EP0418661A1 - Utilisation de copolymérisates à base d'esters non saturés à longue chaîne et d'acides carboxyliques à liaison éthylénique pour hydrophober du cuir ou des peaux - Google Patents

Utilisation de copolymérisates à base d'esters non saturés à longue chaîne et d'acides carboxyliques à liaison éthylénique pour hydrophober du cuir ou des peaux Download PDF

Info

Publication number
EP0418661A1
EP0418661A1 EP90117145A EP90117145A EP0418661A1 EP 0418661 A1 EP0418661 A1 EP 0418661A1 EP 90117145 A EP90117145 A EP 90117145A EP 90117145 A EP90117145 A EP 90117145A EP 0418661 A1 EP0418661 A1 EP 0418661A1
Authority
EP
European Patent Office
Prior art keywords
copolymers
monoethylenically unsaturated
carboxyl groups
acid
carboxylic acids
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP90117145A
Other languages
German (de)
English (en)
Other versions
EP0418661B1 (fr
Inventor
Ortwin Dr. Schaffer
Herbert Dr. Bay
Karl Dr. Stork
Norbert Dr. Greif
Knut Dr. Oppenlaender
Walter Denzinger
Heinrich Dr. Hartmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6389618&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0418661(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by BASF SE filed Critical BASF SE
Publication of EP0418661A1 publication Critical patent/EP0418661A1/fr
Application granted granted Critical
Publication of EP0418661B1 publication Critical patent/EP0418661B1/fr
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

