EP0674701B1 - Aqueous textile softener dispersions - Google Patents
Aqueous textile softener dispersions Download PDFInfo
- Publication number
- EP0674701B1 EP0674701B1 EP94902704A EP94902704A EP0674701B1 EP 0674701 B1 EP0674701 B1 EP 0674701B1 EP 94902704 A EP94902704 A EP 94902704A EP 94902704 A EP94902704 A EP 94902704A EP 0674701 B1 EP0674701 B1 EP 0674701B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- carbon atoms
- mole
- fatty acid
- ethylene oxide
- 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
- 239000006185 dispersion Substances 0.000 title claims abstract description 28
- 239000004753 textile Substances 0.000 title abstract description 13
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims abstract description 20
- 239000002270 dispersing agent Substances 0.000 claims abstract description 17
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 31
- 239000000194 fatty acid Substances 0.000 claims description 26
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 25
- 229930195729 fatty acid Natural products 0.000 claims description 25
- 150000004665 fatty acids Chemical class 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- -1 polyol fatty acid ester Chemical class 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000002191 fatty alcohols Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000002979 fabric softener Substances 0.000 claims description 8
- 239000003760 tallow Substances 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 3
- HOSGXJWQVBHGLT-UHFFFAOYSA-N 6-hydroxy-3,4-dihydro-1h-quinolin-2-one Chemical group N1C(=O)CCC2=CC(O)=CC=C21 HOSGXJWQVBHGLT-UHFFFAOYSA-N 0.000 claims 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000004185 ester group Chemical group 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 9
- 239000004480 active ingredient Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000004744 fabric Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RKHXDCVAPIMDMG-UHFFFAOYSA-N 9-hydroxyoctadecanoic acid Chemical compound CCCCCCCCCC(O)CCCCCCCC(O)=O RKHXDCVAPIMDMG-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-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
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 150000003626 triacylglycerols Chemical class 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-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
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- AGNTUZCMJBTHOG-UHFFFAOYSA-N 3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy]propane-1,2-diol Chemical compound OCC(O)COCC(O)COCC(O)CO AGNTUZCMJBTHOG-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021319 Palmitoleic acid Nutrition 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 239000004665 cationic fabric softener Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 125000001924 fatty-acyl group Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000002811 oleoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000002351 wastewater 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
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
Definitions
- EP-A-0 188 242 discloses textile softening agents whose quaternary ammonium compound content is preferably not higher than 12% by weight and whose fatty amine polyglycol ether content is preferably 1 to 1.8% by weight.
- ethylene oxide adducts on ring opening products of epoxidized triglycerides such as are obtained, for example, by epoxidation of soybean oil, hydrogenation or reaction (epoxy ring opening) with protic compounds, such as with H 2 O, carboxylic acids or alcohols with 1-10 C, are also particularly suitable -Atoms and subsequent ethylene oxide addition.
- protic compounds such as with H 2 O, carboxylic acids or alcohols with 1-10 C
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)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Colloid Chemistry (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft wäßrige Textilweichmacher-Dispersionen, die trotz eines besonders hohen Gehaltes an textilweichmachenden Wirkstoffen eine geringe Viskosität aufweisen, die sich auch nach längerer Lagerzeit nicht oder nur unwesentlich erhöht.The present invention relates to aqueous fabric softener dispersions which, despite a particularly high content of fabric softening active ingredients, have a low viscosity which does not increase, or increases only insignificantly, even after prolonged storage.
Wäßrige Textilweichmacher-Dispersionen neigen bei längerer Lagerung, insbesondere bei Temperaturen unterhalb oder oberhalb der Raumtemperatur, zur Verdickung. Besonders ausgeprägt ist dieses Verhalten bei Textilweichmacher-Dispersionen mit hohem Wirkstoffgehalt. Die marktüblichen Textilweichmacher-Konzentrate enthalten ca. 15 bis 25 Gew.-% Wirkstoff. Zur Herstellung lagerstabiler Dispersionen wird in der Regel mit Hilfe unterschiedlicher Elektrolyte eine sehr niedrige Ausgangsviskosität eingestellt. Bei einem noch höheren Wirkstoffgehalt beobachtet man aber auch in Gegenwart von Elektrolyt bei der Lagerung eine nennenswerte Viskositätserhöhung, die entweder unmittelbar nach der Herstellung oder aber während der Lagerung auftritt.Aqueous textile softener dispersions tend to thicken after prolonged storage, especially at temperatures below or above room temperature. This behavior is particularly pronounced in textile softener dispersions with a high active ingredient content. The commercial fabric softener concentrates contain approx. 15 to 25% by weight of active ingredient. To produce storage-stable dispersions, a very low starting viscosity is generally set using different electrolytes. If the active substance content is even higher, a noteworthy increase in viscosity is observed even in the presence of electrolyte during storage, which either occurs immediately after production or during storage.
