EP0574351B1 - Process for the after-treatment of tanned leather and furs - Google Patents

Process for the after-treatment of tanned leather and furs Download PDF

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Publication number
EP0574351B1
EP0574351B1 EP93810396A EP93810396A EP0574351B1 EP 0574351 B1 EP0574351 B1 EP 0574351B1 EP 93810396 A EP93810396 A EP 93810396A EP 93810396 A EP93810396 A EP 93810396A EP 0574351 B1 EP0574351 B1 EP 0574351B1
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Prior art keywords
fatty
anhydride
polymer
alcohol
process according
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EP93810396A
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German (de)
French (fr)
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EP0574351A1 (en
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Alain Dr. Lauton
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Novartis AG
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Ciba Geigy AG
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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

  • the present invention relates to a process for the aftertreatment of tanned leather and furs, the agent used for this process, a process for producing this agent and the leather or fur material aftertreated by the present process.
  • EP-A-0 428 481 discloses an agent for treating leather and furs, characterized in that it (A) is an anionic syntan and (B) is a polymer and / or copolymer of an unsaturated C 3 -C 5 mono- or dicarboxylic acid and / or contains their hydroxy compounds.
  • the polymers according to the invention are new.
  • the invention also relates to the new polymers, in particular within the scope of the preferred embodiment mentioned above.
  • monethylenically unsaturated polymerizable dicarboxylic acid anhydride there are e.g. Maleic anhydride, citraconic anhydride, methylene malonic anhydride and mixtures of these compounds. Of the anhydrides mentioned, maleic anhydride is preferably used.
  • Suitable C 1 -C 30 alcohols as component (b 1 ) are, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentanol, cyclohexanol, n-hexanol, onanthal alcohol, n-octanol, 2-ethylhexanol, pelargon alcohol, decanol, dodecanol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, ceryl alcohol, cerotyl alcohol, myricyl alcohol, C 9 -C 11 oxo alcohol, tridecyl alcohol, isotrido alfanols or mixtures of linear (8 bisalene alcohols) with mixtures ( 18 carbon atoms.
  • Some representatives of these alfoles are Alfol (8-10), Alfo
  • a cetyl / oleyl alcohol mixture is preferably used as component (b 1 ).
  • Preferred compounds for the optional partial amidation with amines are ammonia, mono- or di-C 1 -C 5 -alkylamine, phenyl-C 1 -C 5 -alkylamine, mono- or di-C 5 -C 7 -cycloalkylamine or morpholine.
  • Examples of the C 1 -C 5 -alkylamines used are monomethyl, dimethyl, monoethyl, diethyl, mono-n-propyl, di-n-propyl, monoisopropyl, diisopropyl, mono-n-butyl , Di-n-butyl, mono-sec-butyl, di-sec-butyl, mono-tert. Butyl, di-tert.
  • Ammonia and morpholine are very particularly preferred.
  • Suitable unsaturated or saturated C 8 -C 22 fatty acids which can be considered as component ( ⁇ ) are, for example, caprylic, capric, lauric, myristic, palmitic, stearic, arachine, behenic, oleic , Linoleic, Linolenic, Arachidonic or coconut fatty acid or the Decenic, Dodecenic, Teradecenic, Hexadecenic or Ricinolic acid.
  • An example of the adduct of a fatty acid with an alkylene oxide is the adduct of 2 to 15 moles of ethylene oxide and 1 mole of a C 8 -C 22 fatty acid.
  • Reaction products of fatty amines and ethylene oxide or propylene oxide such as, for example, fatty acid alkanolamides having 8 to 22 carbon atoms in the fatty acid residue and 2 to 18 carbon atoms in the alkanol residue, are also preferred.
  • fatty acid-alkanolamine reaction products which are prepared from C 8 -C 22 fatty acids, preferably C 8 -C 18 fatty acids and C 2 -C 6 alkanolamines such as ethanolamine, diethanolamine, isopropanolamine or diisopropanolamine, where Diethanolamine is preferred.
  • C 8 -C 18 fatty acid diethanolamides are particularly preferred.
  • Preferred examples of such reaction products are coconut fatty acid diethanolamide and lauric acid or stearic acid diethanolamide.
  • Preferred compounds which can be considered as component ( ⁇ ) are C 8 -C 22 fatty acids.
  • Aqueous bases for partial neutralization and hydrolysis are in particular aqueous solutions of NaOH or KOH (sodium hydroxide solution, potassium hydroxide solution), but also aqueous solutions of amines, such as e.g. Ammonia.
  • polymers are used in which e.g. 5 to 40, preferably 25 to 35%, based on the amounts of monomers, are esterified and / or amidated.
  • the process according to the invention is suitable for the aftertreatment of all customary tanned leather hides, in particular hides tanned with mineral tanning agents, such as chromium III salts. These are usually deacidified before the aftertreatment. They can be colored before the aftertreatment. However, coloring can also take place only after the aftertreatment carried out according to the invention.
  • mineral tanning agents such as chromium III salts.
  • the tanned and optionally colored skins are expediently mixed with the aqueous polymer solution in an aqueous liquor, which can be obtained by diluting the polymer solution with water, at pH values of 4 to 10, preferably 5 to 8 and temperatures of 20 ° to 50 °, preferably 30 to 50 ° C for a period of 0.1 to 5, preferably 0.2 to 2 hours, aftertreated.
  • This aftertreatment is carried out, for example, by milling in a barrel.
  • the required amount of polymer 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 fleet length i.e. the percentage weight ratio of the aftertreatment liquor to the goods, based on the shaved 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 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, and the leather is finished in the customary manner .
  • the leather or furs aftertreated by the process according to the invention are distinguished by a good fullness and an extraordinarily smooth feel.
  • the polymerization of the ethylenically unsaturated anhydrides is carried out according to discontinuous or continuous processes known per se, such as bulk, suspension, precipitation and solvent polymerization.
  • the monomeric ethylenically unsaturated dicarboxylic anhydrides serving as starting compounds are preferably used as uniform compounds in technical purity. Mixtures of different dicarboxylic acid anhydrides can also be used, so that copolymers are formed. The homopolymers are preferred
  • the polymerization of the anhydrides is e.g. carried out at temperatures of 80 to 300, preferably 120 to 200 ° C, the lowest polymerization temperature to be selected is preferably about at least 20 ° C above the glass transition temperature of the polymer formed.
  • the polymerization conditions are selected. Polymerization at a higher temperature results in polymers with a low molecular weight, while polymers with a higher molecular weight are formed at low polymerization temperatures.
  • the conditions for the composition according to the invention are chosen such that polymers with molar masses of 500 to 30,000 g per mol, preferably 500 to 2000 g per mol, are formed.
  • a simple method for producing the polymers is precipitation polymerization.
  • This process uses solvents in which the monomers are soluble and the polymer formed is insoluble and precipitates.
  • solvents are e.g. aromatic compounds, preferably toluene, xylene, benzene or cumene and their mixtures with one another.
  • the preferred method is solvent polymerization. It is carried out in solvents in which both the monomers and the polymers formed are soluble. All solvents that meet these conditions and are inert to the acid anhydrides are suitable for this, such as Acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate and aliphatic hydrocarbons such as n-octane, isooctane, cyclohexane or methylcyclohexane.
  • polymerization is carried out with the aid of compounds which break down into free radicals, such as, for example, peroxides, hydroperoxides, redox initiators and azo compounds.
  • Suitable polymerization initiators are, for example, acetylcyclohexanesulfonyl peroxide, diacetyl peroxidicarbonate, di-2-ethylhexyl peroxidicarbonate, tertiary butyl perneodecanoate, 2,2'-azobis (4-methoxy-2,4-dimethylvalerionitrile), tertiary-butylpermyrobitrate (2,2'-bis-azalobitrate) (tertiary butyl peroxy) cyclohexane, tertiary butyl peroxy isopropyl carbonate, tertiary butyl peracetate, di-tertiary butyl peroxide, ditertiary amyl peroxide, cumene
  • the reaction is carried out in an inert atmosphere, preferably in the absence of oxygen, in particular in an inert gas stream, e.g. Nitrogen or argon.
  • an inert gas stream e.g. Nitrogen or argon.
  • the usual equipment is used for all polymerization reactions, e.g. Autoclaves and kettles equipped with, for example, anchor, blade, impeller or multi-stage impulse countercurrent stirrers.
  • the polymers thus obtainable are then partially esterified and hydrolyzed in a next reaction step, so that the anhydride groups are converted into carboxyl groups. It is also possible to hydrolyze the polymers containing anhydride groups first, so that all anhydride groups are in the form of carboxyl groups, and then to carry out the esterification by known methods. However, the procedure is preferred in which the carboxylic anhydride groups of the polymer are first partially esterified.
  • the partial esterification can in the presence of solvents which are inert to the anhydride groups and dissolve or swell both the starting materials and the esterified copolymers, e.g. Toluene, xylene, ethylene benzene, aliphatic hydrocarbons and ketones such as acetone and methyl ketone can be carried out.
  • solvents which are inert to the anhydride groups and dissolve or swell both the starting materials and the esterified copolymers, e.g. Toluene, xylene, ethylene benzene, aliphatic hydrocarbons and ketones such as acetone and methyl ketone can be carried out.
  • the proportions of the reactants are chosen so that only partial esterification of the anhydride groups occurs.
  • Based on the hydrolyzed partially esterified polymer 5 to 75, preferably 5 to 50% of the carboxyl groups are esterified.
  • the esterification itself is usually carried out at higher temperatures, e
  • esterification reaction is complete after about 0.5 to 20, preferably 1 to 10 hours.
  • solvents are removed from the reaction mixture, e.g. by distillation, if appropriate under reduced pressure, and the remaining partially esterified polymers are dissolved in water with the addition of alkalis.
  • alkalis are e.g. Sodium hydroxide solution, potassium hydroxide solution, ammonia, amines and alkanolamines.
  • the pH of the aqueous, partially esterified polymer solution thus obtained is 4 to 10, preferably 6 to 8.
  • Example 1 240 g of maleic anhydride and 240 g of technical xylene are placed in a polymerization reactor provided with stirrer, cooler, nitrogen inlet and outlet and with metering devices and heated to about 140 ° C. until boiling. 80 g of di-tert are added to the low-boiling solution within 2 hours. Butyl peroxide and the reaction mixture is heated for 2 hours after addition of the initiator with stirring and reflux, 2 phases being formed. The polymer thus produced with a molar mass of about 4000 g per mol is then partially esterified with 230 g of a cetyl / oleyl alcohol mixture in the presence of 1 g of p-toluenesulfonic acid at 130 ° C. within 2 hours with stirring. The remaining xylene is distilled off under reduced pressure.
  • the reaction mixture is cooled to a temperature of 100 ° C and, by simultaneously adding 384 ml of water and 180 g of 30% aqueous sodium hydroxide solution, is processed to a stable, yellowish emulsion which has a solids content of approx. 55% and a pH of 6 , 8 has. Approx. 45 mol% of the total carboxyl groups resulting from the anhydride groups have been esterified and approximately 55 mol% have been neutralized.
  • Example 2 560 g of the polymer prepared in Example 1 in xylene are mixed with 200 g of a cetyl / oleyl alcohol mixture and 200 g of an adduct of 6 moles of ethylene oxide with 1 mole of a C 16 / C 18 oxo alcohol in the presence of 2 g of p-toluenesulfonic acid partially esterified for 3 hours at 130 ° C. The remaining xylene is distilled off under reduced pressure. The reaction mixture is cooled to a temperature of 100 ° C. and processed into a low-viscosity emulsion by simultaneously adding 800 ml of water and 106 g of 30% strength aqueous sodium hydroxide solution. The pale yellowish emulsion thus obtained has a solids content of approximately 40% and a pH of 6.8.
  • Example 3 560 g of the polymer prepared in Example 1 in xylene are partially esterified with 192 g of a cetyl / oleyl alcohol mixture in the presence of 1 g of p-toluenesulfonic acid within 2 hours with stirring. The remaining xylene is distilled off under reduced pressure. 161 g of morpholine are then added over the course of half an hour and the reaction mixture is heated to a temperature of 130 ° C. within 2 hours with stirring. Thereby, further, still existing anhydride groups of the copolymer converted into monoamide groups. The reaction mixture is cooled to 80 ° C.
  • EXAMPLE 5 If the procedure is as described in Example 1, but instead of 230 g of the cetyl / oleyl alcohol mixture, 1505 g of the cetyl / oleyl alcohol mixture and 92 g of laurylamine are used, a dispersion which is viscous at room temperature and has a solids content of about 55% is obtained. .
  • EXAMPLE 6 If the procedure is as described in Example 1, but instead of 230 g of the cetyl / oleyl alcohol mixture, 250 g of the adduct of 8 moles of ethylene oxide and 1 mole of stearic acid are used, a dispersion which is viscous at room temperature and has a solids content of about 52 is obtained %.
  • EXAMPLE 7 If the procedure described in Example 1 is followed, but instead of 230 g of the cetyl / oleyl alcohol mixture, 240 g of the adduct of 4 moles of ethylene oxide and 1 mole of oleylamine are used, a dispersion which is viscous at room temperature and has a solids content of about 50 is obtained %.
  • EXAMPLE 8 If the procedure is as described in Example 1, but 230 g of the adduct of 6 mol of ethylene oxide and 1 mol of lauric acid amide are used instead of 230 g of the cetyl / oleyl alcohol mixture, a dispersion which is viscous at room temperature and has a solids content of approximately 49 is obtained %.
  • Example 9 Chrome-tanned cowhide leather deacidified to a pH of 5.2 with a fold thickness of 1.8 mm is made in the usual way with 1%, based on the weight of the leather, of the dye of the formula colored. The leather is then post-treated with 8% of the product produced in Example 1, based on the shaved weight. The total fleet length is 100%. Then it is adjusted to a pH of 3.8 with formic acid. The leather is then washed, mechanically stretched and dried.
  • the leather obtained is very soft, supple to the touch and shows a brilliant and level coloring.

