EP0193832A1 - Method for the manufacture of waterproof leather or fur - Google Patents
Method for the manufacture of waterproof leather or fur Download PDFInfo
- Publication number
- EP0193832A1 EP0193832A1 EP86102381A EP86102381A EP0193832A1 EP 0193832 A1 EP0193832 A1 EP 0193832A1 EP 86102381 A EP86102381 A EP 86102381A EP 86102381 A EP86102381 A EP 86102381A EP 0193832 A1 EP0193832 A1 EP 0193832A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- impregnating
- leather
- sulfosuccinic acid
- weight
- acid monoester
- 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.)
- Granted
Links
- 239000010985 leather Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 230000020477 pH reduction Effects 0.000 claims description 4
- 125000005907 alkyl ester group Chemical group 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- -1 fatty acid esters Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- 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 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 229920001864 tannin Polymers 0.000 claims 1
- 239000001648 tannin Substances 0.000 claims 1
- 235000018553 tannin Nutrition 0.000 claims 1
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003925 fat Substances 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 150000002191 fatty alcohols Chemical class 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 4
- 235000019197 fats Nutrition 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- FHIDNBAQOFJWCA-UAKXSSHOSA-N 5-fluorouridine Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1N1C(=O)NC(=O)C(F)=C1 FHIDNBAQOFJWCA-UAKXSSHOSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 206010000496 acne Diseases 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000037308 hair color Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000002316 solid fats Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/04—Fixing tanning agents in the leather
Definitions
- Stabilizing the licker liquor with anionic and nonionic emulsifiers such as alkyl sulfates, alkylarylsulfonates or fatty alcohol ethoxylates, is out of the question because of the increase in water absorbency.
- the invention thus relates to a process for the production of waterproof leather or furs using sulfosuccinic acid monoesters in combination with impregnating and / or hydrophobizing greasing agents, characterized in that the leather or furs are subsequently impregnated in an aqueous liquor with impregnating and / or hydrophobizing agents Fatting agents which contain sulfosuccinic acid monoester salts with C 12 -C 24 fat residues are treated and fixed after acidification by adding a chromium and / or aluminum salt.
- the sulfosuccinic acid monoester salts are preferably used in combination with impregnating fatliquoring agents. These include, in particular, oxidized or oxidized and partly sulfonated C 18 -C 26 hydrocarbons or C 32 -C 40 waxes, C P hosphor Textremono- 12 - C 24 - alkyl esters, partial esters of polycarboxylic acids such as CitronenTalkremono-C 16 -C 24 alkyl esters, Partial ester of Polyalcohols, such as sorbitan, glycerol or pentaerythritol C16-C24 fatty acid esters.
- the proportion of sulfosuccinic acid monoester salts in the fatliquor combination is 10 to 60, preferably 20 to 40 percent by weight.
- greasing agents are used in licker lubrication, depending on the type of leather, in an amount of 5 to 20 percent by weight, based on the shaved weight of the leather.
- the leather When using the sulfosuccinic acid monoesters in combinations with neutral oils, such as long-chain hydrocarbons, chlorinated paraffin, animal and vegetable oils and fats or their methyl esters and chlorinated fatty acid methyl esters, the leather also has a reduced water absorbency if acidified after greasing and then with chromium and / or aluminum salts is fixed.
- neutral oils such as long-chain hydrocarbons, chlorinated paraffin, animal and vegetable oils and fats or their methyl esters and chlorinated fatty acid methyl esters
- fatty agents containing sulfosuccinic acid monoester salts can also be used in part in normal leaching with sulfated, sulfited and / or synthetic fatliquors based on chloroparaffin sulfonates, depending on the proportion of impregnating and / or hydrophobizing fatliquoring, a more or less pronounced water resistance is achieved.
- the sulfosuccinic acid monoester salts are prepared in a known manner by esterification of maleic anhydride with approximately one equivalent of the desired ester ester component and subsequent reaction with an approximately equivalent to the maleic anhydride Amount of a sulfite or bisulfite, for example according to DE-OS 16 69 347. Fat residues with 12 to 24 carbon atoms and compounds containing hydroxyl groups are suitable as esterification components. The fat residues can be saturated or unsaturated.
- fatty alcohols or fatty acid mono- or diglycerides for example C 12 -C 18 coconut fatty alcohol, C 16 -C 18 tallow alcohol, C 16 -C 18 tallow fatty acid monoglyceride, or from adducts of 1 to 6 mol of alkylene oxide with the aforementioned Fatty alcohols or fatty acid glycerides or fatty acids, e.g. the adduct of 2 to 3 moles of ethylene oxide with C 16 -C 18 tallow fatty alcohol or from 4 to 6 moles of ethylene oxide to a C 16 -C 24 fatty acid mixture or of 2 moles of ethylene oxide to a C 12 - C 18 fatty acid mixture.