Links

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

Definitions

  • aqueous polyacrylate dispersions in which the copolymer is predominantly composed of acrylic or methacrylic acid esters of alcohols having 1 to 8 carbon atoms, for dressing leather is known from DE-OS 33 44 354 and EP-PS 0 065 253 known.
  • emulsifiers are always required to prepare the aqueous polymer dispersions.
  • the present invention has for its object to provide emulsifier-free agents for the hydrophobization of leather and fur.
  • the copolymers are known for example from DE-OS 38 17 000. They are prepared by copolymerizing the group a) monomers with the group b) monomers. If monoethylenically unsaturated dicarboxylic acid anhydrides are used as monomers of group b) and the copolymerization is carried out with the exclusion of water, the anhydride groups contained in the copolymer are solvolysed after the copolymerization. The solvolysis of the anhydride groups of the copolymers can simultaneously be combined with a partial or complete neutralization of the carboxyl groups by treating the copolymers with bases. If ammonia, primary or secondary amines are used as bases, the copolymers can also be partially amidated.
  • Suitable monomers of group a) for the preparation of the copolymers are C8 to C40 alkyl acrylates and C8 to C40 alkyl methacrylates.
  • Suitable compounds of this type are, for example, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-decyl acrylate, n-decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, isotridecyl acrylate, isotridecyl methacrylate, tetradecyl acrylate, tetra-cadyl acrylate, C1-methacrylate methacrylate, Palmityl acrylate, palmityl methacrylate, n-eicosyl acrylate, n-eicosyl methacrylate, n-docosyl acrylate, n-docosyl methacrylate, tetracosyl acryl
  • acrylates are also suitable. Such mixtures can be prepared, for example, by esterifying alcohols, either using the oxo process or are available using the Ziegler process.
  • the acrylic acid esters and methacrylic acid esters derived from alcohols having 16 to 28 carbon atoms are preferably used.
  • component a) are vinyl esters of carboxylic acids having 8 to 40 carbon atoms.
  • examples of such compounds are vinyl 2-ethylhexanoate, vinyl laurate, vinyl palmitate, vinyl tallow fatty acid ester, vinyl myristate, vinyl stearate, vinyl oleate and mixtures of the vinyl esters mentioned or mixtures of at least one vinyl ester with at least one of the alkyl (meth) acrylates in question.
  • the monomers of group a) are present in the copolymers in amounts of 50 to 90, preferably 65 to 85% by weight in copolymerized form.
  • the monomers of group b) include monoethylenically unsaturated C3 to C12 carboxylic acids and monoethylenically unsaturated dicarboxylic anhydrides.
  • Suitable monoethylenically unsaturated carboxylic acids are, for example, acrylic acid, methacrylic acid, crotonic acid, vinyl lactic acid, allylacetic acid, propylidene acetic acid, ethyl acrylic acid, dimethylacrylic acid, maleic acid, fumaric acid, itaconic acid, glutaconic acid, methylene malonic acid, citric acid and tetrahydrophthalic acid.
  • Examples of ethylenically unsaturated dicarboxylic acid anhydrides which contain a total of 4 to 12 carbon atoms per molecule are maleic anhydride, itaconic anhydride, citric acid anhydride, methylene malonic acid anhydride and tetrahydrophthalic anhydride.
  • monomers of group b) are monoesters of dicarboxylic acids and alcohols with 1 to 40 carbon atoms, for example monomethyl maleate, monobutyl maleate, monododecyl maleate, monooctadecyl maleate, monotetracosyl maleate, monooctadecyl fumarate, monooctadecohexyl compounds and monoethyl hexacetate compounds, monohexadecyl hexaconate compounds,.
  • acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid and itaconic anhydride are preferred.
  • the monomers of group b) also include amides of monoethylenically unsaturated monocarboxylic acids and the half-amides of monoethylenically unsaturated dicarboxylic acids, e.g. Amides and half-amides, each derived from the underlying carboxylic acids and ammonia or amines having 1 to 40 carbon atoms, for example N-isotridecylacrylamide, N-di- (isotridecyl) acrylamide, N-stearylacrylamide, N-stearylmethacrylamide, maleic acid monoisotridecylamide, maleic acid diisotridecylamide , Maleic acid monostearylamide and maleic acid distearylamide.
  • amides of monoethylenically unsaturated monocarboxylic acids and the half-amides of monoethylenically unsaturated dicarboxylic acids e.g. Amides and half-amides, each derived from the
  • the copolymers contain the monomers of group b) in amounts of 10 to 50, preferably 15 to 35,% by weight.
  • the copolymers from the monomers of group a) and b) can optionally also be modified by copolymerization in the presence of monomers from group c).
  • the monomers of group c) include, for example, styrene, methylstyrene, ethylstyrene, butylstyrene, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, methyl acrylate , ethyl acrylate, propyl acrylate, butyl acrylate, Acrylklarehexylester, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, Methacrylklahexylester, hydroxyethyl acrylate, hydroxypropyl acrylate
  • the copolymerization of the monomers of groups a) and b) and optionally c) is carried out by all known batch or continuous polymerization processes, such as bulk, suspension, precipitation and solution polymerization.
  • the copolymerization is preferably carried out in the presence of radical-forming compounds. Up to 10, preferably 0.2 to 5,% by weight, based on the monomers used in the copolymerization, are required. All of the polymerization processes mentioned are carried out in the absence of oxygen, preferably in a stream of nitrogen.
  • the usual apparatuses are used, for example autoclaves and boilers, which are equipped, for example, with armature, blade, impeller or multi-stage impulse countercurrent stirrers.
  • Bulk polymerization of the monomers of groups (a) and (b) is particularly preferred. It is carried out at temperatures from 80 to 300, preferably from 120 to 200 ° C., the lowest polymerization temperature to be chosen preferably being at least about 20 ° C. above the glass transition temperature of the polymer formed. Depending on the molecular weight that the copolymers should have, the polymerization conditions are chosen. Polymerization at high temperatures produces copolymers with low molecular weights, while polymers with higher molecular weights are formed at lower polymerization temperatures. The amount of the polymerization initiator also has an influence on the molecular weight.
  • the monomers (a) and (b) can be copolymerized at temperatures above 200 ° C even in the absence of polymerization initiators, ie the use of initiators is not absolutely necessary because the monomers (a) and (b) at temperatures above 200 ° C free-radically polymerize even in the absence of initiators.