Der Zusatz von ethoxylierten Fettalkoholen zur Verbesserung der Verdünnbarkeit bzw. Auflösbarkeit konzentrierter Dispersionen in der Spülflotte ist bereits in mehreren Druckschriften vorgeschlagen worden, z.B. in EP 0 040 562 B1, EP 0 280 550 B1, EP 0 503 221 Al, EP 0 507 478 Al oder EP 0 523 922 A2. Die dort vorgeschlagenen Ethoxylate müssen jedoch in Konzentrationen von mehr als 1 Gew.-% eingesetzt werden, um in konzentrierten Dispersionen mit mehr als 15 Gew.-% des kationischen Textilweichmachers eine ausreichende Viskositätsstabilisierung und Dispergierbarkeit zu gewährleisten.The addition of ethoxylated fatty alcohols to improve the dilutability or dissolvability of concentrated dispersions in the washing liquor has already been proposed in several publications, for example in EP 0 040 562 B1, EP 0 280 550 B1, EP 0 503 221 Al, EP 0 507 478 Al or EP 0 523 922 A2. However, the ethoxylates proposed there must be used in concentrations of more than 1% by weight in order to ensure adequate viscosity stabilization and dispersibility in concentrated dispersions with more than 15% by weight of the cationic fabric softener.
Aus EP-A-0 188 242 sind Textilweichmachungsmittel bekannt, deren Gehalt an quartären Ammoniumverbindungen bevorzugt nicht höher als 12 Gew.-% und deren Gehalt an Fettaminpolyglycolether bevorzugt 1 bis 1,8 Gew.-% beträgt.EP-A-0 188 242 discloses textile softening agents whose quaternary ammonium compound content is preferably not higher than 12% by weight and whose fatty amine polyglycol ether content is preferably 1 to 1.8% by weight.
In EP-A-0 409 504 sind Gewebeweichspülmittel mit einem Gehalt an quartären Ammoniumverbindungen und Extendermaterialien beschrieben, es sind jedoch nur Zusammensetzungen mit weniger als 15 Gew.-% der quartären Ammoniumverbindung und mehr als 0,5 Gew.-% eines nichtionischen Extenders offenbart.EP-A-0 409 504 describes fabric softening agents containing quaternary ammonium compounds and extender materials, but only compositions with less than 15% by weight of the quaternary ammonium compound and more than 0.5% by weight of a nonionic extender are disclosed .
EP-A-0 354 011 offenbart Gewebeweichspülmittel, die kationische Weichmacher und bis zu 15 Gew.-% eines Elektrolytsalzes enthalten und durch Zusatz von 1 Gew.-% eines Tensids in der Viskosität gesenkt werden.EP-A-0 354 011 discloses fabric softening agents which contain cationic plasticizers and up to 15% by weight of an electrolyte salt and which are reduced in viscosity by adding 1% by weight of a surfactant.
EP-A-0 040 562 beschreibt Wäscheweichspülmittel-Konzentrate, die neben quartären Ammoniumverbindungen auch nichtionogene Tenside zur stabilen Emulgierung von Parfümölen in Mengen von wenigstens 1 Gew.-% enthalten.EP-A-0 040 562 describes laundry detergent concentrates which, in addition to quaternary ammonium compounds, also contain nonionic surfactants for the stable emulsification of perfume oils in amounts of at least 1% by weight.