- the sulfosuccinic acid monoester salts are preferably prepared as sodium or ammonium salts, but other alkalis or organic amines can also be used as cations.
- Water-soluble chromium and / or aluminum salts are used to fix the sulfosuccinic acid monoester salts.
- the application amount is 1 to 10 percent by weight in the liquor.
- the claimed process is carried out in such a way that the sulfosuccinic acid monoester salts and, if appropriate, further fatliquoring agents are used as a licker after the retanning and, if appropriate, dyeing and subsequent washing out of excess tanning agent.
- High temperatures over 50 ° C can be avoided here.
- the aftertreatment is initially carried out in a customary manner by acidification, preferably with formic acid, it being possible, if appropriate, to precede a brief treatment with a polyacrylate tanning agent. Then fix with the chrome and / or aluminum salts at about nH 3.5.
- the claimed Fatliquors be well received by the leather and spread very evenly over the entire leather q uerites. They have a remarkable resistance to water and give the leather excellent waterproofness, especially under dynamic loads. The result is soft, firm-grain leather with a pleasantly slim handle, which is particularly suitable for the production of upper leather, clothing velor and fur velor.
- the sheepskins are worked up to the hair color as usual via switches, laundry, pimples / tanning, retanning and greasing.
- the velor color is impregnated according to the following procedure.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Insulated Conductors (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Gloves (AREA)
Abstract
Description
Zur Herstellung wasserdichter Leder oder Pelze sind insbesondere drei Verfahrensprinzipien bekannt:
- 1) Imprägnierung durch Einlagerung wasserunlöslicher Substanzen, z.B. feste Fette, Wachse oder spezielle Polymere.
- 2) Imprägnierung durch Einlagerung wasserquellender Substanzen, die bei Wasseraufnahme hochviskose Emulsionen bilden und die Faserzwischenräume des Leders verstopfen, z.B. spezielle Emulgatoren vom Wässer-in-öl-(W/O)-Typ.
- 3) Behandlung mit hydrophobierend wirkenden Substanzen, z.B. Aluminium- und Chromkomplexe, Silikone oder organische Fluor-Verbindungen.
- 1) Impregnation by storing water-insoluble substances, e.g. solid fats, waxes or special polymers.
- 2) Impregnation by storing water-swelling substances that form highly viscous emulsions when water is absorbed and clog the interstices of the leather, eg special emulsifiers of the water-in-oil (W / O) type.
- 3) Treatment with substances having a hydrophobic effect, for example aluminum and chromium complexes, silicones or organic fluorine compounds.
Diese Maßnahmen können auch im Zusammenhang mit einer üblichen Lickerung unter Verwendung gebräuchlicher Fettungsmittel durchgeführt, wobei die genannten Mittel in der Lickerflotte eingesetzt werden.These measures can also be carried out in connection with a conventional seepage using customary lubricants, the agents mentioned being used in the liquor fleet.
In der Praxis wird häufig eine Kombination der unter 2) und 3) genannten Maßnahmen angewandt, wobei aus wirtschaftlichen und ökologischen Gründen bevorzugt im Walkfaß in wäßriger Flotte gearbeitet wird. Dabei erfolgt eine Umwandlung der W/0-Emulgatoren in hydrophobierende Metallkomplexsalze durch eine Fixierung mit Chrom- bzw. Aluminiumsalzen. Dieses Verfahren weist aber Nachteile auf, da wegen der Instabilität der gebräuchlichen Lickeremulsionen die Imprägnierung bei relativ hohen pH-Werten (>6) durchgeführt werden muß, um ein oberflächliches Ausfallen der Fettungsmittel und damit Verschmierungen zu vermeiden. Außerdem ist bei diesem Verfahren in der Regel eine hohe Temperatur der Lickerflotte von ca. 60 °C erforderlich, was leicht zu einer Losnarbigkeit des Leders führt. Außerdem zeigen die in der Praxis erhaltenen Penetrometerwerte häufig starke Schwankungen infolge einer ungleichmäßigen Fettverteilung durch den Lederquerschnitt, so daß eine aufwendige Nachbehandlung des Leders durch Spritzen, Gießen oder Plüschen notwendig werden kann.In practice, a combination of the measures mentioned under 2) and 3) is often used, preference being given to working in a drum in an aqueous liquor for economic and ecological reasons. The W / 0 emulsifiers are converted into hydrophobizing metal complex salts by a fixation with Chrome or aluminum salts. However, this method has disadvantages, since, due to the instability of the usual licker emulsions, the impregnation must be carried out at relatively high pH values (> 6) in order to avoid superficial precipitation of the greasing agents and thus smearing. In addition, this process generally requires a high temperature of the licker liquor of approximately 60 ° C., which easily leads to a loose grain of the leather. In addition, the penetrometer values obtained in practice often show large fluctuations as a result of an uneven fat distribution through the leather cross section, so that an expensive aftertreatment of the leather by spraying, pouring or plushing may be necessary.