  • Suitable polymerization initiators are, for example, acetylcyclohexanesulfonyl peroxide, diacetyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-2ethylhexylperoxidicarbonat, tertiary-butyl perneodecanoate, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), tertiary-butyl perpivalate, tertiary-butyl per-2-ethyl-hexanoate, Tertiary butyl permaleinate, 2,2 'azobis (isobutyronitrile), bis (tertiary butyl peroxy) cyclohexane, tertiary butyl peroxy isopropyl carbonate, tertiary butyl peracetate, di-tertiary butyl peroxide, ditertiary terehydro peryl
  • the initiators can be used alone or as a mixture with one another. In bulk polymerization, they are preferably introduced into the polymerization reactor separately or in the form of a solution or dispersion in the monomer of component (a).
  • Redox coinitiators can of course also be used in the copolymerization, for example benzoin, dimethylaniline, ascorbic acid and organically soluble complexes of heavy metals such as copper, cobalt, iron, manganese, nickel and chromium.
  • the use of redox coinitiators allows the polymerization to be carried out at a lower temperature.
  • the amounts of redox coinitiators usually used are about 0.1 to 2000, preferably 0.1 to 1000 ppm, based on the amounts of monomers used.
  • the monomer mixture is at the lower limit of that required for the polymerization in Be polymerized coming temperature range and then polymerized at a higher temperature, it is advisable to use at least two different initiators, which disintegrate at different temperatures, so that a sufficient concentration of radicals is available in each temperature interval.
  • regulators In order to produce low molecular weight polymers, it is often expedient to carry out the copolymerization in the presence of regulators.
  • Common controllers can be used for this, e.g. C1 to C4 aldehydes, allyl alcohol, buten-1-ol-3, formic acid and compounds containing organic SH groups, such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid, tert-butyl mercaptan, n-dodecyl mercaptan and tertiary dodecyl mercaptan .
  • the polymerization regulators are generally used in amounts of 0.1 to 10% by weight, based on the monomers.
  • a pressure vessel with a downstream reaction tube which is provided with a static mixer, can be used with particular advantage.
  • the monomers are preferably polymerized from (meth) acrylic esters, vinyl esters and acid group-containing monoethylenically unsaturated compounds in at least 2 polymerization zones connected in series.
  • One reaction zone can consist of a pressure-tight vessel, the other of a heatable static mixer. You get sales of more than 99%.
  • a copolymer of stearyl acrylate and acrylic acid can be prepared, for example, by continuously feeding the monomers and a suitable initiator to a reactor or two reaction zones connected in series, for example a stirred tank cascade, and the reaction product after a residence time of 2 to 60, preferably 5 to 30 Minutes, continuously discharged from the reaction zone at temperatures between 200 and 400 ° C.
  • the polymerization is expediently carried out at pressures of more than 1 bar, preferably between 1 and 200 bar.
  • the copolymers obtained with solids contents of more than 99% can then be further converted to the corresponding alkali and alkaline earth metal salts or amides and ammonium salts.
  • Another preferred embodiment for the preparation of the copolymers is solution polymerization. It is carried out in solvents in which the monomers and the copolymers formed are soluble. All solvents that meet this requirement and that do not react with the monomers are suitable for this. For example, these are acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, aliphatic, cycloaliphatic and aromatic hydrocarbons substances such as n-octane, isooctane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, cumene, tetrahydrofuran and dioxane, whereby xylene, ethylbenzene, cumene, tetrahydrofuran and dioxane are particularly suitable for achieving
  • solvent and part of the monomer mixture for example about 5 to 20%
  • solvents and (meth) acrylic esters or vinyl esters can also be introduced into the polymerization reactor and then, after the polymerization temperature has been reached, the monomer containing acid groups, optionally dissolved in the solvent, and the initiator, and, if appropriate, coinitiator and regulator, are metered in.
  • concentrations of the monomers to be polymerized are between 20 and 80% by weight, preferably 30 and 70% by weight.
  • the solid copolymer can easily be isolated by evaporating the solvent.
  • Another method for the simple preparation of the copolymers is precipitation polymerization.
  • solvents are used in which the monomers are soluble and the copolymer formed is insoluble and fails.
  • solvents are ethers, such as diethyl ether, dipropyl ether, dibutyl ether, methyl tert-butyl ether, diethylene glycol dimethyl ether and mixtures with one another.
  • ethers such as diethyl ether, dipropyl ether, dibutyl ether, methyl tert-butyl ether, diethylene glycol dimethyl ether and mixtures with one another.
  • Suitable protective colloids are polymeric substances which are readily soluble in the solvents and which do not react with the monomers.
  • Suitable are, for example, copolymers of maleic anhydride with vinyl alkyl ethers and / or olefins with 8 to 20 carbon atoms and corresponding copolymers of the monoesters of maleic acid with C10 to C20 alcohols or the mono- and diamides of maleic acid with C10- to C20-alkylamines and polyalkyl vinyl ethers , whose alkyl group contains 1 to 20 carbon atoms, such as polymethyl, polyethyl, polyisobutyl and polyoctadecyl vinyl ether.
  • the amounts of protective colloid added are usually 0.05 to 4% by weight (based on the monomers used), preferably 0.1 to 2% by weight, it often being advantageous to combine several protective colloids.
  • the feed times for monomer and initiator are generally between 1 and 10 hours, preferably 2 and 5 hours. It is also possible to initially charge all of the starting materials in a reactor and to polymerize them, however, heat dissipation problems may occur, making such an operation less convenient.
  • the concentrations of the monomers to be polymerized are between 20 and 80% by weight, preferably 30 to 70% by weight.
  • the polymers can be isolated from the polymer suspensions, for example by distilling off the suspension medium of the polymer suspensions in evaporators, for example belt dryers, paddle dryers, spray dryers and fluidized bed dryers.
  • the monomers of groups a) and b) and, if appropriate, c) are copolymerized in accordance with the above-described processes in such a way that copolymers with molar masses of 500 to 30,000, preferably 1,000 to 20,000 g, per mol are retained.
  • the copolymers of the long-chain vinyl esters and maleic anhydride preferably contain the monomers copolymerized in a molar ratio of 1: 1.
  • copolymers obtained in the polymerization processes described above are initially largely freed from volatile constituents for the preparation of ready-to-use aqueous preparation solutions or aqueous dispersions.
