EP0418661B1 - 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

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EP0418661B1
EP0418661B1 EP90117145A EP90117145A EP0418661B1 EP 0418661 B1 EP0418661 B1 EP 0418661B1 EP 90117145 A EP90117145 A EP 90117145A EP 90117145 A EP90117145 A EP 90117145A EP 0418661 B1 EP0418661 B1 EP 0418661B1
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copolymers
monoethylenically unsaturated
carboxylic acids
acid
copolymer
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EP0418661A1 (fr
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Ortwin Dr. Schaffer
Herbert Dr. Bay
Karl Dr. Stork
Norbert Dr. Greif
Knut Dr. Oppenlaender
Walter Denzinger
Heinrich Dr. Hartmann
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BASF SE
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BASF SE
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    • 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, cetyl C-acrylate, C1-methacrylate, C1-methacrylate Palmityl acrylate, palmityl methacrylate, n-eicosyl acrylate, n-eicosyl methacrylate, n-docosyl acrylate, n-docosyl methacrylate, tetracosyl acrylate,
  • 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 esters, 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 group b) monomers 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 underlying
  • 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) takes place 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 equipment is used, for example autoclaves and boilers, which are equipped, for example, with anchor, 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-2-ethylhexylperoxidicarbonat, tertiary-butyl perneodecanoate, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), tertiary-butyl perpivalate, tertiary-butyl-2-ethyl- hexanoate, tertiary-butyl permaleinate, 2,2'-azobis (isobutyronitrile), bis- (tertiary-butylperoxy) cyclohexane, tertiary-butylperoxyisopropyl carbonate, tertiary-butylperacetate, di-tertiary-butylperoxide, diterti
  • 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.
  • 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 monoethylenically unsaturated compounds containing acid groups 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 cascade of stirred tanks, 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 over 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 such as n-octane, isooctane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, cumene, tetrahydrofuran and dioxane, xylene, ethylbenzene, cumene, tetrahydrofuran and dioxane being particularly suitable for achieving low mole
  • solvent and part of the monomer mixture for example about 5 to 20%
  • solvents and (meth) acrylic esters or vinyl esters can also be placed in the polymerization reactor and then, after the polymerization temperature has been reached, the monomer containing acid groups, if appropriate dissolved in the solvent, and the initiator, and, if appropriate, coinitiator and regulator, can be 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 the monomer and initiator are generally between 1 and 10 hours, preferably 2 and 5 hours. It is also possible to initially charge all 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.
  • Copolymers of stearyl acrylate and maleic anhydride or maleic acid preferably contain the monomers copolymerized in a molar ratio of 1: 1.
  • copolymers obtained in the polymerization processes described above are initially largely freed of volatile components 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, provided that they are monoethylenically unsaturated in the copolymerization as monomers of group b)
  • 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 to such an extent 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 copolymerized monoethylenically unsaturated dicarboxylic acid anhydrides are amidated and 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 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 amidated by hydrolysis. 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 also depends 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 copolymerized as an monomer of group b) an ethylenically unsaturated carboxylic acid or preferably a monoethylenically unsaturated dicarboxylic anhydride
  • 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, diethylamine 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 Diethanol
  • 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.
  • the aqueous copolymer dispersions or solutions obtainable in this way are stable and stable in storage. They are ideally suited 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, in most cases does not 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, in most cases does not more is needed.
  • aqueous dispersions or polymer solutions to be used according to the invention contain no additional emulsifiers. It is known that leather and fur skins that have been treated with products containing emulsifiers 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 hides, in particular with mineral tanning agents, such as tanned hides containing chromium III salts.
  • the tanned hides are usually deacidified before treatment. They may have been stained before treatment. However, coloring can also only be carried out 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 takes place, for example, by drumming in a barrel.
  • the amount of copolymer dispersion or solution required, 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%, and 50 to 500% for fur skins.
  • 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 be carried out 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 with 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 copolymer's anhydride groups 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. in the course of 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 I, based on the fold weight , tumbled for one and a half hours at 40 ° C in the tanning drum. 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 a water absorption after 24 h 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 15% compression for the water absorption after 24 h and showed no water penetration during this period.