Eine Stabilisierung der Lickerflotte mit anionischen und nichtionischen Emulgatoren, wie Alkylsulfaten, Alkylarylsulfonaten oder Fettalkoholethoxylaten kommt wegen der Erhöhung der Wasserzügigkeit nicht in Frage.Stabilizing the licker liquor with anionic and nonionic emulsifiers, such as alkyl sulfates, alkylarylsulfonates or fatty alcohol ethoxylates, is out of the question because of the increase in water absorbency.
Aus DE-OS 16 69 347 ist die Anwendung von in Nasser emul- gierbaren Sulfobernsteinsäureestern zum Fetten von Leder bekannt, wobei jedoch keine Wasserdichteffekte erzielt werden.DE-A 16 69 347 the use of emulsified g ierbaren in Nasser sulfosuccinic is known for oiling leather, although no waterproof effects.
In der älteren Anmeldung P 34 19 405.3 wird ein Verfahren zur Herstellung von Leder und Pelzen beschrieben, wobei als Fettungsmittel in der Gerbflotte eine Kombination von Sulfobernsteinsäureestern mit bestimmten anionischen oder nichtionischen Emulgatoren während der Chrom- oder Aluminiumgerbung bzw. -Machgerbung angewendet wird. Auch bei diesem Verfahren wird ein Wasserdichteffekt nicht erzielt.In the earlier application P 34 19 405.3, a process for the production of leather and furs is described, a combination of sulfosuccinic acid esters with certain anionic or nonionic emulsifiers during chrome or aluminum tanning or light tanning being used as the fatliquor in the tanning liquor. A waterproof effect is not achieved with this method either.
Es wurde nun die überraschende Feststellung gemacht, daß mit Sulfobernsteinsäuremonoestern gefettete Leder bei hoher Weichheit eine verminderte Wasserzügigkeit aufweisen, wenn nach dem Absäuern der Fettung eine Fixierung mit Chrom- und/oder Aluminiumsalzen vorgenommen wird.It has now been made the surprising finding that leather greased with sulfosuccinic acid monoesters, with high softness, has a reduced water absorbency if fixation with chromium and / or aluminum salts is carried out after acidification of the greasing.
Damit ist es möglich, unter Mitverwendung von Sulfobernsteinsäuremonoestern bei der imprägnierenden und/oder hydrophobierenden Fettung die Stabilität der Lickeremulsionen so zu verbessern, daß die beschriebenen Nachteile der bisherigen Verfahren nicht auftreten.It is thus possible, with the use of sulfosuccinic acid monoesters in the impregnating and / or hydrophobic greasing, to improve the stability of the licker emulsions in such a way that the disadvantages of the previous processes described do not occur.
Gegenstand der Erfindung ist somit ein Verfahren zur Herstellung wasserdichter Leder oder Pelze unter Verwendung von Sulfobernsteinsäuremonoestern in Kombination mit imprägnierenden und/oder hydrophobierenden Fettungsmitteln, dadurch gekennzeichnet, daß man die Leder oder Pelze im Anschluß an die Nachgerbung in wäßriger Flotte mit imprägnierenden und/oder hydrophobierenden Fettungsmitteln, die Sulfobernsteinsäuremonoester-Salze mit C12-C24-Fettresten enthalten, behandelt und nach Absäuern durch Zugabe eines Chrom-und/oder Aluminiumsalzes fixiert.The invention thus relates to a process for the production of waterproof leather or furs using sulfosuccinic acid monoesters in combination with impregnating and / or hydrophobizing greasing agents, characterized in that the leather or furs are subsequently impregnated in an aqueous liquor with impregnating and / or hydrophobizing agents Fatting agents which contain sulfosuccinic acid monoester salts with C 12 -C 24 fat residues are treated and fixed after acidification by adding a chromium and / or aluminum salt.
Die Sulfobernsteinsäuremonoester-Salze werden vorzugsweise in Kombination mit imprägnierenden Fettungsmitteln angewendet. Hierzu zählen insbesondere oxidierte oder oxidierte und teilsulfierte C18-C26-Kohlenwasserstoffe oder C32-C40-wachse, Phosphorsäuremono-C 12-C 24- alkylester, Partialester von Polycarbonsäuren, wie Citronensäuremono-C16-C24-alkylester, Partialester von Polyalkoholen, wie Sorbitan-, Glyzerin- oder Pentaerythrit-C16-C24-fettsäureester.The sulfosuccinic acid monoester salts are preferably used in combination with impregnating fatliquoring agents. These include, in particular, oxidized or oxidized and partly sulfonated C 18 -C 26 hydrocarbons or C 32 -C 40 waxes, C P hosphorsäuremono- 12 - C 24 - alkyl esters, partial esters of polycarboxylic acids such as Citronensäuremono-C 16 -C 24 alkyl esters, Partial ester of Polyalcohols, such as sorbitan, glycerol or pentaerythritol C16-C24 fatty acid esters.