  • the copolymers are preferably heated to temperatures of up to 150 ° C. under reduced pressure. Volatile components distilled off under these conditions.
  • a low-boiling regulator can be removed from copolymers that are produced by bulk polymerization.
  • the solvent used in the polymerization is advantageously distilled off before the preparation of aqueous preparation solutions.
  • Copolymers containing maleic anhydride groups can, however, be converted into the corresponding half-amide groups in the form of the solution in an organic solvent by reacting them with ammonia or amines.
  • the reaction of copolymers containing anhydride groups with alcohols, ammonia or amines is preferably carried out in the absence of solvents.
  • copolymers obtainable by the polymerization processes described above are dissolved or dispersed in water and at least partially neutralized.
  • the copolymers can also be monoethylenically unsaturated if they are monomers of group b) in the copolymerization
  • Carboxylic acids or monoethylenically unsaturated dicarboxylic anhydrides are used, are converted into the corresponding amides or half-amides. For example, ammonia, primary and / or secondary amines are added to a melt of the copolymers from which the volatile constituents have been removed.
  • the reaction is carried out so far that 20 to 50% of the carboxyl groups of the polymerized monoethylenically unsaturated carboxylic acids or 20 to 50% of the carboxyl groups obtainable from the polymerized monoethylenically unsaturated dicarboxylic acid anhydrides are amidated and in each case at least 10% of the total carboxyl groups present in the copolymer are neutralized.
  • Ready-to-use solutions for the hydrophobization of leather and fur are obtained if the copolymers are neutralized after cooling to room temperature or preferably in the form of a melt which has a temperature in the range from 80 to 180, preferably 90 to 150 ° C., or as already described above - partially amidated by adding ammonia, primary and / or secondary amines.
  • the amounts of water and neutralizing agent are chosen so that 10 to 60, preferably 20 to 55% by weight solids-containing dispersions or polymer solutions are formed which are brought onto the market. Preparation solutions with solids contents of 0.5 to 50% by weight are then prepared from this by dilution with water.
  • Solvolysis can also be carried out with aminocarboxylic acids and salts of aminocarboxylic acids, preferably the alkali metal salts.
  • Alkali metal salts of ⁇ -aminocarboxylic acids are particularly preferably used, the alkali metal salts of sarcosine being very particularly advantageous.
  • the solvolysis using salts of aminocarboxylic acids is advantageously carried out in an aqueous medium.
  • the solvolysis is carried out with such amounts of aminocarboxylates that 20 to 50% of the carboxyl groups of the polymerized monoethylenically unsaturated carboxylic acids or 20 to 50% of the carboxyl groups obtainable from the polymerized monoethylenically unsaturated dicarboxylic acid anhydrides are hydrolysed. After the formation of half-amide groups in the copolymer, neutralization takes place. It is carried out so far that at least 10% of the carboxyl groups of the copolymer obtained in bulk polymerization are neutralized.
  • the copolymers containing acid or anhydride groups obtained during the copolymerization can also be esterified by reaction with alcohols.
  • the esterification is carried out only to an extent that 10 to 50% of the acid groups of the copolymer are esterified.
  • the partially esterified copolymers are then neutralized, in which at least 10% of the carboxyl groups be neutralized.
  • the neutralization of the copolymers containing anhydride or acid groups is carried out at least to such an extent that copolymers which are dispersible in water are obtained. This degree of neutralization is at least 10% of the carboxyl groups of the copolymer or at least 10% of the total carboxyl groups resulting from the anhydride groups of the copolymer.
  • the degree of neutralization is also dependent on the chain length of the alkyl acrylate or alkyl methacrylate or vinyl ester used.
  • a copolymer of a C30-alkyl acrylate and maleic acid is neutralized to at least 75%, for example a copolymer of a C20-alkyl acrylate and maleic anhydride at a degree of neutralization of 50% of this Copolymer resulting carboxyl groups are already well dispersible in water.
  • a degree of neutralization of 20% of the carboxyl groups resulting from the copolymerized maleic anhydride is sufficient for dispersing the copolymer in water.
  • copolymers which contain, as a group b) monomer, copolymerized with an ethylenically unsaturated carboxylic acid or preferably a monoethylenically unsaturated dicarboxylic anhydride, in In the absence of water, react with ammonia, primary and / or secondary amines to the corresponding half amides.
  • Suitable primary and secondary amines can have 1 to 40, preferably 3 to 30 carbon atoms.
  • Such substances are, for example, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, hexylamine, cyclohexylamine, methylcyclohexylamine, 2-ethylhexylamine, n-octylamine, isotridecylamine, tallow fatty amine, stearylamine, oleylamine, dimethylamine, dimethylamine Di-n-propylamine, di-isopropylamine, di-n-butylamine, diisobutylamine, dihexylamine, dicyclohexylamine, dimethylcyclohexylamine, di-2-ethylhexylamine, di-n-octylamine, diisotridecylamine, ditallow fatty amine, di-stearylamine, di-oleylamine, ethanol Diethanolamine,
  • the copolymers can be neutralized with the amines or ammonia specified above and with alkali metal and / or alkaline earth metal bases, for example sodium hydroxide solution, potassium hydroxide solution, sodium bicarbonate, sodium carbonate, potassium carbonate, magnesium hydroxide, calcium hydroxide and barium hydroxide.
  • Ready-to-use solutions or are preferably produced Dispersions by adding an aqueous base to a melt of the copolymer.
  • the pH of the ready-to-use agents for hydrophobizing is in the range from about 4 to 10.
  • the aqueous solution or dispersion can also be obtained by introducing the copolymer into an aqueous solution of the alkali metal and / or alkaline earth metal base, preferably at temperatures from 20 to 150 ° C.
  • aqueous copolymer dispersions or solutions obtainable in this way are stable and stable in storage. They are outstandingly suitable for finishing leather and fur skins because they have a particularly pronounced hydrophobic effect and also have a greasy and retanning effect.
  • the leather and fur material treated with these copolymer dispersions shows only a low level of water absorption and water permeability.
  • the dispersions have a softening effect at the same time, so that in most cases no additional fatliquor based on natural or synthetic licker oils is required.
