EP0927271B1 - Novel leather-treatment agents, process for their preparation, and their use for producing low-fogging leathers - Google Patents

Novel leather-treatment agents, process for their preparation, and their use for producing low-fogging leathers Download PDF

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Publication number
EP0927271B1
EP0927271B1 EP97944848A EP97944848A EP0927271B1 EP 0927271 B1 EP0927271 B1 EP 0927271B1 EP 97944848 A EP97944848 A EP 97944848A EP 97944848 A EP97944848 A EP 97944848A EP 0927271 B1 EP0927271 B1 EP 0927271B1
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EP
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Prior art keywords
leather
acid
meth
polymerization
agents according
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EP97944848A
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German (de)
French (fr)
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EP0927271A1 (en
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Kurt Dahmen
Thomas Müller
Reinmar PEPPMÖLLER
Norbert Behlau
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Stockhausen GmbH and Co KG
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Stockhausen GmbH and Co KG
Chemische Fabrik Stockhausen GmbH
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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
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring

Definitions

  • the invention relates to new leather treatment agents for the production of leather with low Contained in volatile components, especially for high-quality car upholstery leather, a process for the preparation of these agents and their use in the manufacture low-fogging leather.
  • Car upholstery leather has to meet certain criteria. Is essential on the one hand the softness, on the other hand the authenticity to light and heat influences and finally the so-called fogging behavior.
  • DIN 75201 defines fogging as condensation of evaporated volatile components from the vehicle interior to the Glass panes, especially on the windshield. In the same standard are also a gravimetric and a reflectometric method to characterize the fogging behavior described by leather.
  • EP 498 634 A2 describes special polymers for the production of low-fogging leather recommended, the aqueous dispersions being essentially free of organic solvents are and contain an amphiphilic copolymer, which consists of a predominant Proportion of at least one hydrophobic monomer and a minor proportion of at least one hydrophilic monomer. Treating the leather with these Dispersions give good results in a gravimetric test according to DIN 75201. Reflectometric Investigations have not been disclosed.
  • amphiphilic copolymers are preferably prepared in an aqueous one Emulsion polymerization.
  • To achieve a Good emulsion stability also requires a sufficient amount of an emulsifier (Lauryl sulfate was used in the examples given) to add what leather processing can lead to wastewater problems.
  • DE 42 05 839 A1 describes the reaction of polymers from a) 30-100 mol% of unsaturated dicarboxylic acid anhydrides, b) 0 to 70 mol% of one or more vinyl aromatics, c) 0-70 mol% of vinyl esters of C 1 -C 8 -carboxylic acids , d) 0-50 mol% of C 2 -C 6 olefins, e) 0-30 mol% of unsaturated C 3 -C 5 carboxylic acids and up to 10% of other copolymerizable monomers with hydrophobic amines or alcohols.
  • the resulting products give treated leather special softness.
  • EP 466 392 B1 describes a process for the preparation of polymers which contain both pendant hydrophobic groups and pendant alkoxylated groups and that by derivatizing polymers after the actual polymerization process can be obtained by conventional methods.
  • So polymers are preferred simple monomers such as acrylamide and / or acrylic acid by conventional polymerization prepared and then with a mixture of primary or secondary hydrophobic Amines and primary or secondary alkoxylated amines derivatized.
  • Such derivatized Polymers are used as thickeners and dirt removers.
  • the object of the invention was therefore to create new, easy to produce, essentially self-emulsifying and agents for leather treatment poor in residual monomers, a process for their To provide manufacture and a process for leather manufacture using these agents, for the leather with very low levels of volatile volatiles (Low-fogging leather), determined according to both gravimetric and reflectometric Measurement methods are obtained, the other important leather properties such as softness, fastness to light and heat influences etc. are not impaired become.
  • the invention further relates to a process for the preparation of the leather treatment agent, which is characterized in that the monomers a1), a2) and a3) are polymerized by free radicals, preferably in solution, then the polymer obtained either immediately or after prior removal of the solvent with the Amines of the formula R 1 -NH-R 2 , in which R 1 and R 2 have the meaning given in claim 1, wherein at least some of the acid groups present in the polymer are converted into the corresponding amide groups, followed by dilute base, optionally with Addition of water, the remaining carboxyl groups are partially or completely neutralized.