In der Fettungsmittel-Kombination beträgt der Anteil der Sulfobernsteinsäuremonoester-Salze 10 bis 60, vorzugsweise 20 bis 40 Gewichtsprozent. Derartige Fettungsmittel werden bei der Lickerfettung je nach Ledertyp in einer Menge von 5 bis 20 Gewichtsprozent, bezogen auf das Falzgewicht der Leder, eingesetzt.The proportion of sulfosuccinic acid monoester salts in the fatliquor combination is 10 to 60, preferably 20 to 40 percent by weight. Such greasing agents are used in licker lubrication, depending on the type of leather, in an amount of 5 to 20 percent by weight, based on the shaved weight of the leather.
Bei Verwendung der Sulfobernsteinsäuremonoester in Kombinationen mit Neutralölen, wie langkettige Kohlenwasserstoffe, Chlorparaffin, tierische und vegetabile öle und Fette bzw. deren Methylester und chlorierte Fettsäuremethylester, als Fettungsmittel tritt ebenfalls eine verminderte Wasserzügigkeit der Leder ein, wenn nach der Fettung abgesäuert und danach mit Chrom-und/oder Aluminiumsalzen fixiert wird.When using the sulfosuccinic acid monoesters in combinations with neutral oils, such as long-chain hydrocarbons, chlorinated paraffin, animal and vegetable oils and fats or their methyl esters and chlorinated fatty acid methyl esters, the leather also has a reduced water absorbency if acidified after greasing and then with chromium and / or aluminum salts is fixed.
Die genannten Sulfobernsteinsäuremonoester-Salze enthaltenden Fettungsmittel können auch anteilig in einer normalen Lickerfettung mit sulfatierten, sulfitierten und/oder synthetischen Fettungsmitteln auf Basis Chlorparaffinsulfonaten mitverwendet werden, wobei je nach Anteil der imprägnierenden und/oder hydrophobierenden Fettungsmittel eine mehr oder weniger stark ausgeprägte Wasserdichtigkeit erzielt wird.The above-mentioned fatty agents containing sulfosuccinic acid monoester salts can also be used in part in normal leaching with sulfated, sulfited and / or synthetic fatliquors based on chloroparaffin sulfonates, depending on the proportion of impregnating and / or hydrophobizing fatliquoring, a more or less pronounced water resistance is achieved.
Die Herstellung der Sulfobernsteinsäuremonoester-Salze erfolgt in bekannter Weise durch Veresterung von Maleinsäureanhydrid mit ca. einem Äquivalent der gewünschten Veresterunaskomponente und anschließende Umsetzung mit einer dem Maleinsäureanhydrid annähernd äquivalenten Menge eines Sulfits oder Bisulfits, z.B. entsprechend DE-OS 16 69 347. Als Veresterungskomponente kommen Fettreste mit 12 bis 24 C-Atomen sowie Hydroxygruppen enthaltende Verbindungen in Betracht. Die Fettreste können gesättigt oder ungesättigt sein. Sie können sich herleiten von Fettalkoholen oder Fettsäuremono- oder -diglyceriden, z.B. C12-C18-Kokosfettalkohol, C16-C18-Talgalkohol, C16-C18-Talgfettsäuremonoglycerid, oder von Addukten von 1 bis 6 Mol Alkylenoxid an die genannten Fettalkohole oder Fettsäureglyceride oder an Fettsäuren, z.B. das Addukt von 2 bis 3 Mol Ethylenoxid an C16-C18-Talgfettalkohol oder von 4 bis 6 Mol Ethylenoxid an ein C16-C24-Fettsäuregemisch oder von 2 Mol Ethylenoxid an ein C12-C18-Fettsäuregemisch. Die Sulfobernsteinsäuremonoester-Salze werden vorzugsweise als Natrium- oder Ammoniumsalze hergestellt, doch kommen als Kationen auch andere Alkalien oder organische Amine in Betracht.The sulfosuccinic acid monoester salts are prepared in a known manner by esterification of maleic anhydride with approximately one equivalent of the desired ester ester component and subsequent reaction with an approximately equivalent to the maleic anhydride Amount of a sulfite or bisulfite, for example according to DE-OS 16 69 347. Fat residues with 12 to 24 carbon atoms and compounds containing hydroxyl groups are suitable as esterification components. The fat residues can be saturated or unsaturated. They can be derived from fatty alcohols or fatty acid mono- or diglycerides, for example C 12 -C 18 coconut fatty alcohol, C 16 -C 18 tallow alcohol, C 16 -C 18 tallow fatty acid monoglyceride, or from adducts of 1 to 6 mol of alkylene oxide with the aforementioned Fatty alcohols or fatty acid glycerides or fatty acids, e.g. the adduct of 2 to 3 moles of ethylene oxide with C 16 -C 18 tallow fatty alcohol or from 4 to 6 moles of ethylene oxide to a C 16 -C 24 fatty acid mixture or of 2 moles of ethylene oxide to a C 12 - C 18 fatty acid mixture. The sulfosuccinic acid monoester salts are preferably prepared as sodium or ammonium salts, but other alkalis or organic amines can also be used as cations.