  • the dispersions give the goods a high level and high tensile and tear strength, so that additional treatment with commercially available tanning agents, for example with vegetable tanning agents or synthetic organic tanning agents (synthetics) based on phenolsulfonic acid / phenol / formaldehyde condensation products, does not in most cases more is needed.
  • commercially available tanning agents for example with vegetable tanning agents or synthetic organic tanning agents (synthetics) based on phenolsulfonic acid / phenol / formaldehyde condensation products
  • aqueous dispersions or polymer solutions to be used according to the invention contain no additional emulsifiers.
  • Leather and fur skins, which have been treated with products containing emulsifiers, are known to have to undergo complex processes after treatment with these agents, e.g. Subsequent treatment with polyvalent metal salts are subjected in order to render the emulsifiers in the leather or in the fur skins ineffective.
  • copolymer dispersions or copolymer solutions are suitable for the treatment of all customary tanned skins, in particular with mineral tanning agents, such as tanned skins containing chromium III salts.
  • the tanned hides are usually deacidified before treatment. They may have been stained before treatment. However, coloring can also be carried out only after the hydrophobization according to the invention has taken place.
  • the tanned skins are expediently mixed with the aqueous dispersions in aqueous liquors, which can be obtained by diluting the copolymer dispersions or solutions with water, at pH values from 4 to 10. preferably 5 to 8 and temperatures of 20 to 60, preferably 30 to 50 ° C, for a period of 0.1 to 5, in particular 0.5 to 2 hours, treated.
  • This treatment is carried out, for example, by drumming in a barrel.
  • the required amount of copolymer dispersion or solution, based on the shaved weight of the leather or the wet weight of the fur skins is 0.1 to 30, preferably 1 to 20,% by weight.
  • the liquor length ie the percentage weight ratio of the treatment liquor to the goods, based on the fold weight of the leather or the wet weight of the fur skins, is usually 10 to 1000%, preferably 30 to 150% for fur skins 50 to 500%.
  • the pH of the treatment liquor is adjusted to a pH of 3 to 5, preferably 3.5 to 4, by adding acids, preferably organic acids, such as formic acid.
  • the treatment with the aqueous dispersions or solutions to be used according to the invention can take place before or after the retanning step or else in several stages, the aqueous dispersions or solutions being used in part before, during and after the retanning step .
  • the aqueous dispersions or solutions to be used as hydrophobizing agents can also be used together with conventional leather and fur finishing agents, such as hydrophobics based on paraffin. In some cases, this improves the water repellent, oiling and retanning effects.
  • the percentages in the examples are percentages by weight.
  • the molecular weights of the copolymers were determined by gel permeation chromatography before neutralization, using tetrahydrofuran as eluent and narrowly distributed fractions of polystyrene for calibration.
  • the treated leather was tested for water absorption and water permeability using the Bally penetrometer in accordance with measurement method IUP 10 of the International Union of Leather Chemists' Associations, Commission for Physical Leather Testing, cf. The leather, volume 12, 36 to 40 (1961).
  • the reaction mixture was then heated for a further 2 hours while stirring and refluxing, and the xylene was then distilled off. The remaining xylene was removed in vacuo (40 millibars) and a temperature of 125 ° C. 79.9 g of morpholine were then added over the course of half an hour and the reaction mixture was heated to a temperature of 130 ° C. with stirring for 2 hours. All of the anhydride groups in the copolymer were converted into monoamide groups. The reactor was then closed in a pressure-tight manner. At a temperature of the polymer melt of 125 ° C., 73.5 g of a 50% strength aqueous sodium hydroxide solution and 1130 g of water were then added within 1 h.
  • the reaction mixture was then stirred for a further 2 hours at a temperature of 125 ° C. and cooled to room temperature. A dispersion which was slightly viscous at room temperature and had a solids content of 25.8% was obtained. The molecular weight of the copolymer was 6400 g per mole.
  • a solution of 75 g of acrylic acid in 15 g of o-xylene and then a solution of 9 g of ditertiary butyl peroxide in 31 g of o-xylene were then uniformly added to the refluxing solution over the course of 2 hours.
  • the reaction mixture was then heated under reflux for a further 2 hours, and then the o-xylene was distilled off. Residual xylene was removed from the polymer melt at a temperature of 140 ° C and a pressure of 40 mbar.
  • the polymer melt was then cooled to a temperature of 125 ° C. and the reactor was closed in a pressure-tight manner.
  • the reaction mixture was stirred under reflux for a further 1 h.
  • the unpolymerized buten-1-ol-3 was then distilled off under a pressure of 40 mbar and a temperature of 125.degree.
  • the reactor was then sealed pressure-tight.
  • 125 g of 50% strength aqueous sodium hydroxide solution and 1173 g of water were added under pressure to the melt heated to 140 ° C. within 1 h.
  • the mixture was then stirred at 120 ° C. for 1 h.
  • An emulsion which was viscous at room temperature and had a solids content of 30.6% was obtained.
  • the molecular weight of the copolymer was 3600 g per mole. 90% of the carboxyl groups of the copolymer were in the form of the sodium salt.
  • Chrome-tanned cowhide with a fold thickness of 1.8 mm which had been deacidified to a pH of 5.0 and dyed with 0.7% by weight of a conventional anionic aniline dye, was mixed with 20 of dispersion 1, based on the fold weight, Tumbled for one and a half hours at 40 ° C in the tanning barrel. Following this treatment, the leather was brought to a pH of 3.6 with formic acid. It was then washed, mechanically stretched and dried.
  • the leather thus obtained was very soft and easy to grip and had a high dynamic water resistance.
  • the test with the Bally penetrometer showed a value of 24.7% by weight for the water absorption after 15 hours at 15% compression and showed no water penetration during this period.
  • the leather was then dyed with 1% by weight of a conventional anionic aniline dye. Then it was adjusted to a pH of 3.8 with formic acid. Including washing, mechanical stretching and drying.
  • the leather obtained was very soft, supple, well filled, evenly colored and had excellent dynamic water resistance.
  • the test with the Bally penetrometer showed a value of 22.9% by weight for the water absorption after 15 hours at 15% compression and showed no water penetration during this period.
  • the leather obtained was extremely soft and pleasant to the touch and showed a high water resistance.
  • the test with the Bally penetrometer showed a value of 19.5% by weight for the water absorption after 15 hours at 15% compression and showed no water penetration during this period.