  • Step A polymerization
  • the polymers are prepared by radical polymerization of, based on the total batch, 70-100% by weight, preferably more than 80% by weight, of acrylic acid and / or methacrylic acid and / or their acid chlorides and / or anhydrides.
  • acrylic acid and / or methacrylic acid and / or their acid chlorides and / or anhydrides are copolymerized.
  • 0 to 30% by weight of further copolymerizable water-soluble monomers are copolymerized.
  • Suitable monomers from this group are (meth) acrylamide, (meth) allyl alcohol, Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyalkylpolyethyleneoxy (meth) acrylate, Alkyloxypolyethyleneoxy (meth) acrylate, polyethylene glycol monoallyl ether, N-vinyl pyrrolidone or N-vinyl imidazole.
  • monomers containing acid groups such as maleic acid, itaconic acid, vinylsulfonic acid, methallylsulfonic acid, 2-acrylamido-2-methylpropylsulfonic acid, 4-vinylphenylsulfonic acid, vinylphosphonic acid and their water-soluble esters, anhydrides, alkali metal, alkaline earth metal and / or ammonium salts can also be used.
  • basic monomers such as dimethylaminoalkyl (meth) acrylate and / or dimethylaminoalkyl (meth) acrylamide and / or their quaternized forms in the polymerization.
  • the polymers from these monomers naturally have a very hydrophilic character. It can therefore make sense to influence the hydrophilicity by using 0 to 20% by weight of one or more monomers from the group of hydrophobic monomers.
  • This group includes, for example, C 1 -C 30 alkyl (meth) acrylates, vinyl esters of C 1 -C 30 carboxylic acids, vinyl ethers of C 1 -C 30 alcohols or ethylenically unsaturated aromatic monomers such as styrene.
  • the polymerization itself can be carried out by the process of bulk, solution, suspension or emulsion polymerization.
  • the process of solution polymerization is preferred, the solvent having to meet the condition that it can dissolve all the monomers used. Accordingly, water, C 1 -C 4 alcohols and their ethylene oxide adducts, glycols and ketones such as acetone or methyl ethyl ketone are suitable, with higher-boiling organic solvents being preferred in the end product because of their more favorable fogging behavior.
  • the use of butyl glycol and butyl diglycol as a solvent in the polymerization is particularly preferred.
  • the polymerization can be carried out batchwise or continuously, can be carried out, for example, in a cascade of reaction vessels.
  • the reaction becomes batch carried out, a feed process is preferred, in which over a period of time of several hours monomers and initiator at constant temperature in the Template be dosed.
  • Adiabatic driving is also possible, however which all or part of the monomers are introduced and the heat of polymerization that arises to increase the temperature and accelerate the conversion of the monomers of the approach leads.
  • the radical polymerization is initiated by conventional starters, for example through the thermally or photochemically induced decay of radical-forming peroxide and / or azo compounds and / or triggered by suitable redox systems, the Selection of the suitable system according to the intended reaction temperature and the conversion rate judges.
  • the adiabatic polymerization of the monomers can it makes sense to use several starters, for example with different decomposition temperatures. As a rule, those systems are preferred which are adequate in the reaction medium Have solubility.
  • the initiator amounts are preferably in the range of 0.01 up to 1 wt .-%, based on the sum of the monomers.
  • the molecular weight of the polymers is regulated via the reaction conditions and / or by using regulators such as mercaptans.
  • the regulator set is preferably in the range from 0 to 5% by weight, based on the sum of the monomers.
  • the number average molecular weights determined by means of gel permeation chromatography The polymers obtained are between 1000 and 100,000 g / mol.
  • Reaction temperatures in the range from 20 to 200 ° C. are preferred, where appropriate the polymerization can also be carried out under pressure.
  • the polymerization time are advantageously 0.5 - 8 hours.
  • step B either the polymer-analogous reaction of the polymer according to step B) is continued immediately or else the solvent is first separated from the polymer, for example by distillation.
  • the latter is in aqueous polymerization Medium necessary to achieve sufficient conversion in the subsequent reaction of the polymer.