Zur Fixierung der Sulfobernsteinsäuremonoester-Salze dienen wasserlösliche Chrom- un/oder Aluminiumsalze. Bevorzugt werden basische Chrom- oder Aluminiumsalze oder deren Mischungen, wie sie auch als Ledergerbstoffe verwendet werden. Die Anwendungsmenge beträgt 1 bis 10 Gewichtsprozent in der Flotte.Water-soluble chromium and / or aluminum salts are used to fix the sulfosuccinic acid monoester salts. Basic chromium or aluminum salts or mixtures thereof, as are also used as leather tanning agents, are preferred. The application amount is 1 to 10 percent by weight in the liquor.
Das beanspruchte Verfahren wird in der Weise durchgeführt, daß die Sulfobernsteinsäuremonoester-Salze und gegebenenfalls weiteren Fettungsmittel im Anschluß an die Nachgerbung und gegebenenfalls Färbung und nachfolgendes Auswaschen überschüssigen Gerbmittels als Licker angewendet werden. Hohe Temperaturen über 50 °C können hierbei vermieden werden. Die Nachbehandlung erfolgt zunächst in üblicher Weise durch Absäuern, vorzugsweise mit Ameisensäure, wobei gegebenenfalls eine kurze Behandlung mit einem Polyacrylat-Gerbstoff vorgeschaltet werden kann. Danach erfolgt Fixierung mit den Chrom- und/oder Aluminiumsalzen bei etwa nH 3,5.The claimed process is carried out in such a way that the sulfosuccinic acid monoester salts and, if appropriate, further fatliquoring agents are used as a licker after the retanning and, if appropriate, dyeing and subsequent washing out of excess tanning agent. High temperatures over 50 ° C can be avoided here. The aftertreatment is initially carried out in a customary manner by acidification, preferably with formic acid, it being possible, if appropriate, to precede a brief treatment with a polyacrylate tanning agent. Then fix with the chrome and / or aluminum salts at about nH 3.5.
Die beanspruchten Fettungsmittel werden vom Leder gut aufgenommen und verteilen sich sehr gleichmäßig über den gesamten Lederquerschnitt. Sie besitzen eine bemerkenswerte Beständigkeit gegen Wasser und verleihen dem Leder eine hervorragende Wasserdichtigkeit, insbesondere auch unter dynamischer Belastung. Man erhält weiche, festnarbige Leder mit angenehm schmalzigem Griff, die sich besonders zur Herstellung von Schuhoberleder, Bekleidungsvelour und Pelzvelour eignen.The claimed Fatliquors be well received by the leather and spread very evenly over the entire leather q uerschnitt. They have a remarkable resistance to water and give the leather excellent waterproofness, especially under dynamic loads. The result is soft, firm-grain leather with a pleasantly slim handle, which is particularly suitable for the production of upper leather, clothing velor and fur velor.
In üblicher Weise, jedoch ohne Zusätze anionischer Tenside, chromgegerbte Rind-Wet-blue, pH 3,8, Falzstärke 1,8 mm, werden wie folgend weiterbehandelt:
Die Schaffelle werden bis zur Haarfarbe wie üblich über Weiche, Wäsche, Pickel/Gerbung, Nachgerbung und Fettung gearbeitet. In der Velourfarbe erfolgt nach nachstehender Arbeitsweise die Imprägnierung.