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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)

Description

Die vorliegende Erfindung betrifft ein Verfahren zum Nachbehandeln von gegerbtem Leder und Pelzen, das für dieses Verfahren eingesetzte Mittel, ein Verfahren zur Herstellung dieses Mittels sowie das nach dem vorliegenden Verfahren nachbehandelte Leder- oder Pelzmaterial.The present invention relates to a process for the aftertreatment of tanned leather and furs, the agent used for this process, a process for producing this agent and the leather or fur material aftertreated by the present process.

EP-A-0 428 481 offenbart ein Mittel zur Behandlung von Leder und Pelzen, dadurch gekennzeichnet, daß es (A) ein anionisches Syntan und (B) ein Polymerisat und/oder Copolymerisat einer ungesättigten C3-C5-Mono- oder Dicarbonsäure und/oder deren Hydroxyverbindungen enthält.EP-A-0 428 481 discloses an agent for treating leather and furs, characterized in that it (A) is an anionic syntan and (B) is a polymer and / or copolymer of an unsaturated C 3 -C 5 mono- or dicarboxylic acid and / or contains their hydroxy compounds.

Das vorliegende Verfahren zum Nachbehandeln von gegerbtem Leder und Pelzen ist dadurch gekennzeichnet, dass man das Leder oder die Pelze mit einem Polymerisat nachbehandelt, das erhältlich ist durch

  • (a) Polymerisation eines monoethylenisch ungesättigten Dicarbonsäureanhydrids mit 4 bis 8 Kohlenstoffatomen oder Mischungen dieser Dicarbonsäureanhydride und
  • (b) anschliessende partielle Veresterung und/oder Amidierung dieses Polymeren mit einem
    • (b1) C1-C30Alkohol und/oder einer primären oder sekundären Aminverbindung und/oder
    • (b2) dem Umsetzungssprodukt aus einem
      • (α) ungesättigten oder gesättigten C1-C30-Fettalkohol, einer C8-C22-Fettsäure, einem C8-C22- Fettamin oder einem C8-C22- Fettamid und
      • (β) Ethylenoxid und/oder Propylenoxid
      im Molverhaltnis 1:2 bis 1:20
und gegebenenfalls anschliessende Hydrolyse der Anhydridgruppen der Homopolymerisate mit wässrigen Basen.The present process for the aftertreatment of tanned leather and furs is characterized in that the leather or the furs is aftertreated with a polymer which is obtainable from
  • (a) Polymerization of a monoethylenically unsaturated dicarboxylic acid anhydride with 4 to 8 carbon atoms or mixtures of these dicarboxylic acid anhydrides and
  • (b) subsequent partial esterification and / or amidation of this polymer with a
    • (b 1 ) C 1 -C 30 alcohol and / or a primary or secondary amine compound and / or
    • (b 2 ) the reaction product from one
      • (α) unsaturated or saturated C 1 -C 30 fatty alcohol, a C 8 -C 22 fatty acid, a C 8 -C 22 fatty amine or a C 8 -C 22 fatty amide and
      • (β) ethylene oxide and / or propylene oxide
      in a molar ratio of 1: 2 to 1:20
and optionally subsequent hydrolysis of the anhydride groups of the homopolymers with aqueous bases.