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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
EP90117145A 1989-09-16 1990-09-06 Utilisation de copolymérisates à base d'esters non saturés à longue chaîne et d'acides carboxyliques à liaison éthylénique pour hydrophober du cuir ou des peaux Revoked EP0418661B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3931039 1989-09-16
DE3931039A DE3931039A1 (de) 1989-09-16 1989-09-16 Verwendung von copolymerisaten auf basis von langkettigen ungesaettigten estern und ethylenisch ungesaettigten carbonsaeuren zum hydrophobieren von leder und pelzfellen

Publications (2)

Publication Number Publication Date
EP0418661A1 true EP0418661A1 (fr) 1991-03-27
EP0418661B1 EP0418661B1 (fr) 1994-12-28

Family

ID=6389618

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90117145A Revoked EP0418661B1 (fr) 1989-09-16 1990-09-06 Utilisation de copolymérisates à base d'esters non saturés à longue chaîne et d'acides carboxyliques à liaison éthylénique pour hydrophober du cuir ou des peaux

Country Status (11)

Country Link
US (1) US5124181A (fr)
EP (1) EP0418661B1 (fr)
JP (1) JPH03207800A (fr)
KR (1) KR910006561A (fr)
AT (1) ATE116377T1 (fr)
AU (1) AU628646B2 (fr)
CA (1) CA2024759A1 (fr)
DE (2) DE3931039A1 (fr)
ES (1) ES2066068T3 (fr)
NZ (1) NZ235305A (fr)
PT (1) PT95319B (fr)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0498634A2 (fr) * 1991-02-05 1992-08-12 Rohm And Haas Company L'emploi d'une matière de retannage polymère pour la nourriture de cuir garniture à faible condensation
WO1993017130A1 (fr) * 1992-02-26 1993-09-02 Basf Aktiengesellschaft Utilisation de produits de reaction d'homo- ou de copolymerisats a base d'anhydrides d'acide dicarboxylique monoethyleniquement insatures avec des amines ou des alcools pour nourrir et fouler des cuirs et des peaux en poils
DE4214011C1 (de) * 1992-04-29 1993-11-04 Muenzing Chemie Gmbh Copolymerisate
EP0574351A1 (fr) * 1992-06-09 1993-12-15 Ciba-Geigy Ag Procédé pour l'après-traitement de cuir tanné et de fourrures
WO1994001587A1 (fr) * 1992-07-14 1994-01-20 Henkel Kommanditgesellschaft Auf Aktien Nouveaux agents de graissage du cuir et leur utilisation
EP0583973A2 (fr) * 1992-08-18 1994-02-23 Ciba Specialty Chemicals Water Treatments Limited Composition d'imprégnation pour cuir
WO1995019451A1 (fr) * 1994-01-12 1995-07-20 Henkel Kommanditgesellschaft Auf Aktien Agents pour l'appretage graisseux du cuir
WO1995020056A1 (fr) * 1994-01-25 1995-07-27 Basf Aktiengesellschaft Solutions ou dispersions aqueuses de copolymeres
US5489389A (en) * 1992-07-14 1996-02-06 Henkel Kommanditgesellschaft Auf Aktien New leather oiling preparations 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
WO1996035815A2 (fr) * 1995-05-12 1996-11-14 Stockhausen Gmbh & Co. Kg Procede d'impermeabilisation de cuirs sous de faibles valeurs de ph et cuirs ainsi impermeabilises
WO1998010103A1 (fr) * 1996-09-09 1998-03-12 Stockhausen Gmbh & Co. Kg Nouveaux produits pour le traitement du cuir, leur procede de fabrication et leur utilisation dans la fabrication de cuirs a faible exsudation
US5728313A (en) * 1994-02-18 1998-03-17 Henkel Corporation Leather oiling compositions and their use
WO1998039488A1 (fr) * 1997-03-03 1998-09-11 Henkel Kommanditgesellschaft Auf Aktien Utilisation de polymeres pour le nourrissage a l'huile du cuir
WO1999014380A1 (fr) * 1997-09-18 1999-03-25 Minnesota Mining And Manufacturing Company Polydienes modifies a l'aide de perfluoroalkyle amphiphile et leur utilisation dans le traitement du cuir
US6294103B1 (en) 1996-11-07 2001-09-25 3M Innovative Properties Company Use of amphiphilic copolymers containing a fluorinated monomer to impart waterproofness to leather
WO2012156165A1 (fr) * 2011-05-19 2012-11-22 Evonik Rohmax Additives Gmbh Poly(méth)acrylates en tant qu'additif multifonctionnel dans des matières plastiques

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TNSN89128A1 (fr) * 1988-12-02 1991-02-04 Rohn And Haas Company Independance Mall West Traitement du cuir avec des copolymeres amphiphites choisis
DE3926168A1 (de) * 1989-08-08 1991-02-14 Basf Ag Verwendung von copolymerisaten auf basis von langkettigen alkylvinylethern und ethylenisch ungesaettigten dicarbonsaeureanhydriden zum hydrophobieren von leder und pelzfellen
US5451432A (en) * 1990-08-31 1995-09-19 Rohm And Haas Company Treating flexible, porous substrates with formaldehyde free binder
DE4139090A1 (de) * 1991-11-28 1993-06-03 Stockhausen Chem Fab Gmbh Verwendung von copolymerisaten mit polysiloxan-einheiten zur behandlung von leder und pelzen
DE4209243A1 (de) * 1992-03-21 1993-09-23 Basf Ag Verfahren zum fetten, fuellen und hydrophobieren von ledern und pelzen
DE4236556A1 (de) * 1992-10-29 1994-05-05 Stockhausen Chem Fab Gmbh Verfahren zur Weichmachung/Fettung von Ledern und Pelzen
DE4242039A1 (de) * 1992-12-12 1994-06-16 Stockhausen Chem Fab Gmbh Copolymerisate und ihre Verwendung zur Behandlung von Leder
US5417723A (en) * 1993-03-25 1995-05-23 Bayer Aktiengesellschaft Use of ester urethanes for retanning
DE4334796A1 (de) * 1993-10-13 1995-04-20 Bayer Ag Weichmachende und hydrophobierende Nachgerbstoffe
DE4439990A1 (de) * 1994-11-09 1996-05-15 Bayer Ag Ledergerbstoffe und Stellmittel für Farstoffe
JP3087105B2 (ja) * 1995-04-20 2000-09-11 敏 瀧川 シリコンオイルとポリメタアクリル酸アルキルエステルよりなる塗剤
EP0841405B1 (fr) 1996-11-07 1999-12-29 Minnesota Mining And Manufacturing Company Utilisation de copolymères amphiphiles contenant des monomères fluorés pour imperméabiliser des cuirs
US6242042B1 (en) 1998-09-14 2001-06-05 Lrc Products Ltd. Aqueous coating composition and method
US6525127B1 (en) 1999-05-11 2003-02-25 3M Innovative Properties Company Alkylated fluorochemical oligomers and use thereof in the treatment of fibrous substrates
US7049379B2 (en) * 1999-05-11 2006-05-23 3M Innovative Properties Company Alkylated fluorochemical oligomers and use thereof in the treatment of fibrous substrates
US7637961B2 (en) * 2002-03-05 2009-12-29 Rohm And Haas Company Composition and method for preparing leather
CN100422251C (zh) * 2003-09-30 2008-10-01 日本瑞翁株式会社 交联性橡胶组合物及交联物
DE102005029627A1 (de) * 2005-06-23 2007-01-04 Basf Ag Verfahren zur Herstellung von Leder
CN101583639B (zh) * 2006-10-11 2013-02-20 智利大学 用于制备纳米复合材料、微米复合材料和聚合物共混物的增容剂及其获得方法
EP2045276A1 (fr) * 2007-10-05 2009-04-08 E.I. Du Pont De Nemours And Company Fluoropolymère
ES2569913T3 (es) 2008-07-07 2016-05-13 Basf Se Composición de enzima que comprende partículas poliméricas que contienen enzima
CA2779173A1 (fr) 2009-10-30 2011-05-05 Fln Feuerloeschgeraete Neuruppin Vertriebs Gmbh Composition destinee a la production d'agents extincteurs en mousse

