active ingredients and visual indication for wetness |
US20130338227A1 (en) | 2012-06-13 | 2013-12-19 | Marie-Esther Saint Victor | Green Glycine Betaine Derivative Compounds And Compositions Containing Same |
US9585826B2 (en) | 2012-11-07 | 2017-03-07 | Kimberly-Clark Worldwide, Inc. | Triggerable compositions for two-stage, controlled release of active chemistry |
US9119780B2 (en) | 2013-10-30 | 2015-09-01 | Kimberly-Clark Worldwide, Inc. | Triggerable compositions for two-stage, controlled release of proactive chemistry |
US9890350B2 (en) | 2015-10-28 | 2018-02-13 | Ecolab Usa Inc. | Methods of using a soil release polymer in a neutral or low alkaline prewash |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2742434A (en) | 1952-01-19 | 1956-04-17 | Gen Aniline & Film Corp | Cleaner-sanitizer |
US3539520A (en) | 1967-07-12 | 1970-11-10 | West Laboratories Inc | Compositions comprising quaternary ammonium germicides and nonionic surfactants |
AU5697073A (en) | 1972-07-10 | 1974-12-19 | Colgate Palmolive Co | Liquid cleaner liquid cleaner |
US3959157A (en) | 1973-06-04 | 1976-05-25 | Colgate-Palmolive Company | Non-phosphate detergent-softening compositions |
US3951879A (en) | 1973-12-14 | 1976-04-20 | Colgate-Palmolive Company | Detergent that reduces electrostatic cling of synthetic fabrics |
US4260529A (en) | 1978-06-26 | 1981-04-07 | The Procter & Gamble Company | Detergent composition consisting essentially of biodegradable nonionic surfactant and cationic surfactant containing ester or amide |
US4239660A (en) | 1978-12-13 | 1980-12-16 | The Procter & Gamble Company | Detergent composition comprising a hydrolyzable cationic surfactant and specific alkalinity source |
US4370272A (en) | 1980-01-14 | 1983-01-25 | Stepan Chemical Company | Alkoxylated quaternary ammonium surfactants |
DE3505269A1 (de) | 1985-02-15 | 1986-08-21 | Hoechst Ag, 6230 Frankfurt | Quarternaere alkylamidobetainester, ein verfahren zu ihrer herstellung und ihre verwendung in waescheweichspuelmitteln |
DE19520884A1 (de) * | 1995-06-08 | 1996-12-12 | Wella Ag | Wasserhaltiges Weichspülmittel fürdie Behandlung von Textilien |
EP0799885A1 (fr) * | 1996-04-01 | 1997-10-08 | The Procter & Gamble Company | Composés bétaine ester des aclcools actifs |
DE10153183A1 (de) * | 2001-10-27 | 2003-05-15 | Henkel Kgaa | Betainesterhaltige Mittel |
DE10217705A1 (de) * | 2002-04-20 | 2003-11-06 | Goldschmidt Ag Th | Wäscheweichspülformulierungen enthaltend Betainesterderivate sowie Verfahren zur Verbesserung der Waschleistung von Waschmitteln |
-
2002
- 2002-04-20 DE DE10217705A patent/DE10217705A1/de not_active Withdrawn
-
2003
- 2003-04-15 WO PCT/EP2003/003912 patent/WO2003089558A1/fr active IP Right Grant
- 2003-04-15 EP EP03718759A patent/EP1497402B1/fr not_active Expired - Lifetime
- 2003-04-15 DE DE50306660T patent/DE50306660D1/de not_active Expired - Fee Related
- 2003-04-15 AT AT03718759T patent/ATE355353T1/de not_active IP Right Cessation
- 2003-04-15 CA CA002482998A patent/CA2482998A1/fr not_active Abandoned
- 2003-04-15 AU AU2003222815A patent/AU2003222815A1/en not_active Abandoned
-
2004
- 2004-10-19 US US10/967,777 patent/US7056878B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
US20050227904A1 (en) | 2005-10-13 |
DE50306660D1 (de) | 2007-04-12 |
CA2482998A1 (fr) | 2003-10-30 |
WO2003089558A1 (fr) | 2003-10-30 |
AU2003222815A1 (en) | 2003-11-03 |
EP1497402A1 (fr) | 2005-01-19 |
DE10217705A1 (de) | 2003-11-06 |
ATE355353T1 (de) | 2006-03-15 |
US7056878B2 (en) | 2006-06-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE3926740C2 (de) | Wässrige Weichspülmittel und deren Verwendung | |
DE2617589A1 (de) | Hydrophile polyurethane | |
DE2215371A1 (de) | Waschmittel | |
DE2810703A1 (de) | Nichtiogenes tensid | |
EP0170144B1 (fr) | Procédé de lavage pour textiles sensibles | |
DE2211576C3 (de) | Verwendung von quaternären Benzimidazolen als Textilweichmacher mit gleichzeitiger schmutzfreisetzender Wirkung | |
EP1497402B1 (fr) | Compositions d'adoucissant textile contenant des derives d'ester de betaine et procede d'amelioration du pouvoir lavant de lessives | |