In einer bevorzugten Ausführungsform des erfindungsgemässen Verfahrens werden Polymerisate eingesetzt, die erhältlich sind durch

  • (a) Polymerisation eines monoethylenisch ungesättigten Dicarbonsäureanhydrids mit 4 bis 8 Kohlenstoffatomen oder Mischungen dieser Dicarbonsäureanhydride und
  • (b) anschliessende partielle Veresterung und/oder Amidierung dieses Polymeren mit dem Umsetzungsprodukt aus
    • (α) einem ungesättigten oder gesättigten C1-C30-Fettalkohol, einer C8-C22-Fettsäure, einem C8-C22- Fettamin oder C8-C22- Fettamid und
    • (β) Ethylenoxid und/oder Propylenoxid
    im Molverhältnis 1:2 bis 1:20
und anschliessende Hydrolyse der Anhydridgruppen der Homopolymerisate mit wässrigen Basen.In a preferred embodiment of the process according to the invention, polymers are used which are obtainable from
  • (a) Polymerization of a monoethylenically unsaturated dicarboxylic acid anhydride with 4 to 8 carbon atoms or mixtures of these dicarboxylic acid anhydrides and
  • (b) subsequent partial esterification and / or amidation of this polymer with the reaction product
    • (α) an unsaturated or saturated C 1 -C 30 fatty alcohol, a C 8 -C 22 fatty acid, a C 8 -C 22 fatty amine or C 8 -C 22 fatty amide and
    • (β) ethylene oxide and / or propylene oxide
    in a molar ratio of 1: 2 to 1:20
and subsequent hydrolysis of the anhydride groups of the homopolymers with aqueous bases.

Die erfindungsgemässen Polymerisate sind neu. Die Erfindung betrifft auch die neuen Polymerisate, insbesondere im Umfang der vorstehend genannten bevorzugten Ausführungsform.The polymers according to the invention are new. The invention also relates to the new polymers, in particular within the scope of the preferred embodiment mentioned above.

Als monethylenisch ungesättigtes polymerisierbares Dicarbonsäureanhydrid kommen z.B. Maleinsäureanhydrid, Citraconsäureanhydrid, Methylenmalonsäureanhydrid und Mischungen dieser Verbindungen untereinender in Betracht. Von den genannten Anhydriden wird vorzugsweise Maleinsäureanhydrid verwendet.As the monethylenically unsaturated polymerizable dicarboxylic acid anhydride there are e.g. Maleic anhydride, citraconic anhydride, methylene malonic anhydride and mixtures of these compounds. Of the anhydrides mentioned, maleic anhydride is preferably used.

Geeignete C1-C30-Alkohole als Komponente (b1) sind z.B. Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol, Isobutanol, tert.Butanol, Pentanol, Cyclohexanol, n-Hexanol, Önanthalkohol, n-Octanol, 2-Ethylhexanol, Pelargonalkohol, Decanol, Dodecanol, Myristylalkohol, Cetylalkohol, Stearylalkohol, Arachidylalkohol, Behenylalkohol, Cerylalkohol, Cerotylalkohol, Myricylalkohol, C9-C11-Oxoalkohol, Tridecylalkohol, Isotridecanol oder Gemische aus linearen primären Alkoholen (®Alfole) mit 8 bis 18 Kohlenstoffatomen. Einige Vertreter dieser Alfole sind Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) oder Alfol (16-18).Suitable C 1 -C 30 alcohols as component (b 1 ) are, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentanol, cyclohexanol, n-hexanol, onanthal alcohol, n-octanol, 2-ethylhexanol, pelargon alcohol, decanol, dodecanol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, ceryl alcohol, cerotyl alcohol, myricyl alcohol, C 9 -C 11 oxo alcohol, tridecyl alcohol, isotrido alfanols or mixtures of linear (8 bisalene alcohols) with mixtures ( 18 carbon atoms. Some representatives of these alfoles are Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) or Alfol (16-18).

Vorzugsweise wird als Komponente (b1) ein Cetyl/Oleyl-Alkoholgemisch vewendet.A cetyl / oleyl alcohol mixture is preferably used as component (b 1 ).

Bevorzugte Verbindungen für die fakultative Partialamidierung mit Aminen sind Ammoniak, Mono- oder Di-C1-C5-Alkylamin, Phenyl-C1-C5-Alkylamin, Mono- oder Di-C5-C7-Cycloalkylamin oder Morpholin.Preferred compounds for the optional partial amidation with amines are ammonia, mono- or di-C 1 -C 5 -alkylamine, phenyl-C 1 -C 5 -alkylamine, mono- or di-C 5 -C 7 -cycloalkylamine or morpholine.

Beispiele für die verwendeten C1-C5-Alkylamine sind Monomethyl-, Dimethyl-, Monoethyl-, Diethyl-, Mono-n-propyl-, Di-n-propyl-, Monoisopropyl-, Diisopropyl-, Mono-n-Butyl-, Di-n-Butyl-, Mono-sek.-Butyl-, Di-sek.-Butyl-, Mono-tert. Butyl-, Di-tert. Butyl-, Monoamyl-, Diamyl-, Monoisoamyl- oder Diisoamylamin sowie Monocyclopentyl-, Di-cyclopentyl-, Monocyclohexyl-, Dicyclohexyl-, Monocycloheptyl- oder Dicycloheptylamin als Vertreter für C5-C7-Cycloalkylaminverbindungen.Examples of the C 1 -C 5 -alkylamines used are monomethyl, dimethyl, monoethyl, diethyl, mono-n-propyl, di-n-propyl, monoisopropyl, diisopropyl, mono-n-butyl , Di-n-butyl, mono-sec-butyl, di-sec-butyl, mono-tert. Butyl, di-tert. Butyl, monoamyl, diamyl, monoisoamyl or diisoamylamine and monocyclopentyl, di-cyclopentyl, monocyclohexyl, dicyclohexyl, monocycloheptyl or dicycloheptylamine as representatives for C 5 -C 7 cycloalkylamine compounds.

Ganz besonders bevorzugt sind Ammoniak und Morpholin.Ammonia and morpholine are very particularly preferred.

Geeignete ungesättigte oder gesättigte C8-C22-Fettsäuren, die als Komponente (α) in Betracht kommen, sind z.B. Capryl-, Caprin-, Laurin-, Myristin-, Palmitin-, Stearin-, Arachin-, Behen-, Olein-, Linol-, Linolen-, Arachidon- oder Kokosfettsäure bzw. die Decen-, Dodecen-, Teradecen-, Hexadecen- oder Ricinolsäure.Suitable unsaturated or saturated C 8 -C 22 fatty acids which can be considered as component (α) are, for example, caprylic, capric, lauric, myristic, palmitic, stearic, arachine, behenic, oleic , Linoleic, Linolenic, Arachidonic or Coconut fatty acid or the Decenic, Dodecenic, Teradecenic, Hexadecenic or Ricinolic acid.

Als Beispiel für das Anlagerungsprodukt einer Fettsäure an ein Alkylenoxid sei das Addukt aus 2 bis 15 Mol Ethylenoxid und 1 Mol einer C8-C22-Fettsäure genannt.An example of the adduct of a fatty acid with an alkylene oxide is the adduct of 2 to 15 moles of ethylene oxide and 1 mole of a C 8 -C 22 fatty acid.