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4190687A (en) * 1972-05-09 1980-02-26 Sumitomo Chemical Company, Limited Method for treating leather
DE3344354A1 (de) * 1983-12-08 1985-06-13 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von waessrigen polyacrylat-copolymer-dispersionen und ihre verwendung bei der zurichtung von leder
EP0065253B1 (fr) * 1981-05-20 1985-11-21 BASF Aktiengesellschaft Procédé de préparation de dispersions polyacryliques concentrées
DE3817000A1 (de) * 1988-05-19 1989-11-23 Basf Ag Kraftstoffe fuer ottomotoren

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4009228A (en) * 1975-05-12 1977-02-22 The Goodyear Tire & Rubber Company Primary amine-modified anhydride resin
DE2946435C2 (de) * 1979-11-17 1982-02-18 Bayer Ag, 5090 Leverkusen Verfahren zum Zurichten von Leder durch Behandlung mit Kautschuklatices

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4190687A (en) * 1972-05-09 1980-02-26 Sumitomo Chemical Company, Limited Method for treating leather
EP0065253B1 (fr) * 1981-05-20 1985-11-21 BASF Aktiengesellschaft Procédé de préparation de dispersions polyacryliques concentrées
DE3344354A1 (de) * 1983-12-08 1985-06-13 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von waessrigen polyacrylat-copolymer-dispersionen und ihre verwendung bei der zurichtung von leder
DE3817000A1 (de) * 1988-05-19 1989-11-23 Basf Ag Kraftstoffe fuer ottomotoren

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0581327A1 (fr) * 1991-02-05 1994-02-02 Rohm And Haas Company Matière de retannage polymère pour la nourriture de air d'ameublement à faible condensation
EP0498634A3 (en) * 1991-02-05 1992-09-23 Rohm & Haas Polymeric retan fat liquor for low fogging upholstery leather
EP0498634A2 (fr) * 1991-02-05 1992-08-12 Rohm And Haas Company L'emploi d'une matière de retannage polymère pour la nourriture de cuir garniture à faible condensation
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
WO1993017130A1 (fr) * 1992-02-26 1993-09-02 Basf Aktiengesellschaft Utilisation de produits de reaction d'homo- ou de copolymerisats a base d'anhydrides d'acide dicarboxylique monoethyleniquement insatures avec des amines ou des alcools pour nourrir et fouler des cuirs et des peaux en poils
DE4214011C1 (de) * 1992-04-29 1993-11-04 Muenzing Chemie Gmbh Copolymerisate
EP0574351A1 (fr) * 1992-06-09 1993-12-15 Ciba-Geigy Ag Procédé pour l'après-traitement de cuir tanné et de fourrures
US5558675A (en) * 1992-06-09 1996-09-24 Ciba-Geigy Corporation Process for aftertreating tanned leather and pelts
US5567343A (en) * 1992-07-14 1996-10-22 Henkel Kommanditgesellschaft Auf Aktien New leather oiling preparations and their use
WO1994001587A1 (fr) * 1992-07-14 1994-01-20 Henkel Kommanditgesellschaft Auf Aktien Nouveaux agents de graissage du cuir et leur utilisation
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
EP0583973A2 (fr) * 1992-08-18 1994-02-23 Ciba Specialty Chemicals Water Treatments Limited Composition d'imprégnation pour cuir
EP0583973A3 (fr) * 1992-08-18 1994-04-27 Allied Colloids Ltd
WO1995019451A1 (fr) * 1994-01-12 1995-07-20 Henkel Kommanditgesellschaft Auf Aktien Agents pour l'appretage graisseux du cuir
US5683611A (en) * 1994-01-12 1997-11-04 Henkel Kommanditgesellschaft Auf Aktien Preparations for the oiling of leather
WO1995020056A1 (fr) * 1994-01-25 1995-07-27 Basf Aktiengesellschaft Solutions ou dispersions aqueuses de copolymeres
US5728313A (en) * 1994-02-18 1998-03-17 Henkel Corporation Leather oiling compositions and their use
WO1996035815A2 (fr) * 1995-05-12 1996-11-14 Stockhausen Gmbh & Co. Kg Procede d'impermeabilisation de cuirs sous de faibles valeurs de ph et cuirs ainsi impermeabilises
WO1996035815A3 (fr) * 1995-05-12 1996-12-12 Stockhausen Chem Fab Gmbh Procede d'impermeabilisation de cuirs sous de faibles valeurs de ph et cuirs ainsi impermeabilises
WO1998010103A1 (fr) * 1996-09-09 1998-03-12 Stockhausen Gmbh & Co. Kg Nouveaux produits pour le traitement du cuir, leur procede de fabrication et leur utilisation dans la fabrication de cuirs a faible exsudation
US6294103B1 (en) 1996-11-07 2001-09-25 3M Innovative Properties Company Use of amphiphilic copolymers containing a fluorinated monomer to impart waterproofness to leather
WO1998039488A1 (fr) * 1997-03-03 1998-09-11 Henkel Kommanditgesellschaft Auf Aktien Utilisation de polymeres pour le nourrissage a l'huile du cuir
WO1999014380A1 (fr) * 1997-09-18 1999-03-25 Minnesota Mining And Manufacturing Company Polydienes modifies a l'aide de perfluoroalkyle amphiphile et leur utilisation dans le traitement du cuir
WO2012156165A1 (fr) * 2011-05-19 2012-11-22 Evonik Rohmax Additives Gmbh Poly(méth)acrylates en tant qu'additif multifonctionnel dans des matières plastiques