Aufgabe der vorliegenden Erfindung war daher die Bereitstellung einer wäßrigen Textilweichmacher-Dispersion mit hohem Wirkstoffgehalt, deren Viskosität niedrig ist und die auch bei Lagerung nicht wesentlich ansteigt und die sich leicht mit kaltem Wasser weiterverdünnen läßt. Dabei soll der Anteil an nichtionischem, nicht textilweichmachendem Dispergiermittel möglichst niedrig sein. Der textilweichmachende kationische Wirkstoff soll darüber hinaus in einer Menge von mehr als 15 Gew.-% vorliegen, er soll den behandelten Textilien eine gute Weichheit verleihen, das Wiederbenutzungsvermögen nicht beeinträchtigen und im Abwasser leicht und rasch biologisch abgebaut werden.The object of the present invention was therefore to provide an aqueous textile softener dispersion with a high active ingredient content, the viscosity of which is low and which does not increase significantly even during storage and which can easily be further diluted with cold water. The proportion of nonionic, non-fabric softening dispersant should be as low as possible. The textile-softening cationic active ingredient should moreover be present in an amount of more than 15% by weight, it should give the treated textiles a good softness, not impair the reusability and be easily and rapidly biodegraded in the waste water.
Es wurden nun spezielle nichtionische Dispergatoren gefunden, die bereits in Mengen von weniger als 0,5 Gew.-% solchen Dispersionen eine gute Viskositätskonstanz und ein gutes Kaltwasser-Dispergiervermögen verleihen.Special nonionic dispersants have now been found which, even in amounts of less than 0.5% by weight, give such dispersions good viscosity constancy and good cold water dispersibility.
Gegenstand der vorliegenden Erfindung ist dementsprechend eine wäßrige Textilweicher-Dispersion mit einem Gehalt an textilweichmachenden quartären Ammoniumverbindungen und nichtionischen Dispergatoren, dadurch gekennzeichnet, daß die Dispersion
- a) 15 - 60 Gew.-% quartäre Ammoniumverbindungen mit zwei oder drei über Ester- oder Amidbindungen damit verknüpften linearen Alkyl- oder Acylgruppen mit jeweils 12 - 22 C-Atomen
- b) 0,001 - 0,5 Gew.-% nichtionische Dispergatoren enthält, die ausgewählt sind aus
- Anlagerungsprodukten von 40 - 200 Mol Ethylenoxid an 1 Mol linearen Fettalkohol mit 12 - 22 C-Atomen
- Anlagerungsprodukten von 10 - 150 Mol Ethylenoxid an 1 Mol einer linearen Fettsäure oder Hydroxyfettsäure mit 12 - 22 C-Atomen, an ein Mol eines linearen Fettalkylamins mit 12 - 22 C-Atomen oder an ein Mol eines C1-C4-Niedrigalkylesters einer Fettsäure oder Hydroxyfettsäure mit 12 - 22 C-Atomen
- Anlagerungsprodukten von 3 - 100 Mol Ethylenoxid an l/m Mol eines Polyol-fettsäureesters aus m Mol einer Fettsäure oder Hydroxyfettsäure mit 12 - 22 C-Atomen und einem Mol eines Polyols mit 1 - 6 C-Atomen und 2 - 6 Hydroxylgruppen, wobei m einen Wert von 1 bis 6 annehmen kann, oder
- Gemischen aus solchen Ethylenoxid-Anlagerungsprodukten.
- a) 15-60% by weight of quaternary ammonium compounds with two or three linear alkyl or acyl groups linked to them via ester or amide bonds, each having 12-22 carbon atoms
- b) contains 0.001-0.5% by weight of nonionic dispersants selected from
- Addition products of 40-200 moles of ethylene oxide with 1 mole of linear fatty alcohol with 12-22 carbon atoms
- Addition products of 10-150 moles of ethylene oxide with 1 mole of a linear fatty acid or hydroxy fatty acid with 12-22 carbon atoms, with one mole of a linear fatty alkylamine with 12-22 carbon atoms or with one mole of a C1-C4-lower alkyl ester of a fatty acid or hydroxy fatty acid with 12 - 22 carbon atoms
- Addition products of 3 - 100 moles of ethylene oxide with 1 / m mole of a polyol fatty acid ester from m moles of a fatty acid or hydroxy fatty acid with 12-22 C atoms and one mole of a polyol with 1-6 C atoms and 2-6 hydroxyl groups, where m can have a value from 1 to 6, or
- Mixtures of such ethylene oxide addition products.