Bevorzugt sind auch Umsetzungsprodukte aus Fettaminen und Ethylenoxid oder Propylenoxid, wie z.B. Fettsäurealkanolamide mit 8 bis 22 Kohlenstoffatomen im Fettsäurerest und 2 bis 18 Kohlenstoffatomen im Alkanolrest. Hierbei handelt es sich z.B. um Fettsäure-Alkanolamin-Umsetzungsprodukte, welche aus C8-C22-Fettsäuren, vorzugsweise C8-C18-Fettsäuren und C2-C6-Alkanolaminen wie Ethanolamin, Diethanolamin, Isopropanolamin oder Diisopropanolamin hergestellt werden, wobei Diethanolamin bevorzugt ist. Besonders bevorzugt sind C8-C18-Fettsäurediethanolamide. Bevorzugte Beispiele derartiger Umsetzungsprodukte sind das Kokosfettsäurediethanolamid, sowie das Laurinsäure- oder Stearinsäurediethanolamid.Reaction products of fatty amines and ethylene oxide or propylene oxide, such as, for example, fatty acid alkanolamides having 8 to 22 carbon atoms in the fatty acid residue and 2 to 18 carbon atoms in the alkanol residue, are also preferred. These are, for example, fatty acid-alkanolamine reaction products which are prepared from C 8 -C 22 fatty acids, preferably C 8 -C 18 fatty acids and C 2 -C 6 alkanolamines such as ethanolamine, diethanolamine, isopropanolamine or diisopropanolamine, where Diethanolamine is preferred. C 8 -C 18 fatty acid diethanolamides are particularly preferred. Preferred examples of such reaction products are coconut fatty acid diethanolamide and lauric acid or stearic acid diethanolamide.

Bevorzugte Verbindungen, die als Komponente (α) in Betracht kommen, sind C8-C22-Fettsäuren.Preferred compounds which can be considered as component (α) are C 8 -C 22 fatty acids.

Wässrige Basen für die Teilneutralisation und Hydrolyse sind insbesondere wässrige Lösungen von NaOH oder KOH (Natronlauge, Kalilauge), aber auch wässrige Lösungen von Aminen, wie z.B. Ammoniak.Aqueous bases for partial neutralization and hydrolysis are in particular aqueous solutions of NaOH or KOH (sodium hydroxide solution, potassium hydroxide solution), but also aqueous solutions of amines, such as e.g. Ammonia.

Für das erfindungsgemässe Verfahren werden Poylmerisate verwendet, bei denen z.B. 5 bis 40, vorzugsweise 25 bis 35 %, bezogen auf die Mengen an Monomeren, verestert und/oder amidiert sind.For the process according to the invention, polymers are used in which e.g. 5 to 40, preferably 25 to 35%, based on the amounts of monomers, are esterified and / or amidated.

Das erfindungsgemässe Verfahren eignet sich zur Nachbehandlung von allen üblichen gegerbten Lederhäuten, insbesondere mit Mineralgerbstoffen, wie Chrom-III-Salzen gegerbten Häuten. Diese werden üblicherweise vor der Nachbehandlung entsäuert. Sie können bereits vor der Nachbehandlung gefärbt sein. Eine Färbung kann jedoch auch erst nach der erfindungsgemäss vorgenommenen Nachbehandlung erfolgen.The process according to the invention is suitable for the aftertreatment of all customary tanned leather hides, in particular hides tanned with mineral tanning agents, such as chromium III salts. These are usually deacidified before the aftertreatment. They can be colored before the aftertreatment. However, coloring can also take place only after the aftertreatment carried out according to the invention.

Die gegerbten und gegebenenfalls gefärbten Häute werden mit der wässrigen Polymerlösung zweckmässigerweise in wässriger Flotte, die durch Verdünnen der Polymerlösung mit Wasser erhältlich ist, bei pH-Werten von 4 bis 10, vorzugsweise 5 bis 8 und Temperaturen von 20° bis 50°, vorzugsweise 30 bis 50°C wahrend eines Zeitraums von 0,1 bis 5, vorzugsweise 0,2 bis 2 Stunden, nachbehandelt. Diese Nachbehandlung erfolgt beispielsweise durch Walken in einem Fass. Die benötigte Menge an Polymerlösung beträgt, bezogen auf das Falzgewicht des Leders oder das Nassgewicht der Pelzfelle, 0,1 bis 30, vorzugsweise 1 bis 20 Gew.%. Die Flottenlänge, d.h. das prozentuale Gewichtsverhältnis der Nachbehandlungsflotte zur Ware, bezogen auf das Falzgewicht des Leders bzw. das Nassgewicht der Pelzfelle, beträgt üblicherweise 10 bis 1000, vorzugsweise 30 bis 150%, bei Pelzfellen 50 bis 500 %.The tanned and optionally colored skins are expediently mixed with the aqueous polymer solution in an aqueous liquor, which can be obtained by diluting the polymer solution with water, at pH values of 4 to 10, preferably 5 to 8 and temperatures of 20 ° to 50 °, preferably 30 to 50 ° C for a period of 0.1 to 5, preferably 0.2 to 2 hours, aftertreated. This aftertreatment is carried out, for example, by milling in a barrel. The required amount of polymer 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 fleet length, i.e. the percentage weight ratio of the aftertreatment liquor to the goods, based on the shaved 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%.

Nach der Nachbehandlung mit der oben beschriebenen wässrigen Flotte wird der pH-Wert der Flotte durch Zusatz von Säuren, vorzugsweise organischer Säuren wie Ameisensäure, auf einen pH-Wert von 3 bis 5, vorzugsweise 3,5 bis 4 eingestellt und das Leder wie üblich fertiggestellt.After the aftertreatment with the aqueous liquor described above, the pH of the 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, and the leather is finished in the customary manner .

Die nach dem erfindungsgemässen Verfahren nachbehandelten Leder oder Pelze zeichnen sich durch eine gute Fülle und einen ausserordentlich geschmeidigen Griff aus.The leather or furs aftertreated by the process according to the invention are distinguished by a good fullness and an extraordinarily smooth feel.

Die Erfindung betrifft auch ein wässriges Nachbehandlungsmittel, erhältlich durch

  • (a) Polymerisation eines monoethylenisch ungesättigten Dicarbonsäureanhydrids mit 4 bis 8 Kohlenstoffatomen oder Mischungen dieser Dicarbonsäureanhydride und
  • (b) anschliessende partielle Veresterung und/oder Amidierung dieses Polymeren mit einem
    • (b1) C1-C30Alkohol und/oder einer primären oder sekundären Aminverbindung und/oder
    • (b2) dem Umsetzungssprodukt aus einem
      • (α) ungesättigten oder gesättigten C1-C30-Fettalkohol, einer C8-C22-Fettsäure, einem C8-C22-Fettamin oder einem C8-C22-Fettamid und
      • (β) Ethylenoxid und/oder Propylenoxid
      im Molverhältnis 1:2 bis 1:20
und gegebenenfalls anschliessende Hydrolyse der Anhydridgruppen der Homopolymerisate mit wässrigen Basen.The invention also relates to an aqueous aftertreatment agent obtainable by
  • (a) Polymerization of a monoethylenically unsaturated dicarboxylic acid anhydride with 4 to 8 carbon atoms or mixtures of these dicarboxylic acid anhydrides and
  • (b) subsequent partial esterification and / or amidation of this polymer with a
    • (b 1 ) C 1 -C 30 alcohol and / or a primary or secondary amine compound and / or
    • (b 2 ) the reaction product from one
      • (α) unsaturated or saturated C 1 -C 30 fatty alcohol, a C 8 -C 22 fatty acid, a C 8 -C 22 fatty amine or a C 8 -C 22 fatty amide and
      • (β) ethylene oxide and / or propylene oxide
      in a molar ratio of 1: 2 to 1:20
and optionally subsequent hydrolysis of the anhydride groups of the homopolymers with aqueous bases.

Bevorzugte wässrige Nachbehandlungsmittel sind erhältlich durch

  • (a) Polymerisation eines monoethylenisch ungesättigten Dicarbonsäureanhydrids mit 4 bis 8 Kohlenstoffatomen oder Mischungen dieser Dicarbonsäureanhydride und
  • (b) anschliessende partielle Veresterung und/oder Amidierung dieses Polymeren mit dem Umsetzungsprodukt aus
    • (α) einem ungesättigten oder gesättigten C1-C30-Fettalkohol,einer C8-C22- Fettsäure, einem C8-C22- Fettamin oder C8-C22- Fettamid und
    • (β) Ethylenoxid und/oder Propylenoxid
    im Molverhältnis 1:2 bis 1:20
und anschliessende Hydrolyse der Anhydridgruppen der Homopolymerisate mit wässrigen Basen.Preferred aqueous aftertreatment agents are obtainable from
  • (a) Polymerization of a monoethylenically unsaturated dicarboxylic acid anhydride with 4 to 8 carbon atoms or mixtures of these dicarboxylic acid anhydrides and
  • (b) subsequent partial esterification and / or amidation of this polymer with the reaction product
    • (α) an unsaturated or saturated C 1 -C 30 fatty alcohol, a C 8 -C 22 fatty acid, a C 8 -C 22 fatty amine or C 8 -C 22 fatty amide and
    • (β) ethylene oxide and / or propylene oxide
    in a molar ratio of 1: 2 to 1:20
and subsequent hydrolysis of the anhydride groups of the homopolymers with aqueous bases.