Claims (7)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT86102381T ATE36349T1 (en) | 1985-03-01 | 1986-02-24 | PROCESS FOR MAKING WATERPROOF LEATHER OR FUR. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19853507241 DE3507241A1 (en) | 1985-03-01 | 1985-03-01 | METHOD FOR PRODUCING WATERPROOF LEATHER OR FUR |
DE3507241 | 1985-03-01 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0193832A1 true EP0193832A1 (en) | 1986-09-10 |
EP0193832B1 EP0193832B1 (en) | 1988-08-10 |
Family
ID=6263905
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86102381A Expired EP0193832B1 (en) | 1985-03-01 | 1986-02-24 | Method for the manufacture of waterproof leather or fur |
Country Status (11)
Country | Link |
---|---|
US (1) | US4755187A (en) |
EP (1) | EP0193832B1 (en) |
JP (1) | JPS61211399A (en) |
AT (1) | ATE36349T1 (en) |
BR (1) | BR8600857A (en) |
CA (1) | CA1256655A (en) |
DE (2) | DE3507241A1 (en) |
ES (1) | ES8706211A1 (en) |
IN (1) | IN166295B (en) |
MX (1) | MX164625B (en) |
TR (1) | TR22674A (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0324536A1 (en) * | 1988-01-07 | 1989-07-19 | Exxon Chemical Patents Inc. | Improved leather |
EP0362134A2 (en) * | 1988-09-28 | 1990-04-04 | Ciba-Geigy Ag | Leather treating agent |
WO1993005188A1 (en) * | 1991-09-03 | 1993-03-18 | Henkel Kommanditgesellschaft Auf Aktien | Aqueous dispersions of novel amphiphilic co-oligomers for imparting a washing and cleaning-resistant finish to leather and pelts and their use |
WO1995019452A1 (en) * | 1994-01-12 | 1995-07-20 | Henkel Kommanditgesellschaft Auf Aktien | Use of aminopropionic acid derivatives for the fatty treatment of leather |
US5489389A (en) * | 1992-07-14 | 1996-02-06 | Henkel Kommanditgesellschaft Auf Aktien | New leather oiling preparations and their use |
US5567343A (en) * | 1992-07-14 | 1996-10-22 | Henkel Kommanditgesellschaft Auf Aktien | New leather oiling preparations and their use |
WO1997002240A1 (en) * | 1995-07-04 | 1997-01-23 | Henkel Kommanditgesellschaft Auf Aktien | Sulfosuccinates used as leather-stuffing agents and as cleaning agents |
EP0761823A1 (en) * | 1995-07-26 | 1997-03-12 | Hans J. Scheen | Leather tanning processes and the products thereof |
US5683611A (en) * | 1994-01-12 | 1997-11-04 | Henkel Kommanditgesellschaft Auf Aktien | Preparations for the oiling of leather |
US5728313A (en) * | 1994-02-18 | 1998-03-17 | Henkel Corporation | Leather oiling compositions and their use |
WO2002085845A2 (en) * | 2001-03-08 | 2002-10-31 | Basf Aktiengesellschaft | Mixtures of sulfogroup-containing esters of polybasic organic acids with long-chain alkanols |
US10947605B2 (en) | 2016-01-12 | 2021-03-16 | Fraunhofer-Gesellschaft Zur Forderung Der Angewand | Method for hydrophobising leather, and leather produced by means of same |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3620780A1 (en) * | 1986-06-20 | 1987-12-23 | Henkel Kgaa | LUBRICANTS BASED ON SULPHONIC ACID MONOAMIDES |
DE3909614A1 (en) * | 1989-03-23 | 1990-09-27 | Zschimmer & Schwarz Gmbh & Co | Process for fatliquoring and hydrophobicising leather and fur skins |
US5069935A (en) * | 1990-11-07 | 1991-12-03 | Wilson Sporting Goods Co. | Method of making water-repellent leather game ball |
DE4214150A1 (en) * | 1992-04-29 | 1993-11-11 | Stockhausen Chem Fab Gmbh | Process for the hydrophobization of materials of fibrous structure and means for carrying out the process |
DE4240159A1 (en) * | 1992-11-30 | 1994-06-01 | Henkel Kgaa | Sulphited fatty substances with a reduced content of free hydrogen sulphite |
US7066852B1 (en) | 1998-11-02 | 2006-06-27 | Callaway Golf Company | Game ball with improved moisture resistance |
US6123632A (en) * | 1998-11-02 | 2000-09-26 | Spalding Sports Worldwide, Inc. | Game ball with improved moisture resistance |
US6726582B1 (en) * | 2000-01-11 | 2004-04-27 | Classic Sport Companies, Inc. | Sport ball having improved surface and method for manufacture thereof |
DE10012722A1 (en) * | 2000-03-16 | 2001-09-20 | Basf Ag | Mixtures of di- or tri-basic carboxylic acid monoesters with OH group free 18-45 C ethers and esters, useful for leather treatment, contain up to 85 wt.% ether groups and up to 16 wt.% ester groups |
KR100469808B1 (en) * | 2002-07-27 | 2005-02-02 | 김홍립 | manufacture method of a section dyeing leather |
KR100617978B1 (en) * | 2006-03-08 | 2006-08-28 | 한국신발피혁연구소 | Manufacturing Method of Cow-like Beef Leather Using Raw Bull Skin |
CN103060483B (en) * | 2013-01-08 | 2015-01-28 | 四川大学 | Double waterproof chromium-free tanned sheep fur and its making method |
CN114622043B (en) * | 2022-04-13 | 2023-12-01 | 瑞泰(漳浦)皮业有限公司 | Manufacturing method of waterproof leather with head layer |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1559985A (en) * | 1967-03-25 | 1969-03-14 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2693996A (en) * | 1949-11-28 | 1954-11-09 | Fuchs George Hugo Von | Water resistant leather and process of making the same |