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  • 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)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

Claims (5)

  1. Utilisation de copolymères qui contiennent, en liaison polymère.
    a) de 50 à 90% en poids d'acrylates d'alkyle en C₈-C₄₀, de méthacrylates d'alkyle en C₈-C₄₀, d'esters vinyliques d'acides carboxyliques en C₈-C₄₀ ou de mélanges de ceux-si et
    b) de 10 à 50% en poids d'acides carboxyliques en C₃-C₁₂ à insaturation monoéthylénique, d'anhydrides dicarboxyliques à insaturation monoéthylénique, de semi-esters ou de semi-amides d'acides dicarboxyliques en C₄-C₁₂ à insaturation monoéthylénique, d'amides d'acides monocarboxyliques en C₃-C₁₂ à insaturation monoéthylénique ou de mélanges de ceux-ci,
    et qui ont des masses moléculaires de 500 à 30 000 g par mole, sous forme au moins partiellement neutralisée, en solution aqueuse ou en dispersion aqueuse, comme agent dépourvu d'émulsifiant pour l'imperméabilisation de cuirs et de peaux en poils.
  2. Utilisation selon la revendication 1, caractérisée en ce que les copolymères peuvent être obtenus par polymérisation en masse des monomères a) et b) à des températures de 80 à 300°C et en ce que la masse fondue des copolymères ainsi formée est neutralisée au moins partiellement et éventuellement amidée partiellement par addition de bases.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce qu'on ajoute, à une masse fondue des copolymères de a) et b), de l'eau et de l'ammoniac, des amines, des bases de métaux alcalins ou de métaux alcalino-terreux, dans des quantités telles qu'au moins 10% des groupements carboxyle des copolymères soient neutralisés.
  4. Utilisation selon la revendication 1 ou 2, caractérisée en ce qu'on ajoute, à une masse fondue ou à une solution pratiquement anhydre des copolymères de a) et b) dans un solvant organique inerte, des amines primaires et/ou secondaires, de telle sorte que 20 à 50% des groupements carboxyle des acides carboxyliques à insaturation monoéthylénique contenus en liaison polymère, ou que 20 à 50% des groupements carboxyle, obtenus par hydrolyse à partir des anhydrides dicarboxyliques à insaturation monoéthylénique contenus en liaison polymère, soient amidés et qu'au moins 10% des groupements carboxyle présents au total dans le copolymère soient neutralisés.
  5. Utilisation selon la revendication 1 ou 2, caractérisée en ce qu'on solvolyse en milieu aqueux les copolymères par addition de sels d'acides aminocarboxyliques, de telle sorte que 20 à 50% des groupements carboxyle des acides carboxyliques à insaturation monoéthylénique contenus en liaison polymère, ou que 20 à 50% des groupements carboxyle, obtenus par hydrolyse à partir des anhydrides dicarboxyliques à insaturation monoéthylénique contenus en liaison polymère, soient amidés et qu'au moins 10% des groupements carboxyle présents au total dans le copolymère soient neutralisés par neutralisation subséquente.
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
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
DE3931039 1989-09-16

Publications (2)

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

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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)

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DE4223111A1 (de) * 1992-07-14 1994-01-20 Henkel Kgaa Neue Lederfettungsmittel und ihre Verwendung
DE4223110A1 (de) * 1992-07-14 1994-01-20 Henkel Kgaa Neue Lederfettungsmittel und ihre Verwendung (II)
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DE4402029A1 (de) * 1994-01-25 1995-07-27 Basf Ag Wäßrige Lösungen oder Dispersionen von Copolymerisaten
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DE19636494C2 (de) * 1996-09-09 2000-11-16 Stockhausen Chem Fab Gmbh Restmonomerarme, aminfreie Polymerisate, Verfahren zu ihrer Herstellung und ihre Verwendung bei der Herstellung foggingarmer Leder
DE69605925T2 (de) 1996-11-07 2000-07-20 Minnesota Mining & Mfg Verwendung amphiphiler Copolymere, enthaltend fluorhaltige Monomer zur wasserfesten Ausrüstung von Leder
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
DE19708501A1 (de) * 1997-03-03 1998-09-10 Henkel Kgaa Verwendung von Polymeren zur fettenden Ausrüstung von Leder
AU4569897A (en) * 1997-09-18 1999-04-05 Minnesota Mining And Manufacturing Company Amphiphilic perfluoroalkyl modified polydienes and their use in the treatment ofleather
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JPWO2005030859A1 (ja) * 2003-09-30 2006-12-07 日本ゼオン株式会社 架橋性ゴム組成物及び架橋物
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Also Published As

Publication number Publication date
KR910006561A (ko) 1991-04-29
CA2024759A1 (fr) 1991-03-17
ATE116377T1 (de) 1995-01-15
JPH03207800A (ja) 1991-09-11
US5124181A (en) 1992-06-23
NZ235305A (en) 1992-02-25
PT95319A (pt) 1991-05-22
DE3931039A1 (de) 1991-03-28
AU628646B2 (en) 1992-09-17
ES2066068T3 (es) 1995-03-01
PT95319B (pt) 1997-06-30
EP0418661A1 (fr) 1991-03-27
AU6252790A (en) 1991-03-21
DE59008123D1 (de) 1995-02-09

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