Ein weiterer Gegenstand der vorliegenden Erfindung sind Polymerisate, die erhältlich sind durch

  • (a) Polymerisation eines monoethylenisch ungesättigten Dicarbonsäureanhydrids mit 4 bis 8 Kohlenstoffatomen oder Mischungen dieser Dicarbonsäureanhydride und
  • (b) anschliessende partielle Veresterung und/oder Amidierung dieses Polymeren mit einem
    • (b1) C1-C30Alkohol und/oder einer primären oder sekundären Aminverbindung und/oder
    • (b2) dem Umsetzungssprodukt aus einem
      • (α) ungesättigten oder gesättigten C1-C30-Fettalkohol, einer C8-C22- Fettsäure, einem C8-C22- Fettamin oder einem C8-C22- Fettamid und
      • (β) Ethylenoxid und/oder Propylenoxid
      im Molverhältnis 1:2 bis 1:20
und gegebenenfalls anschliessende Hydrolyse der Anhydridgruppen der Homopolymerisate mit wässrigen Basen.The present invention furthermore relates to polymers which are obtainable by
  • (a) Polymerization of a monoethylenically unsaturated dicarboxylic acid anhydride with 4 to 8 carbon atoms or mixtures of these dicarboxylic acid anhydrides and
  • (b) subsequent partial esterification and / or amidation of this polymer with a
    • (b 1 ) C 1 -C 30 alcohol and / or a primary or secondary amine compound and / or
    • (b 2 ) the reaction product from one
      • (α) unsaturated or saturated C 1 -C 30 fatty alcohol, a C 8 -C 22 fatty acid, a C 8 -C 22 fatty amine or a C 8 -C 22 fatty amide and
      • (β) ethylene oxide and / or propylene oxide
      in a molar ratio of 1: 2 to 1:20
and optionally subsequent hydrolysis of the anhydride groups of the homopolymers with aqueous bases.

Die Polymerisation der ethylenisch ungesättigten Anhydride wird nach an sich bekannten diskontinuierlichen oder kontinuierlichen Verfahren durchgeführt, wie Masse-, Suspensions-, Fällungs- und Lösemittelpolymerisation.The polymerization of the ethylenically unsaturated anhydrides is carried out according to discontinuous or continuous processes known per se, such as bulk, suspension, precipitation and solvent polymerization.

Die als Ausgangsverbindungen dienenden monomeren ethylenisch ungesättigten Dicarbonsäureanhydride werden vorzugsweise als einheitliche Verbindungen in technischer Reinheit eingesetzt. Es können aber auch Mischungen verschiedener Dicarbonsäureanhydride verwendet werden, so dass Mischpolymerisate gebildet werden. Die Homopolymerisate sind bevorzugtThe monomeric ethylenically unsaturated dicarboxylic anhydrides serving as starting compounds are preferably used as uniform compounds in technical purity. Mixtures of different dicarboxylic acid anhydrides can also be used, so that copolymers are formed. The homopolymers are preferred

Die Polymerisation der Anhydride wird z.B. bei Temperaturen von 80 bis 300, vorzugsweise 120 bis 200°C durchgeführt, wobei die niedrigste zu wählende Polymerisationstemperatur vorzugsweise etwa mindestens 20°C über der Glastemperatur des gebildeten Polymers liegt. Je nach Molekulargewicht, das die Polymerisate haben sollen, werden die Polymerisationsbedingungen gewählt Polymerisation bei höherer Temperatur ergibt Polymerisate mit niedrigem Molekulargewicht, während bei niedrigen Polymerisationstemperaturen Polymerisate mit höherem Molekulargewicht entstehen. Für die erfindungsgemässe Zusammensetzung werden die Bedingungen so gewählt, dass Polymerisate mit Molmassen von 500 bis 30,000 g pro Mol, vorzugsweise 500 bis 2000 g pro Mol entstehen.The polymerization of the anhydrides is e.g. carried out at temperatures of 80 to 300, preferably 120 to 200 ° C, the lowest polymerization temperature to be selected is preferably about at least 20 ° C above the glass transition temperature of the polymer formed. Depending on the molecular weight that the polymers should have, the polymerization conditions are selected. Polymerization at a higher temperature results in polymers with a low molecular weight, while polymers with a higher molecular weight are formed at low polymerization temperatures. The conditions for the composition according to the invention are chosen such that polymers with molar masses of 500 to 30,000 g per mol, preferably 500 to 2000 g per mol, are formed.

Eine einfache Methode zur Herstellung der Polymerisate ist die Fällungspolymerisation. Bei diesem Verfahren werden Lösungsmittel eingesetzt, in denen die Monomeren löslich sind und das gebildete Polymer unlöslich ist und ausfällt. Solche Lösemittel sind z.B. aromatische Verbindungen, vorzugsweise Toluol, Xylol, Benzol oder Cumol und deren Mischungen untereinander.A simple method for producing the polymers is precipitation polymerization. This process uses solvents in which the monomers are soluble and the polymer formed is insoluble and precipitates. Such solvents are e.g. aromatic compounds, preferably toluene, xylene, benzene or cumene and their mixtures with one another.

Die bevorzugte Methode ist die Lösungsmittelpolymerisation. Sie wird in Lösungsmitteln durchgeführt, in denen sowohl die Monomeren als auch die gebildeten Polymerisate löslich sind. Es sind hierfür alle Lösungsmittel geeignet, die diese Bedingungen erfüllen und gegenüber den Säureanhydriden inert sind, wie z.B. Aceton, Methylethylketon, Diethylketon, Methylisobutylketon, Ethylacetat, Butylacetat sowie aliphatische Kohlenwasserstoffe wie n-Oktan, Isooktan, Cyclohexan oder Methylcyclohexan.The preferred method is solvent polymerization. It is carried out in solvents in which both the monomers and the polymers formed are soluble. All solvents that meet these conditions and are inert to the acid anhydrides are suitable for this, such as Acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate and aliphatic hydrocarbons such as n-octane, isooctane, cyclohexane or methylcyclohexane.

Die Polymerisation wird bei allen Verfahren mit Hilfe von in Radikale zerfallende Verbindungen, wie z.B. Peroxide, Hydroperoxide, Redoxinitiatoren und Azoverbindungen durchgeführt. Geeignete Polymerisationsinitiatoren sind beispielsweise Acetylcyclohexansulfonylperoxid, Diacetylperoxidicarbonat, Di-2-ethylhexylperoxidicarbonat, Tertiärbutylperneodecanoat, 2,2'-Azobis(4-methoxy-2,4-dimethylvalerionitril), Tertiär-butylpermaleinat, 2,2'-Azobis(isobutyronitril), Bis-(tertiär-butylperoxi)cyclohexan, Tertiär-butylperoxiisopropylcarbonat, Tertiär-butylperacetat, Di-tertiär-butylperoxid, Ditertiäramylperoxid, Cumolhydroperoxid und Tertiär-butylhydroperoxid. Die Initiatoren können allein oder in Mischung untereinander eingesetzt werden. Die Polymerisationsinitiatoren werden dabei vorzugsweise in Mengen von 5 bis 40%, bezogen auf die jeweils eingesetzte Menge an monomerem Anhydrid, eingesetzt.In all processes, the polymerization is carried out with the aid of compounds which break down into free radicals, such as, for example, peroxides, hydroperoxides, redox initiators and azo compounds. Suitable polymerization initiators are, for example, acetylcyclohexanesulfonyl peroxide, diacetyl peroxidicarbonate, di-2-ethylhexyl peroxidicarbonate, tertiary butyl perneodecanoate, 2,2'-azobis (4-methoxy-2,4-dimethylvalerionitrile), tertiary-butylpermyrobitrate (2,2'-bis-azalobitrate) (tertiary butyl peroxy) cyclohexane, tertiary butyl peroxy isopropyl carbonate, tertiary butyl peracetate, di-tertiary butyl peroxide, ditertiary amyl peroxide, cumene hydroperoxide and tertiary butyl hydroperoxide. The initiators can be used alone or as a mixture with one another. The polymerization initiators are preferably used in amounts of 5 to 40%, based on the amount used in each case of monomeric anhydride.