US3291557A (en) * | 1963-01-07 | 1966-12-13 | Battelle Development Corp | Alkyl dicarboxylic acid treatment of leather |
US3668124A (en) * | 1970-05-13 | 1972-06-06 | Pennwalt Corp | Composition and method for treating dry-cleanable soil-resistant leathers |
US4386491A (en) * | 1980-11-17 | 1983-06-07 | Sunkist Growers, Inc. | Apparatus for selectively packing layers of objects in boxes of different depths |
DE3419405A1 (en) * | 1984-05-24 | 1985-11-28 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR PRODUCING LEATHER AND FURS |
-
1985
- 1985-03-01 DE DE19853507241 patent/DE3507241A1/en not_active Withdrawn
- 1985-10-31 IN IN872/MAS/85A patent/IN166295B/en unknown
-
1986
- 1986-02-24 DE DE8686102381T patent/DE3660494D1/en not_active Expired
- 1986-02-24 AT AT86102381T patent/ATE36349T1/en not_active IP Right Cessation
- 1986-02-24 EP EP86102381A patent/EP0193832B1/en not_active Expired
- 1986-02-28 MX MX1714A patent/MX164625B/en unknown
- 1986-02-28 CA CA000502991A patent/CA1256655A/en not_active Expired
- 1986-02-28 ES ES552548A patent/ES8706211A1/en not_active Expired
- 1986-02-28 TR TR10291/86A patent/TR22674A/en unknown
- 1986-02-28 BR BR8600857A patent/BR8600857A/en not_active IP Right Cessation
- 1986-03-01 JP JP61045137A patent/JPS61211399A/en active Granted
- 1986-03-03 US US06/835,499 patent/US4755187A/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1559985A (en) * | 1967-03-25 | 1969-03-14 |
Non-Patent Citations (1)
Title |
---|
DAS LEDER, Band 33, Nr. 3, März 1982, Seite 45, Darmstadt, DE; & SU - A - 715625 (MOSC LIGHT IND. TECH.) 25.02.1980 * |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0324536A1 (en) * | 1988-01-07 | 1989-07-19 | Exxon Chemical Patents Inc. | Improved leather |
US5457835A (en) * | 1988-01-07 | 1995-10-17 | Exxon Chemical Patents Inc. | Leather |
EP0362134A2 (en) * | 1988-09-28 | 1990-04-04 | Ciba-Geigy Ag | Leather treating agent |
EP0362134A3 (en) * | 1988-09-28 | 1992-01-08 | Ciba-Geigy Ag | Leather treating agent |
WO1993005188A1 (en) * | 1991-09-03 | 1993-03-18 | Henkel Kommanditgesellschaft Auf Aktien | Aqueous dispersions of novel amphiphilic co-oligomers for imparting a washing and cleaning-resistant finish to leather and pelts and their use |
US5501707A (en) * | 1991-09-03 | 1996-03-26 | Henkel Kommanditgesellschaft Auf Aktien | Aqueous dispersions of new amphiphilic co-oligomers for the washing- and cleaning-resistant oiling of leather and skins and their use |
US5741434A (en) * | 1992-07-14 | 1998-04-21 | Henkel Kommanditgesellschaft Auf Aktien | Leather oiling preparations and their use |
US5489389A (en) * | 1992-07-14 | 1996-02-06 | Henkel Kommanditgesellschaft Auf Aktien | New leather oiling preparations and their use |
US5567343A (en) * | 1992-07-14 | 1996-10-22 | Henkel Kommanditgesellschaft Auf Aktien | New leather oiling preparations and their use |
WO1995019452A1 (en) * | 1994-01-12 | 1995-07-20 | Henkel Kommanditgesellschaft Auf Aktien | Use of aminopropionic acid derivatives for the fatty treatment of leather |
US5683611A (en) * | 1994-01-12 | 1997-11-04 | Henkel Kommanditgesellschaft Auf Aktien | Preparations for the oiling of leather |
US5728313A (en) * | 1994-02-18 | 1998-03-17 | Henkel Corporation | Leather oiling compositions and their use |
WO1997002240A1 (en) * | 1995-07-04 | 1997-01-23 | Henkel Kommanditgesellschaft Auf Aktien | Sulfosuccinates used as leather-stuffing agents and as cleaning agents |
EP0761823A1 (en) * | 1995-07-26 | 1997-03-12 | Hans J. Scheen | Leather tanning processes and the products thereof |
WO2002085845A2 (en) * | 2001-03-08 | 2002-10-31 | Basf Aktiengesellschaft | Mixtures of sulfogroup-containing esters of polybasic organic acids with long-chain alkanols |
WO2002085845A3 (en) * | 2001-03-08 | 2003-12-04 | Basf Ag | Mixtures of sulfogroup-containing esters of polybasic organic acids with long-chain alkanols |
US10947605B2 (en) | 2016-01-12 | 2021-03-16 | Fraunhofer-Gesellschaft Zur Forderung Der Angewand | Method for hydrophobising leather, and leather produced by means of same |
Also Published As
Publication number | Publication date |
---|---|
ES8706211A1 (en) | 1987-05-16 |
JPH0574640B2 (en) | 1993-10-18 |
TR22674A (en) | 1988-02-26 |
US4755187A (en) | 1988-07-05 |
EP0193832B1 (en) | 1988-08-10 |
ES552548A0 (en) | 1987-05-16 |
DE3660494D1 (en) | 1988-09-15 |
IN166295B (en) | 1990-04-07 |
DE3507241A1 (en) | 1986-09-04 |
MX164625B (en) | 1992-09-10 |
BR8600857A (en) | 1986-11-11 |
CA1256655A (en) | 1989-07-04 |
JPS61211399A (en) | 1986-09-19 |
ATE36349T1 (en) | 1988-08-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0193832B1 (en) | Method for the manufacture of waterproof leather or fur | |
EP0638128B1 (en) | Process and agents for waterproofing materials having a fibrous structure | |