Die genannten quartären Ammoniumverbindungen sind wegen der darin in den langen Resten enthaltenen Ester- oder Amidgruppen biologisch leicht und schnell abbaubar und haben deswegen in letzter Zeit an Interesse gewonnen. Zu den genannten Verbindungen zählen beispielsweise die aus der DE-A-16 19 058, der DE-A-19 35 499 oder der US 3,915,867 bekannten Verbindungen mit 1, 2 oder 3 Fettacyloxyalkylresten am Stickstoffatom. Man kann diese Verbindungen beispielsweise leicht durch Veresterung von Alkanolaminen mit Fettsäure oder durch Umesterung von Fettsäureestern mit Alkanolamin und anschließender Quaternierung herstellen. Entsprechende Verfahren zur Herstellung in großtechnischem Maßstab sind ebenfalls seit langem bekannt; nach diesen Verfahren hergestellte Verbindungen sind handelsübliche Verbindungen.The quaternary ammonium compounds mentioned are easily and rapidly biodegradable because of the ester or amide groups contained in the long residues and have therefore recently gained interest. The compounds mentioned include, for example, the compounds known from DE-A-16 19 058, DE-A-19 35 499 or US 3,915,867 having 1, 2 or 3 fatty acyloxyalkyl radicals on the nitrogen atom. These compounds can easily be prepared, for example, by esterification of alkanolamines with fatty acid or by transesterification of fatty acid esters with alkanolamine and subsequent quaternization. Corresponding processes for the production on an industrial scale have also been known for a long time; Compounds made by these methods are commercially available compounds.
Hinsichtlich der Stabilität der Viskosität der damit hergestellten wäßrigen Dispersionen besonders interessante Verbindungen sind solche, deren Fettacylgruppen sich ganz oder teilweise von ungesättigten Fettsäuren ableiten, die zu wenigstens 30, vorzugsweise zu wenigstens 55 % in cis-Form vorliegen.Compounds which are particularly interesting with regard to the stability of the viscosity of the aqueous dispersions prepared therewith are those whose fatty acyl groups are wholly or partly unsaturated Derive fatty acids which are present in at least 30, preferably at least 55% in cis form.
Geeignete quartäre Ammoniumverbindungen sind auch aus US-A-5,066,414, EP 0 293 953 A2, EP 0 309 052 A2 und EP 0 345 842 A2 bekannt.Suitable quaternary ammonium compounds are also known from US-A-5,066,414, EP 0 293 953 A2, EP 0 309 052 A2 and EP 0 345 842 A2.
Zu den geeigneten quartären Ammoniumverbindungen zählen auch die von Dimethylaminopropandiol-1,2 abgeleiteten Verbindungen mit zwei Estergruppen. Sie werden beispielsweise in der DE-A-27 28 841 beschrieben. Ein Herstellungsverfahren, das zu derartigen Produkten mit einem niedrigen Fließpunkt führt, ist Gegenstand der EP-A-420 465.Suitable quaternary ammonium compounds also include those derived from dimethylaminopropanediol-1,2 with two ester groups. They are described for example in DE-A-27 28 841. A manufacturing process which leads to such products with a low pour point is the subject of EP-A-420 465.
Die genannten quartären Ammoniumverbindungen lassen sich überraschenderweise auch dann zu viskositätsstabilen wäßrigen Dispersionen verarbeiten, wenn der Gehalt an quartären Ammoniumverbindungen besonders hoch ist, d.h. beispielsweise 15 bis 60 Gew.-%, bezogen auf die wäßrige Dispersion, vorzugsweise 20 bis 40 Gew.-% beträgt. Dies ist durch die erfindungsgemäße Auswahl von nichtionischen Dispergatoren bereits bei Gehalten von weniger als 0,5 Gew.-% der Dispergatoren erreicht worden.The quaternary ammonium compounds mentioned can surprisingly also be processed into viscosity-stable aqueous dispersions if the content of quaternary ammonium compounds is particularly high, i.e. for example 15 to 60 wt .-%, based on the aqueous dispersion, preferably 20 to 40 wt .-%. This has already been achieved by selecting nonionic dispersants according to the invention at contents of less than 0.5% by weight of the dispersants.
Unter Hydroxyfettsäuren werden insbesondere die Ricinolfettsäure und die 9-Hydroxystearinsäure verstanden. Als Hydroxyfettsäuren im Sinne dieser Erfindung eignen sich aber auch Hydroxylgruppen enthaltende Fettsäuren, die durch Epoxidation von Palmitoleinsäure, Ölsäure oder Erucasäure und anschließende Epoxid-Ringöffnung mit protischen Reagenzien wie z.B. Wasser, Alkoholen oder Carbonsäuren erhältlich sind.Hydroxy fatty acids are understood in particular to mean ricinole fatty acid and 9-hydroxystearic acid. Also suitable as hydroxy fatty acids in the sense of this invention are hydroxyl-containing fatty acids which are obtained by epoxidation of palmitoleic acid, oleic acid or erucic acid and subsequent epoxy ring opening with protic reagents such as e.g. Water, alcohols or carboxylic acids are available.