Bei allen genannten Polymerisationsverfahren wird in einer reaktionsinerten Atmosphäre, vorzugsweise unter Ausschluss von Sauerstoff gearbeitet, insbesondere in einem Inertgasstrom wie z.B. Stickstoff oder Argon. Für alle Polymerisationsreaktionen werden die üblichen Apparaturen verwendet, z.B. Autoklaven und Kessel, die beispielsweise mit Anker-, Blatt-, Impeller- oder Mehrstufenimpuls-Gegenstrom-Rührern ausgestattet sind.In all of the polymerization processes mentioned, the reaction is carried out in an inert atmosphere, preferably in the absence of oxygen, in particular in an inert gas stream, e.g. Nitrogen or argon. The usual equipment is used for all polymerization reactions, e.g. Autoclaves and kettles equipped with, for example, anchor, blade, impeller or multi-stage impulse countercurrent stirrers.

Die so erhältlichen Polymerisate werden anschliessend in einem nächsten Reaktionsschritt partiell verestert und hydrolysiert, so dass die Anhydridgruppen in Carboxylgruppen umgewandelt werden. Es ist auch möglich, die Anhydridgruppen enthaltenden Polymerisate zunächst zu hydrolysieren, so dass sämtliche Anhydridgruppen als Carboxylgruppen vorliegen und dann die Veresterung nach bekannten Methoden durchzuführen. Bevorzugt ist jedoch die Arbeitsweise, bei der man zunächst die Carbonsäureanhydridgruppen des Polymerisats partiell verestert.The polymers thus obtainable are then partially esterified and hydrolyzed in a next reaction step, so that the anhydride groups are converted into carboxyl groups. It is also possible to hydrolyze the polymers containing anhydride groups first, so that all anhydride groups are in the form of carboxyl groups, and then to carry out the esterification by known methods. However, the procedure is preferred in which the carboxylic anhydride groups of the polymer are first partially esterified.

Die partielle Veresterung kann in Gegenwart von Lösungsmitteln, die gegenüber den Anhydridgruppen inert sind und sowohl die Ausgangsstoffe als auch die veresterten Copolymerisate lösen oder quellen, z.B. Toluol, Xylol, Ethylenbenzol, aliphatische Kohlenwasserstoffe und Ketone, wie Aceton und Methylketon, durchgeführt werden. Die Mengenverhältnisse der Reaktanden werden dabei so gewählt, dass nur eine partielle Veresterung der Anhydridgruppen eintritt. Bezogen auf das hydrolysierte partiell veresterte Polymerisat sind 5 bis 75, vorzugsweise 5 bis 50 % der Carboxylgruppen verestert. Die Veresterung selbst wird in der Regel bei höheren Temperaturen, z.B. 50° bis 200°, vorzugsweise 80 bis 150°C in Gegenwart der üblichen Veresterungskatalysatoren vorgenommen. Besonders geeignet ist p-Toluolsulfonsäure. Die Veresterungsreaktion ist nach etwa 0,5 bis 20, vorzugsweise 1 bis 10 Stunden beendet. Nach der partiellen Veresterung werden die Lösungsmittel aus dem Reaktionsgemisch entfernt, z.B. durch Abdestillieren, gegebenenfalls unter vermindertem Druck, und die verbleibenden partiell veresterten Polymerisate werden in Wasser unter Zusatz von Alkalien gelöst. Hierbei werden die noch in dem Polymerisat vorhandenen Anhydridgruppen hydrolysiert. Geeignete Alkalien sind z.B. Natronlauge, Kalilauge, Ammoniak, Amine und Alkanolamine.The partial esterification can in the presence of solvents which are inert to the anhydride groups and dissolve or swell both the starting materials and the esterified copolymers, e.g. Toluene, xylene, ethylene benzene, aliphatic hydrocarbons and ketones such as acetone and methyl ketone can be carried out. The proportions of the reactants are chosen so that only partial esterification of the anhydride groups occurs. Based on the hydrolyzed partially esterified polymer, 5 to 75, preferably 5 to 50% of the carboxyl groups are esterified. The esterification itself is usually carried out at higher temperatures, e.g. 50 ° to 200 °, preferably 80 to 150 ° C in the presence of the usual esterification catalysts. P-Toluenesulfonic acid is particularly suitable. The esterification reaction is complete after about 0.5 to 20, preferably 1 to 10 hours. After the partial esterification, the solvents are removed from the reaction mixture, e.g. by distillation, if appropriate under reduced pressure, and the remaining partially esterified polymers are dissolved in water with the addition of alkalis. Here, the anhydride groups still present in the polymer are hydrolyzed. Suitable alkalis are e.g. Sodium hydroxide solution, potassium hydroxide solution, ammonia, amines and alkanolamines.

Der pH-Wert der so erhaltenen, wässrigen, partiell veresterten Polymerlösung beträgt 4 bis 10, vorzugsweise 6 bis 8.The pH of the aqueous, partially esterified polymer solution thus obtained is 4 to 10, preferably 6 to 8.

Die nachfolgenden Beispiele dienen zur Veranschaulichung der Erfindung. Die Prozentangaben beziehen sich dabei, wenn nicht anders angegeben, auf das Gewicht.The following examples serve to illustrate the invention. Unless otherwise stated, the percentages relate to the weight.

Beispiel 1: In einem mit Rührer, Kühler, Stickstoffein- und -auslass sowie mit Dosiervorrichtungen versehenen Polymerisationsreaktor werden 240 g Maleinsäureanhydrid und 240 g technisches Xylol vorgelegt und auf ca. 140°C bis zum Sieden erhitzt. Zu der schwach siedenden Lösung gibt man innerhalb von 2 Stunden 80 g Di-tert. Butylperoxid und erhitzt das Reaktionsgemisch nach Zugabe des Initiators noch 2 Stunden unter Rühren und Rückfluss, wobei sich 2 Phasen bilden. Das so hergestellte Polymerisat mit einer Molmasse von ca. 4000 g pro Mol wird dann mit 230 g eines Cetyl/Oleylalkoholgemisches in Gegenwart von 1 g p-Toluolsulfonsäure bei 130°C innerhalb von 2 Stunden unter Rühren partiell verestert. Das restliche Xylol wird dabei unter vermindertem Druck abdestilliert. Example 1: 240 g of maleic anhydride and 240 g of technical xylene are placed in a polymerization reactor provided with stirrer, cooler, nitrogen inlet and outlet and with metering devices and heated to about 140 ° C. until boiling. 80 g of di-tert are added to the low-boiling solution within 2 hours. Butyl peroxide and the reaction mixture is heated for 2 hours after addition of the initiator with stirring and reflux, 2 phases being formed. The polymer thus produced with a molar mass of about 4000 g per mol is then partially esterified with 230 g of a cetyl / oleyl alcohol mixture in the presence of 1 g of p-toluenesulfonic acid at 130 ° C. within 2 hours with stirring. The remaining xylene is distilled off under reduced pressure.

Das Reaktionsgemisch wird auf eine Temperatur von 100°C abgekühlt und durch gleichzeitige Zugabe von 384 ml Wasser und 180 g 30%iger wässriger Natronlauge zu einer stabilen, gelblichen Emulsion verarbeitet, die einen Feststoffgehalt von ca. 55% und einen pH-Wert von 6,8 aufweist. Ca. 45 Mol % der insgesamt aus den Anhydridgruppen entstandenen Carboxylgruppen sind verestert worden und ca. 55 Mol % sind neutralisiert worden.The reaction mixture is cooled to a temperature of 100 ° C and, by simultaneously adding 384 ml of water and 180 g of 30% aqueous sodium hydroxide solution, is processed to a stable, yellowish emulsion which has a solids content of approx. 55% and a pH of 6 , 8 has. Approx. 45 mol% of the total carboxyl groups resulting from the anhydride groups have been esterified and approximately 55 mol% have been neutralized.