EP0118023B1 (en) | Process for water-proofing leather and furs | |
DE3437443A1 (en) | METHOD FOR THE PRODUCTION OF LUBRICANT FOR LEATHER AND FUR | |
EP0247490B1 (en) | Sulphited fatty materials | |
EP0165481B1 (en) | Method for the manufacture of leather and pelts | |
EP0026423B1 (en) | Method of greasing and impregnating leather and furs | |
DE4405205A1 (en) | New leather greasing agents and their use | |
EP0824600B1 (en) | Process for treating leathers with surfactants to improve their water-proofing | |
DE1800244C2 (en) | Process for the simultaneous greasing and impregnation of leather | |
DE844784C (en) | Fatliquor for materials with a fibrous structure such as leather | |
DE3317422A1 (en) | Fat-liquoring agent for leather | |
EP0249908A2 (en) | Fat liquoring agent based on sulphosuccinic-acid monoamide | |
AT207497B (en) | Process for making leather and fur skins water repellent | |
DE2355503C3 (en) | Process for the production of a fatty chrome tanning agent and its use for tanning and retanning | |
DE2629537C3 (en) | Process to increase the softness, suppleness and tear resistance of fur skins or leather by treatment in organic solvents | |
DE857424C (en) | Process for tanning hides and skins using iron compounds | |
DE629996C (en) | Process for greasing animal skins and leather | |
DE740456C (en) | Process for degreasing skins and furs | |
DE716747C (en) | Procedure for de-liming ashed bare | |
DE10005669A1 (en) | Degreasing of pickled hides, especially sheepskins, using surfactants, especially nonionic adducts of ethylene oxide with 10-16C fatty alcohols | |
DE2551915C3 (en) | Process for greasing leather, fur skins and fibrous materials | |
CH336154A (en) | Fatliquor for fur skins | |
DE1147001B (en) | Process for the production of water-repellent leather | |
DE1494827C3 (en) | Process for the production of soft, optionally water-repellent leathers with small amounts of extractable fat |
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 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
17P | Request for examination filed |
Effective date: 19861110 |
|
17Q | First examination report despatched |
Effective date: 19870603 |
|
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 FR GB IT LI NL SE |
|
REF | Corresponds to: |
Ref document number: 36349 Country of ref document: AT Date of ref document: 19880815 Kind code of ref document: T |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) | ||
REF | Corresponds to: |
Ref document number: 3660494 Country of ref document: DE Date of ref document: 19880915 |
|
ET | Fr: translation filed | ||
ITF | It: translation for a ep patent filed | ||
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
26 | Opposition filed |
Opponent name: SCHILL & SEILACHER GMBH & CO. Effective date: 19890509 |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: SCHILL & SEILACHER GMBH & CO. |
|
PLBN | Opposition rejected |
Free format text: ORIGINAL CODE: 0009273 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: OPPOSITION REJECTED |
|
27O | Opposition rejected |
Effective date: 19900628 |
|
NLR2 | Nl: decision of opposition | ||
ITTA | It: last paid annual fee | ||
EAL | Se: european patent in force in sweden |
Ref document number: 86102381.0 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19960125 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19960201 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19960215 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19960229 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19960412 Year of fee payment: 11 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Effective date: 19970224 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19970225 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Effective date: 19970228 |
|
BERE | Be: lapsed |
Owner name: HENKEL K.G.A.A. Effective date: 19970228 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19970901 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19971030 |
|
EUG | Se: european patent has lapsed |
Ref document number: 86102381.0 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 19970901 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19980216 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19980302 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19980310 Year of fee payment: 13 |
|
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 NON-PAYMENT OF DUE FEES Effective date: 19990224 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990228 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990228 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19990224 |
|
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: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19991201 |
|
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 NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050224 |