Die Anlagerungsprodukte von 3 - 100 Mol Ethylenoxid an 1/m Mol eines Polyolfettalkoholesters umfassen z.B. Ethoxylate von Fettsäuremono- und -diglyceriden, von Sorbitanmono-, -di- und -sesquiestern von C12-C22-Fettsäuren, an Mono- und Di-fettsäureester des Di- und Triglycerins sowie auch an Triglyceride wie z.B. an Ricinusöl.The adducts of 3-100 moles of ethylene oxide with 1 / mole of a polyol fatty alcohol ester include, for example, ethoxylates of fatty acid mono- and -diglycerides, of sorbitan mono-, di- and sesquiesters of C 12 -C 22 fatty acids, on mono- and di-fatty acid esters of di- and triglycerol as well as on triglycerides such as castor oil.
Besonders gut geeignet sind auch die Ethylenoxid-Anlagerungsprodukte an Ringöffnungsprodukte epoxidierter Triglyceride, wie sie z.B. erhalten werden durch Epoxidation von Sojaöl, Hydrierung oder Umsetzung (Epoxid-Ringöffnung) mit protischen Verbindungen wie z.B. mit H2O, Carbonsäuren oder Alkoholen mit 1 - 10 C-Atomen und anschließende Ethylenoxid-Anlagerung. Solche Produkte sind z.B. aus DE 39 23 394 Al bekannt.The ethylene oxide adducts on ring opening products of epoxidized triglycerides, such as are obtained, for example, by epoxidation of soybean oil, hydrogenation or reaction (epoxy ring opening) with protic compounds, such as with H 2 O, carboxylic acids or alcohols with 1-10 C, are also particularly suitable -Atoms and subsequent ethylene oxide addition. Such products are known, for example, from DE 39 23 394 A1.
Gut geeignet sind auch die Ethylenoxid-Anlagerungsprodukte an Fettsäure(C12-C22)-methylester, von diesen sind insbesondere solche mit 10 - 50 Mol Ethylenoxid bevorzugt. Weiterhin eignen sich auch Ethylenoxid-Anlagerungsprodukte, die zusätzlich 1 - 10 Oxypropylgruppen enthalten und die durch Anlagerung von Propylenoxid und Ethylenoxid, gleichzeitig oder nacheinander, erhalten werden. Die ausgewählten, erfindungsgemäß zu verwendenden Dispergatoren sind in bevorzugten Textilweichmacher-Dispersionen bereits in einer Zusatzmenge von 0,001 bis 0,1 Gew.-% in der Lage, die Viskosität merklich zu senken und ein Nachdicken bei Lagerung so weit verhindern, daß die Fließ- und Gießfähigkeit und eine gute Weiterverdünnbarkeit mit Wasser erhalten bleiben.The ethylene oxide adducts with fatty acid (C 12 -C 22 ) methyl ester are also very suitable, of which those with 10-50 mol ethylene oxide are particularly preferred. Ethylene oxide addition products which additionally contain 1-10 oxypropyl groups and which are obtained by addition of propylene oxide and ethylene oxide, simultaneously or in succession, are also suitable. The selected dispersants to be used according to the invention are already in an added amount of 0.001 to 0.1% by weight in preferred textile plasticizer dispersions capable of markedly reducing the viscosity and preventing subsequent thickening during storage to such an extent that the flow and Pourability and good further dilutability with water are retained.