Beispiel 2: 560 g des in Beispiel 1 hergestellten Polymerisates in Xylol werden mit 200 g eines Cetyl/Oleylalkoholgemisches und 200 g eines Anlagerungsproduktes von 6 Mol Ethylenoxid an 1 Mol eines C16/C18-Oxoalkohols in Gegenwart von 2 g p-Toluolsulfonsäure innerhalb von 3 Stunden bei 130°C partiell verestert. Das restliche Xylol wird dabei unter vermindertem Druck abdestilliert. Das Reaktionsgemisch wird auf eine Temperatur von 100°C abgekühlt und durch gleichzeitige Zugabe von 800 ml Wasser und 106 g 30%iger wässriger Natronlauge zu einer niedrigviskosen Emulsion verarbeitet. Die so erhaltene schwach gelbliche Emulsion hat einen Feststoffgehalt von ca. 40% und einen pH-Wert von 6,8. Example 2: 560 g of the polymer prepared in Example 1 in xylene are mixed with 200 g of a cetyl / oleyl alcohol mixture and 200 g of an adduct of 6 moles of ethylene oxide with 1 mole of a C 16 / C 18 oxo alcohol in the presence of 2 g of p-toluenesulfonic acid partially esterified for 3 hours at 130 ° C. The remaining xylene is distilled off under reduced pressure. The reaction mixture is cooled to a temperature of 100 ° C. and processed into a low-viscosity emulsion by simultaneously adding 800 ml of water and 106 g of 30% strength aqueous sodium hydroxide solution. The pale yellowish emulsion thus obtained has a solids content of approximately 40% and a pH of 6.8.

Beispiel 3: 560 g des im Beispiel 1 hergestellten Polymerisates in Xylol werden mit 192 g eines Cetyl/Oleylalkoholgemisch in Anwesenheit von 1 g p-Toluolsulfonsäure innerhalb von 2 Stunden unter Rühren partiell verestert. Das restliche Xylol wird dabei unter vermindertem Druck abdestilliert. Man fügt dann 161 g Morpholin innerhalb von einer halben Stunde zu und erhitzt das Reaktionsgemisch unter Rühren innerhalb von 2 Stunden auf eine Temperatur von 130°C. Dabei werden weitere, noch vorhandene Anhydridgruppen des Copolymerisats in Monoamidgruppen umgewandelt. Das Reaktionsgemisch wird auf 80°C abgekühlt und durch gleichzeitige Zugabe von 257 ml Wasser und 115 g 30 %iger wässriger Natronlauge zu einer wässrigen Lösung verarbeitet. Es entsteht dabei eine hellbraune, niedrigviskose Lösung mit einem Trockengehalt von ca. 60%. Der pH-Wert dieser Lösung beträgt 7,0. Example 3: 560 g of the polymer prepared in Example 1 in xylene are partially esterified with 192 g of a cetyl / oleyl alcohol mixture in the presence of 1 g of p-toluenesulfonic acid within 2 hours with stirring. The remaining xylene is distilled off under reduced pressure. 161 g of morpholine are then added over the course of half an hour and the reaction mixture is heated to a temperature of 130 ° C. within 2 hours with stirring. Thereby, further, still existing anhydride groups of the copolymer converted into monoamide groups. The reaction mixture is cooled to 80 ° C. and processed into an aqueous solution by simultaneously adding 257 ml of water and 115 g of 30% strength aqueous sodium hydroxide solution. This creates a light brown, low-viscosity solution with a dry content of approx. 60%. The pH of this solution is 7.0.

Beispiel 4: Arbeitet man wie im Beispiel 1 beschrieben, verwendet jedoch anstelle von 230 g des Cetyl-/Oleylalkoholgemisches 115 g Octanol, so erhält man eine bei Raumtemperatur viskose Dispersion mit einem Feststoffgehalt von ca. 45 %.EXAMPLE 4 If the procedure is as described in Example 1, but 115 g of octanol are used instead of 230 g of the cetyl / oleyl alcohol mixture, a dispersion which is viscous at room temperature and has a solids content of approximately 45% is obtained.

Beispiel 5: Arbeitet man wie im Beispiel 1 beschrieben, verwendet jedoch anstelle von 230 g des Cetyl-/Oleylalkoholgemisches 1505 g des Cetyl-/Oleylalkoholgemisches und 92 g Laurylamin, so erhält man eine bei Raumtemperatur viskose Dispersion mit einem Feststoffgehalt von ca. 55 %.EXAMPLE 5 If the procedure is as described in Example 1, but instead of 230 g of the cetyl / oleyl alcohol mixture, 1505 g of the cetyl / oleyl alcohol mixture and 92 g of laurylamine are used, a dispersion which is viscous at room temperature and has a solids content of about 55% is obtained. .

Beispiel 6: Arbeitet man wie im Beispiel 1 beschrieben, verwendet jedoch anstelle von 230 g des Cetyl-/Oleylalkoholgemisches 250 g des Anlagerungsproduktes von 8 Mol Ethylenoxid an 1 Mol Stearinsäure, so erhält man eine bei Raumtemperatur viskose Dispersion mit einem Feststoffgehalt von ca. 52 %.EXAMPLE 6 If the procedure is as described in Example 1, but instead of 230 g of the cetyl / oleyl alcohol mixture, 250 g of the adduct of 8 moles of ethylene oxide and 1 mole of stearic acid are used, a dispersion which is viscous at room temperature and has a solids content of about 52 is obtained %.

Beispiel 7: Arbeitet man wie im Beispiel 1 beschrieben, verwendet jedoch anstelle von 230 g des Cetyl-/Oleylalkoholgemisches 240 g des Anlagerungsproduktes von 4 Mol Ethylenoxid an 1 Mol Oleylamin, so erhält man eine bei Raumtemperatur viskose Dispersion mit einem Feststoffgehalt von ca. 50 %.EXAMPLE 7 If the procedure described in Example 1 is followed, but instead of 230 g of the cetyl / oleyl alcohol mixture, 240 g of the adduct of 4 moles of ethylene oxide and 1 mole of oleylamine are used, a dispersion which is viscous at room temperature and has a solids content of about 50 is obtained %.

Beispiel 8: Arbeitet man wie im Beispiel 1 beschrieben, verwendet jedoch anstelle von 230 g des Cetyl-/Oleylalkoholgemisches 230 g des Anlagerungsproduktes von 6 Mol Ethylenoxid an 1 Mol Laurinsäureamid, so erhält man eine bei Raumtemperatur viskose Dispersion mit einem Feststoffgehalt von ca. 49 %.EXAMPLE 8 If the procedure is as described in Example 1, but 230 g of the adduct of 6 mol of ethylene oxide and 1 mol of lauric acid amide are used instead of 230 g of the cetyl / oleyl alcohol mixture, a dispersion which is viscous at room temperature and has a solids content of approximately 49 is obtained %.

Beispiel 9: Chromgegerbtes, auf einen pH-Wert von 5,2 entsäuertes Rindsleder mit einer Falzstärke von 1,8 mm wird auf übliche Weise mit 1 %, bezogen auf das Gewicht des Leders, des Farbstoffes der Formel

Figure imgb0001
gefärbt. Anschliessend wird das Leder mit 8% des gemäss Beispiel 1 hergestellten Produktes, bezogen auf das Falzgewicht, nachbehandelt. Die Gesamtflottenlänge beträgt 100%. Danach wird es mit Ameisensäure auf einen pH-Wert von 3,8 eingestellt. Anschliessend wird das Leder gewaschen, mechanisch ausgereckt und getrocknet. Example 9: Chrome-tanned cowhide leather deacidified to a pH of 5.2 with a fold thickness of 1.8 mm is made in the usual way with 1%, based on the weight of the leather, of the dye of the formula
Figure imgb0001
 colored. The leather is then post-treated with 8% of the product produced in Example 1, based on the shaved weight. The total fleet length is 100%. Then it is adjusted to a pH of 3.8 with formic acid. The leather is then washed, mechanically stretched and dried.

Das erhaltene Leder ist sehr weich, im Griff geschmeidig und zeigt eine brillante und egale Färbung.The leather obtained is very soft, supple to the touch and shows a brilliant and level coloring.

Bei der Prüfung des Foggingverhaltens nach DIN 75201, Verfahren B (gravimetrische Prüfung), zeigt das so nachbehandelte Leder einen geringeren Foggingniederschlag als ein mit einem üblichen Fettungsmittel (Derivat von Fischöl) nachbehandeltes Leder.When testing the fogging behavior according to DIN 75201, method B (gravimetric test), the leather treated in this way shows a lower fogging precipitation than a leather treated with a conventional fatliquor (derivative of fish oil).