Also Published As

Publication number Publication date
PT95319A (pt) 1991-05-22
NZ235305A (en) 1992-02-25
AU628646B2 (en) 1992-09-17
US5124181A (en) 1992-06-23
ES2066068T3 (es) 1995-03-01
JPH03207800A (ja) 1991-09-11
KR910006561A (ko) 1991-04-29
DE3931039A1 (de) 1991-03-28
ATE116377T1 (de) 1995-01-15
CA2024759A1 (fr) 1991-03-17
DE59008123D1 (de) 1995-02-09
AU6252790A (en) 1991-03-21
PT95319B (pt) 1997-06-30
EP0418661B1 (fr) 1994-12-28

Similar Documents

Publication Publication Date Title
EP0418661B1 (fr) Utilisation de copolymérisates à base d'esters non saturés à longue chaîne et d'acides carboxyliques à liaison éthylénique pour hydrophober du cuir ou des peaux
EP0412389B1 (fr) Utilisation de copolymères à base d'oléfines à longue chaîne et d'anhydrides d'acides carboxyliques à insaturation éthylénique pour l'imperméabilisation du cuir et des fourrures
EP0486608B1 (fr) Utilisation de copolymerisats a base d'ethers vinyliques d'alkyle a chaines longues et d'anhydrides d'acide dicarboxylique ethyleniquement insatures pour impermeabiliser des cuirs et des peaux
EP0682044B1 (fr) Copolymères à base d'anhydrides dicarboxyliques, d'oléfines à longue chaine et de fluoro-oléfines, leur préparation et leur utilisation
DE68929279T2 (de) Lederbehandlung mit ausgewählten amphiphilen Copolymeren
US5279613A (en) Copolymers based on long-chain olefins and ethylenically unsaturated dicarboxylic anhydrides for rendering leathers and skins water-repellent
EP0628085B1 (fr) Utilisation de produits de reaction d'homo- ou de copolymerisats a base d'anhydrides d'acide dicarboxylique monoethyleniquement insatures avec des amines ou des alcools pour nourrir et fouler des cuirs et des peaux en poils
EP0891430A1 (fr) Utilisation de copolymerisats a base d'acides dicarboxyliques ou d'anhydrides d'acides dicarboxyliques ethyleniquement insatures, d'olefines inferieures et de comonomeres hydrophobes pour le retannage, la mise en suif et l'impermeabilisation du cuir et des fourrures
EP0084134A2 (fr) Procédé de retannage
EP1084279B1 (fr) Substances tannantes contenant des unites n-vinyliques
EP0815149B1 (fr) Solutions ou dispersions aqueuses de copolymeres d'acides dicarboxyliques monoethyleniquement insatures ou de leurs anhydrides et d'oligomeres ou polymeres a chaine ramifiee
EP0574351B1 (fr) Procédé pour l'après-traitement de cuir tanné et de fourrures
AU662071B2 (en) Use of graft polymers for stuffing and fulling leathers and fur pelts
DE4214011C1 (de) Copolymerisate
EP1651781A1 (fr) Procede de production de cuir au moyen de produits de polymerisation
EP1670859B1 (fr) Dispersions aqueuses de copolymerisats, fabrication et utilisation

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: 19901129

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT CH DE ES FR GB IT LI NL SE

17Q First examination report despatched

Effective date: 19940222

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT CH DE ES FR GB IT LI NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19941228

REF Corresponds to:

Ref document number: 116377

Country of ref document: AT

Date of ref document: 19950115

Kind code of ref document: T

RIN1 Information on inventor provided before grant (corrected)

Inventor name: HARTMANN, HEINRICH, DR.

Inventor name: DENZINGER, WALTER

Inventor name: OPPENLAENDER, KNUT, DR.

Inventor name: GREIF, NORBERT, DR.

Inventor name: STORK, KARL, DR.

Inventor name: BAY, HERBERT, DR.

Inventor name: SCHAFFER, ORTWIN, DR.

REF Corresponds to:

Ref document number: 59008123

Country of ref document: DE

Date of ref document: 19950209

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19950112

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2066068

Country of ref document: ES

Kind code of ref document: T3

ITF It: translation for a ep patent filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19950328

ET Fr: translation filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19950906

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

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: 19950930

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19950930

26 Opposition filed

Opponent name: CHEMISCHE FABRIK STOCKHAUSEN GMBH PATENTABTEILUNG

Effective date: 19950926

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19960820

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19960902

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19960919

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19960923

Year of fee payment: 7

RDAH Patent revoked

Free format text: ORIGINAL CODE: EPIDOS REVO

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 19970421

GBPR Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state

Free format text: 970421