DE68926584T2 (de) | Wäscheweichmacherzusammensetzung | |
DE2300658C2 (de) | Weichmachungsmittel für Textilien mit gleichzeitiger schmutzfreisetzender und antistatischer Wirkung | |
DE2812118A1 (de) | Gewebeweichmach-zusammensetzung mit antistatischer wirkung | |
DE2615704A1 (de) | Zusammensetzungen zur behandlung von textilien | |
DE2060849A1 (de) | Waschmittel zum gleichzeitigen Reinigen und Weichmachen | |
DE3730444C2 (fr) | ||
DE60019600T2 (de) | Wäschepflegemittel sowie ein textilbehandlungsverfahren | |
DE1901194C3 (de) | Detergens-verträgliches wäßriges Weichmachungsmittel und dessen Verwendung zum Weichmachen von Geweben während des Waschens oder während des Spiilens | |
DE4215689A1 (de) | Stickstofffreie Wirkstoffkomponente in Wäscheweichspülerformulierungen | |
EP0924291B2 (fr) | Adoucissant aqueux à souplesse améliorée | |
EP0747468A1 (fr) | Agents adoucissants aqueux pour le traitement des textiles | |
DE2226934A1 (de) | Quaternaere ammoniumverbindungen und ihre verwendung zur oberflaechenbehandlung | |
DE2243806C3 (de) | Wässriges Mittel zum Weichmachen von Textilgut | |
DE60105763T3 (de) | Zusammensetzung zur textilpflege | |
DE2144592B2 (de) | Waschmittel | |
AT354971B (de) | Zusammensetzung fuer die oberflaechenbehandlung | |
DE60027138T2 (de) | Weichmacherzusammensetzung | |
DE3328879A1 (de) | Koerniges wasch- und reinigungsmittel mit gewebeweichmacheffekt |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20041009 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070228 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070228 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070228 Ref country code: IE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070228 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070228 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REF | Corresponds to: |
Ref document number: 50306660 Country of ref document: DE Date of ref document: 20070412 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20070529 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070531 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070608 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070730 |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
RIN2 | Information on inventor provided after grant (corrected) |
Inventor name: FENDER, MICHAEL Inventor name: TOMUSCHAT, PHILIPP Inventor name: WEYERSHAUSEN, BERND Inventor name: SIMPELKAMP, JOERG |
|
GBV | Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed] |
Effective date: 20070228 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FD4D |
|
EN | Fr: translation not filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070228 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070228 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070228 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070228 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20071129 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070430 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070430 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20071030 Year of fee payment: 5 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070228 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070529 Ref country code: FR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20071019 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20080418 Year of fee payment: 6 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070415 |
|
BERE | Be: lapsed |
Owner name: GOLDSCHMIDT REWO G.M.B.H. & CO. KG Effective date: 20080430 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070228 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070228 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070430 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080430 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070228 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070415 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070228 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070901 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20091103 |