Claims (14)

  1. A process for aftertreating tanned leather and pelts, which comprises subjecting the leather or pelts to an aftertreatment with a polymer which is obtainable by
    (a) polymerizing a monoethylenically unsaturated dicarboxylic anhydride of 4 to 8 carbon atoms or a mixture of these dicarboxylic anhydrides, and
    (b) thereafter partially esterifying and/or amidating said polymer with a
    (b1) C1-C30alcohol and/or a primary or secondary amine compound and/or
    (b2) the reaction product of an
    (α) unsaturated or saturated C1-C30fatty alcohol, a C8-C22fatty acid, a C8-C22fatty amine or a C8-C22fatty amide and
    (β) ethylene oxide and/or propylene oxide
    in the molar ratio of 1:2 to 1:20,
    and, in an optical subsequent step, hydrolysing the anhydride groups of the homopolymers with aqueous bases.
  2. A process according to claim 1, which comprises using a polymer which is obtainable by
    (a) polymerizing a monoethylenically unsaturated dicarboxylic anhydride of 4 to 8 carbon atoms or a mixture of these dicarboxylic anhydrides, and
    (b) thereafter partially esterifying and/or amidating said polymer with the reaction product of
    (α) an unsaturated or saturated C1-C30fatty alcohol, a C8-C22fatty acid, a C8-C22fatty amine or C8-C22fatty amide and
    (β) ethylene oxide and/or propylene oxide in the molar ratio of 1:2 to 1:20,
    and subsequently hydrolysing the anhydride groups of the homopolymers with aqueous bases.
  3. A process according to claim 1 or 2, which comprises using a polymer in which the degree of esterification is 5 to 40%, preferably 25 to 35%, based on the amount of monomers.
  4. A process according to one of claims 1 to 3, wherein the unsaturated dicarboxylic anhydride used is maleic anhydride, citraconic anhydride, methylenemalonic anhydride or mixtures of these compounds with one another.
  5. A process according to claim 4, wherein the dicarboxylic anhydride used is maleic anhydride.
  6. A process according to one of claims 1 to 5, wherein the C1-C30alcohol used as component (b1) is a mixture of cetyl/oleyl alcohol.
  7. A process according to claim 1, wherein the amine compound used for the optional partial amidation is ammonia, mono- or di-C1-C5alkylamine, phenyl-C1-C5alkylamine, mono-or di-C5-C7cycloalkylamine or morpholine.
  8. A process according to claim 1 or 2, wherein component (α) is a C8-C22fatty acid.
  9. A process according to one of claims 1 to 8, wherein the leather or pelts are aftertreated with the polymer from an aqueous liquor at a pH from 4 to 10.
  10. An aqueous formulation for aftertreating leather or pelts, which is obtainable by
    (a) polymerizing a monoethylenically unsaturated dicarboxylic anhydride of 4 to 8 carbon atoms or a mixture of these dicarboxylic anhydrides, and
    (b) thereafter partially esterifying and/or amidating said polymer with a
    (b1) C1-C30alcohol and/or a primary or secondary amine compound and/or
    (b2) the reaction product of an
    (α) unsaturated or saturated C1-C30fatty alcohol, a C8-C22fatty acid, a C8-C22fatty amine or a C8-C22fatty amide and
    (β) ethylene oxide and/or propylene oxide
    in the molar ratio of 1:2 to 1:20,
    and, in an optional subsequent step, hydrolysing the anhydride groups of the homopolymers with aqueous bases.
  11. An aqueous formulation according to claim 10, which is obtainable by
    (a) polymerizing a monoethylenically unsaturated dicarboxylic anhydride of 4 to 8 carbon atoms or a mixture of these dicarboxylic anhydrides, and
    (b) thereafter partially esterifying and/or amidating said polymer with the reaction product of
    (α) an unsaturated or saturated C1-C30fatty alcohol, a C8-C22fatty acid, a C8-C22fatty amine or a C8-C22fatty amide and
    (β) ethylene oxide and/or propylene oxide
    in the molar ratio of 1:2 to 1:20,
    and subsequently hydrolysing the anhydride groups of the homopolymers with aqueous bases.
  12. A process for the preparation of a formulation according to claim 10 or 11, wherein the polymerisation (a) is initiated by a polymerisation initiator which is employed in amounts of 5 to 40%, based on the amount of monomeric anhydride employed in each case, and the partial esterification (b) is carried out such that 5 to 75% of the carboxyl groups are esterified.
  13. Leather or pelts aftertreated according to any one of claims 1 to 9.
  14. A polymer which is obtainable by
    (a) polymerizing a monoethylenically unsaturated dicarboxylic anhydride of 4 to 8 carbon atoms or a mixture of these dicarboxylic anhydrides, and
    (b) thereafter partially esterifying and/or amidating said polymer with a
    (b1) C1-C30alcohol and/or a primary or secondary amine compound and/or
    (b2) the reaction product of an
    (α) unsaturated or saturated C1-C30fatty alcohol, a C8-C22fatty acid, a C8-C22fatty amine or a C8-C22fatty amide and
    (β) ethylene oxide and/or propylene oxide
    in the molar ratio of 1:2 to 1:20,
    and, in an optional subsequent step, hydrolysing the anhydride groups of the homopolymers with aqueous bases.
EP93810396A 1992-06-09 1993-06-01 Process for the after-treatment of tanned leather and furs Expired - Lifetime EP0574351B1 (en)

Applications Claiming Priority (2)

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CH1836/92 1992-06-09
CH183692 1992-06-09

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EP0574351B1 true EP0574351B1 (en) 1996-08-21

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DE4405205A1 (en) * 1994-02-18 1995-08-24 Henkel Kgaa New leather greasing agents and their use
DE19636494C2 (en) * 1996-09-09 2000-11-16 Stockhausen Chem Fab Gmbh Low-monomer, amine-free polymers, processes for their preparation and their use in the production of low-fogging leather
US6091995A (en) * 1996-11-08 2000-07-18 Surx, Inc. Devices, methods, and systems for shrinking tissues
DE19942681B4 (en) * 1999-09-07 2006-04-27 Dr. Th. Böhme KG Chem. Fabrik GmbH & Co Copolymer for the treatment of leather and fur skins
IT201700007426A1 (en) 2017-01-24 2018-07-24 Re Al Color S R L TANNING AGENTS AND TANNING PROCESS
SI3597778T1 (en) 2018-07-18 2021-08-31 Re. Al. Color S.r.l. Chrome-free tanning agents and tanning process

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GB1411063A (en) * 1973-02-14 1975-10-22 Ciba Geigy Uk Ltd Polymerisation process
US4018702A (en) * 1974-03-11 1977-04-19 Calgon Corporation Corrosion inhibition with amine adducts of maleic anhydride polymers
US4196271A (en) * 1975-12-24 1980-04-01 Toagosei Chemical Industry Co., Ltd. Adhesive composition
US4086177A (en) * 1976-02-09 1978-04-25 Shell Oil Company Activated bleaching process and compositions therefor
DE2629748C2 (en) * 1976-07-02 1979-06-07 Zschimmer & Schwarz Chemische Fabriken, 5420 Lahnstein Use of copolymers of monoolefins and maleic anhydride for filling and greasing leather and fur skins
GB2164339A (en) * 1984-09-11 1986-03-19 Ciba Geigy Ag Polymaleic anhydride derivatives
CA1321851C (en) * 1988-01-11 1993-08-31 Kathleen Anne Hughes Process for preparing functionalized polymeric compositions
DE3926167A1 (en) * 1989-08-08 1991-02-14 Basf Ag USE OF COPOLYMERISATS BASED ON LONG-CHAIN OLEFINS AND ETHYLENICALLY UNSATURATED DICARBONIC ACID ANHYDRIDES FOR THE HYDROPHOBICATION OF LEATHER AND FUR SKINS
DE3926168A1 (en) * 1989-08-08 1991-02-14 Basf Ag USE OF COPOLYMERISATS BASED ON LONG-CHAIN ALKYLVINYL ETHERS AND ETHYLENICALLY UNSATURATED DICARBONIC ACID ANHYDRIDES FOR THE HYDROPHOBICATION OF LEATHER AND FUR SKINS
DE3931039A1 (en) * 1989-09-16 1991-03-28 Basf Ag USE OF COPOLYMERISATS BASED ON LONG-CHAIN UNSATURATED ESTERS AND ETHYLENICALLY UNSATURATED CARBONIC ACIDS FOR THE HYDROPHOBICATION OF LEATHER AND FUR SKINS
ES2066189T3 (en) * 1989-11-13 1995-03-01 Ciba Geigy Ag PROCEDURE FOR THE PREPARATION OF LEATHERS AND SKINS.

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MX9303386A (en) 1994-01-31
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AR248430A1 (en) 1995-08-18
DE59303477D1 (en) 1996-09-26

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