Überraschend wurde festgestellt, daß bei Verwendung einer textilweichmachenden quartären Ammoniumverbindung des Typs der Formel I (Handelsname: Stepantex(R)VS90)
Falls die wäßrigen Textilweichmacher-Dispersionen nicht schon ohnehin eine geringe Ausgangsviskosität haben, beispielsweise durch die Verwendung von quartären Ammoniumverbindungen geeigneter Struktur, ist es zweckmäßig, eine niedrige Viskosität durch den Zusatz eines Elektrolyten einzustellen. Geeignete Elektrolyten sind beispielsweise Natriumchlorid, Natriumacetat, Magnesiumsulfat oder Calciumchlorid und insbesondere Magnesiumchlorid. Zur Einstellung einer niedrigen Ausgangsviskosität durch Zusatz eines Elektrolyts reichen ebenfalls geringe Mengen aus. Der Elektrolyt liegt beispielsweise in Konzentrationen von 0,01 bis 3 Gew.-%, bezogen auf die fertige Dispersion, in der Dispersion vor.If the aqueous textile plasticizer dispersions do not already have a low initial viscosity, for example by using quaternary ammonium compounds of a suitable structure, it is advisable to set a low viscosity by adding an electrolyte. Suitable electrolytes are, for example, sodium chloride, sodium acetate, magnesium sulfate or calcium chloride and in particular magnesium chloride. Small amounts are also sufficient to set a low initial viscosity by adding an electrolyte. The electrolyte is present in the dispersion, for example, in concentrations of 0.01 to 3% by weight, based on the finished dispersion.
Die genannten Dispersionen zeichnen sich dadurch aus, daß deren Ausgangsviskosität nach der Herstellung auch bei längerer Lagerung in einem breiten Temperaturbereich nicht oder nur geringfügig ansteigt, daß sie einen hohen Wirkstoffgehalt aufweisen, daß sie auch mit kaltem Wasser leicht verdünnbar sind, was sich besonders beim Einspülen in automatischen Waschmaschinen positiv bemerkbar macht, und daß die damit behandelten Textilien nach dem Trocknen nicht nur einen weichen Griff sondern auch eine gute Wiederbenetzbarkeit aufweisen, was insbesondere für Textilien, die auf der Haut getragen werden, von besonderer Bedeutung ist.The dispersions mentioned are distinguished by the fact that their initial viscosity does not increase or only increases slightly after production, even after prolonged storage in a wide temperature range, that they have a high active ingredient content, and that they can easily be diluted with cold water, which is particularly evident when washing them in positively noticeable in automatic washing machines, and that the textiles treated with them do not just soften after drying Handle but also have good rewettability, which is particularly important for textiles that are worn on the skin.
In den folgenden Beispielen wird gezeigt, daß wäßrige Textilweichmacher-Dispersionen, die als textilweichmachende, quartäre Ammoniumverbindung 34 Gew.-% einer Verbindung der Formel I (Stepantex(R)-VS90, ein mit Dimethylsulfat quaterniertes Veresterungsprodukt von Triethanolamin mit zwei Mol Talgfettsäure) enthalten, eine hohe Viskositätsstabilität bei Zusatz von sehr niedrigen Mengen an nichtionischen Dispergatoren aufweisen. Demgegenüber zeigen die Vergleichs-Ansätze ohne Dispergator oder mit Fettalkohol-Ethoxylaten mit nur 5 oder 7 Mol Ethylenoxid (Beispiel 9V, 10V) schon nach 1-wöchiger Lagerung einen nicht akzeptablen Viskositätsanstieg.The following examples show that aqueous fabric softener dispersions which contain 34% by weight of a compound of the formula I (Stepantex (R) -VS90, an esterification product of triethanolamine quaternized with dimethyl sulfate with two moles of tallow fatty acid ) as the fabric softening quaternary ammonium compound , have a high viscosity stability with the addition of very low amounts of nonionic dispersants. In contrast, the comparative batches without dispersant or with fatty alcohol ethoxylates with only 5 or 7 moles of ethylene oxide (example 9V, 10V) already show an unacceptable increase in viscosity after 1 week of storage.
Die Viskosität (mPas) wurde in allen Fällen mit einem Brookfield-Rotationsviskosimeter mit Spindel 2 und 20 Umdrehungen pro Minute bei 20 °C gemessen.The viscosity (mPas) was measured in all cases with a Brookfield rotary viscometer with spindle 2 and 20 revolutions per minute at 20 ° C.
Die geprüften Textilweichmacher-Dispersionen weisen folgende Zusammensetzung auf:
Die Viskosität (mPas) wurde mit einem Brookfield-Rotationsviskosimeter (Spindel 2, 20 Umdrehungen pro Minute) bei 20°C frisch, d.h. unmittelbar nach der Herstellung und nach 1 Woche Lagerung gemessen.
Claims (4)
- A water-based fabric softener dispersion containing fabric-softening quaternary ammonium compounds and nonionic dispersants, characterized in that the dispersion containsa) 15 to 60% by weight of quaternary ammonium compounds containing two or three linear alkyl or acyl groups with 12 to 22 carbon atoms attached thereto by ester or amide bonds andb) 0.001 to 0.5% by weight of nonionic dispersants selected from- products of the addition of 40 to 200 moles of ethylene oxide to 1 mole of a linear fatty alcohol containing 12 to 22 carbon atoms,- products of the addition of 10 to 150 moles of ethylene oxide to 1 mole of a linear fatty acid or hydroxyfatty acid with 12 to 22 carbon atoms, to 1 mole of a linear fatty alkyl amine with 12 to 22 carbon atoms or to 1 mole of a C1-4 lower alkyl ester of a fatty acid or hydroxyfatty acid with 12 to 22 carbon atoms or- products of the addition of 3 to 100 moles of ethylene oxide to 1/m mole of a polyol fatty acid ester of m moles of a fatty acid or hydroxyfatty acid with 12 to 22 carbon atoms and 1 mole of a polyol with 1 to 6 carbon atoms and 2 to 6 hydroxyl groups, m having a value of 1 to 6, or- mixtures of such ethylene oxide addition products.
- A water-based fabric softener dispersion as claimed in claim 1, characterized in that it contains 20 to 40% by weight of a compound corresponding to formula I:
- A water-based fabric softener dispersion as claimed in claim 1, characterized in that the nonionic dispersant is present in a quantity of 0.001 to 0.1% by weight and preferably in a quantity of 0.01 to 0.1% by weight.
- A fabric softener dispersion as claimed in claim 1, characterized in that an electrolyte, preferably magnesium chloride, is additionally present in a quantity of 0.01 to 3% by weight.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4242480 | 1992-12-16 | ||
| DE4242480A DE4242480A1 (en) | 1992-12-16 | 1992-12-16 | Aqueous textile softener dispersions |
| PCT/EP1993/003441 WO1994013772A1 (en) | 1992-12-16 | 1993-12-07 | Aqueous textile softener dispersions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0674701A1 EP0674701A1 (en) | 1995-10-04 |
| EP0674701B1 true EP0674701B1 (en) | 1997-06-18 |
Family
ID=6475439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94902704A Expired - Lifetime EP0674701B1 (en) | 1992-12-16 | 1993-12-07 | Aqueous textile softener dispersions |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0674701B1 (en) |
| AT (1) | ATE154632T1 (en) |
| DE (2) | DE4242480A1 (en) |
| ES (1) | ES2102809T3 (en) |
| WO (1) | WO1994013772A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5916863A (en) | 1996-05-03 | 1999-06-29 | Akzo Nobel Nv | High di(alkyl fatty ester) quaternary ammonium compound from triethanol amine |
| US5919750A (en) * | 1997-07-24 | 1999-07-06 | Akzo Nobel Nv | Fabric softener composition |
| DE10134224B4 (en) * | 2001-07-13 | 2012-12-20 | Clariant Produkte (Deutschland) Gmbh | Additives for inhibiting gas hydrate formation |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2482636A1 (en) * | 1980-05-14 | 1981-11-20 | Lesieur Cotelle Et Associes Sa | CONCENTRATED SOFTENING COMPOSITION FOR TEXTILE FIBERS |
| DE3218667A1 (en) * | 1982-05-18 | 1983-11-24 | Hoechst Ag, 6230 Frankfurt | CONCENTRATED SOFT SOFTENER |
| DE3501521A1 (en) * | 1985-01-18 | 1986-07-24 | Henkel KGaA, 4000 Düsseldorf | AQUEOUS CONCENTRATED TEXTILE SOFTENER |
| GB8818593D0 (en) * | 1988-08-04 | 1988-09-07 | Albright & Wilson | Fabric conditioners |
| GB8916307D0 (en) * | 1989-07-17 | 1989-08-31 | Unilever Plc | Fabric softening composition |
| GB9115255D0 (en) * | 1991-07-15 | 1991-08-28 | Unilever Plc | Fabric softening composition |
-
1992
- 1992-12-16 DE DE4242480A patent/DE4242480A1/en not_active Withdrawn
-
1993
- 1993-12-07 DE DE59306802T patent/DE59306802D1/en not_active Expired - Lifetime
- 1993-12-07 EP EP94902704A patent/EP0674701B1/en not_active Expired - Lifetime
- 1993-12-07 AT AT94902704T patent/ATE154632T1/en active
- 1993-12-07 ES ES94902704T patent/ES2102809T3/en not_active Expired - Lifetime
- 1993-12-07 WO PCT/EP1993/003441 patent/WO1994013772A1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| ES2102809T3 (en) | 1997-08-01 |
| DE59306802D1 (en) | 1997-07-24 |
| DE4242480A1 (en) | 1994-06-23 |
| WO1994013772A1 (en) | 1994-06-23 |
| EP0674701A1 (en) | 1995-10-04 |
| ATE154632T1 (en) | 1997-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE69707864T2 (en) | LONG-CHAIN QUATERNARY AMMONIUM DIALKYL FATTIC ACID ESTER MADE OF TRIALCANOLAMINE | |
| EP2563889B1 (en) | Textile softening composition | |
| EP0675941B1 (en) | Aqueous textile softener dispersions | |
| EP1141189B1 (en) | Clear softening agent formulations | |
| EP0188242B1 (en) | Concentrated aqueous textile softener | |
| DE2631114B2 (en) | Fabric softeners | |
| DE3612479A1 (en) | AQUEOUS CONCENTRATED TEXTILE SOFTENER | |
| DE3602089C2 (en) | A durable, aqueous, pourable and water-dispersible fabric softening composition | |
| EP0613457B1 (en) | Esters of fatty acids with ethoxylated polyols | |
| DE602004008217T2 (en) | Easily dispersible concentrated esterquat compositions | |
| DE69532508T2 (en) | Fabric softening composition | |
| EP0498050A2 (en) | Aqueous emulsions comprising fatty acid esters of N-methyl-N,N,N-trihydroxyethyl-ammonium-methyl-sulfate | |
| EP0267551A2 (en) | Quaternary ammonium compounds, their preparation and use as textile-finishing agents | |
| EP0718275B1 (en) | Quaternary fatty-acid triethanolamine esters | |
| EP0213519A2 (en) | Textile-treating composition | |
| EP0346634A1 (en) | Liquid aqueous composition for the aftertreatment of laundry | |
| EP0295386A2 (en) | Concentrated fabric softener | |
| DE2258564A1 (en) | COMPOUNDS WITH SURFACTANT AND SOFTENING PROPERTIES AND THEIR USE | |
| EP0248365A1 (en) | Quaternary salts of 2-alkyl imidazolines, process for their production and their use | |
| EP0391392B1 (en) | Low-foam, cold-stable aqueous detergents containing nonionic, anionic and cationic surface active agents and their utilization | |
| EP0674701B1 (en) | Aqueous textile softener dispersions | |
| EP0688356B1 (en) | Aqueous textile softener compositions | |
| DE60312204T3 (en) | ESTERQUATED SOFT WATER CONCENTRATE WITH SPECIAL ESTER DISTRIBUTION AND ELECTROLYTE | |
| DE2721847C2 (en) | ||
| EP0230910B2 (en) | Means for treating textiles |
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: 19950607 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE ES FR IT LI NL |
|
| 17Q | First examination report despatched |
Effective date: 19960531 |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE ES FR IT LI NL |
|
| REF | Corresponds to: |
Ref document number: 154632 Country of ref document: AT Date of ref document: 19970715 Kind code of ref document: T |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
| ET | Fr: translation filed | ||
| REF | Corresponds to: |
Ref document number: 59306802 Country of ref document: DE Date of ref document: 19970724 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2102809 Country of ref document: ES Kind code of ref document: T3 |
|
| ITF | It: translation for a ep patent filed | ||
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20121205 Year of fee payment: 20 Ref country code: CH Payment date: 20121213 Year of fee payment: 20 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20121227 Year of fee payment: 20 Ref country code: IT Payment date: 20121213 Year of fee payment: 20 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20121208 Year of fee payment: 20 Ref country code: AT Payment date: 20121127 Year of fee payment: 20 Ref country code: FR Payment date: 20130107 Year of fee payment: 20 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20121217 Year of fee payment: 20 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R071 Ref document number: 59306802 Country of ref document: DE |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: V4 Effective date: 20131207 |
|
| BE20 | Be: patent expired |
Owner name: *HENKEL K.G.A.A. Effective date: 20131207 |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK07 Ref document number: 154632 Country of ref document: AT Kind code of ref document: T Effective date: 20131207 |
|
| 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 EXPIRATION OF PROTECTION Effective date: 20131210 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20140925 |
|
| 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 EXPIRATION OF PROTECTION Effective date: 20131208 |