  • Step B implementation with fatty amines
  • part of the acid groups present in the polymer is reacted with fatty amines of the formula I.
  • the amount of fatty amine used according to the invention determines the degree of softness of the Leather.
  • alkyl chain In addition to the amount of fatty amine used, the length of the alkyl chain has an influence the achievable softness. Generally, alkyl chains with 12-30 C atoms give a good one Availability of funds. For particularly soft leather types, fatty amines with a Carbon number between 16 and 22 preferred. The use of is particularly preferred Oleylamine and stearylamine for polymer-analogous implementation.
  • the reaction of the polymers with the fatty amines is preferably carried out in the presence acidic catalysts, for example with p-toluenesulfonic acid.
  • the amount of catalyst should Do not exceed 1 mol%, based on the carboxyl groups present.
  • the duration of the reaction depends on the desired conversion, for example can be followed by thin layer chromatography and should be greater than 90%.
  • the reaction temperature is between 60 and 200 ° C, especially lower Reaction temperature a reaction under reduced pressure is advantageous. To achieve For sales of more than 99%, the water of reaction formed may be necessary to remove azeotropically.
  • Step C Conversion of residual fatty amine to N-substituted- ⁇ -aminopropionic acids This optional step is carried out if a particularly low residual amine content in the Final product is required.
  • the details of this reaction are in described in DE 37 17 961 C2.
  • One advantage of this step is that it does this it is not absolutely necessary to achieve low amounts of residual amine during step B, which is why with the fatty amine in excess, that is, with more than 80 mol%, based on carboxyl groups.
  • Step D neutralization and dispersion
  • carboxyl groups partially or completely neutralized with dilute base, if necessary with the addition of water, wherein the polymer is dispersed or dissolved.
  • dilute base if necessary with the addition of water, wherein the polymer is dispersed or dissolved.
  • bases Alkali and alkaline earth hydroxides, ammonia, amines or amino alcohols.
  • the amount of base is chosen so that a pH value between 5 and 9 is established.
  • the invention aqueous emulsions are adjusted to a solids content of 20 to 80 wt .-%.
  • the invention further relates to the use of the compositions according to the invention for the production upper leather with a low content of volatile volatiles, especially car upholstery leather.
  • the agents according to the invention which contain the modified polymers, can either as such or in combination with other fatliquoring agents in the manufacture of Car upholstery leather can be used.
  • the products according to the invention are suitable also for the production of waterproof leather or washable clothing leathers.
  • the amount of use of the products is 2 to 20% by weight, preferably 5 to 15% by weight, based on the fold weight of the leather. They are usually used in the fat level of leather processing.
  • the dosing time is approximately one hour.
  • the mixture is stirred at 80 ° C. for a further 30 minutes and then 58 g (0.22 mol) of oleylamine and 0.4 g of p-toluenesulfonic acid were added.
  • the temperature is raised to 150 ° C. and the mixture is stirred for 4 hours, with 15 g of distillate decreased.
  • the mixture was examined by thin layer chromatography. There was a residual amine content of 5% based on the total product accordingly a turnover of approx. 85%. It was cooled to approx. 95 ° C.
  • the addition was then carried out 2.0 g of acrylic acid followed by the addition of 1.8 g of maleic anhydride.
  • Example 1 was repeated, but 0.5 g hypophosphorous were used as the catalyst for the amidation Acid added. There was a residual amine content after the polymer-analogous amidation of 0.8%, which is why the reaction with acrylic acid and MSA is dispensed with has been. It became a clear yellow product with an active substance of 40% by weight and one Obtained pH of 6.6.
  • Example 1 was repeated, but 110 g of oleylamine (0.42 mol) were used. It resulted a yellow emulsion with a pH of 7.5 and an active substance of 40 % By weight.
  • Example 5 Production of a car upholstery leather
  • the leathers are wet-stretched on the trestle overnight, dried, moistened, and chugged and grilled.
  • Comparative examples were a low-fogging polymer lubricant (V1: commercial product "Magnopal®” SOF, manufacturer Stockhausen GmbH & Co. KG) and a low-fogging lubricant based on fish oils (V2: commercial product "Chromopol®” LFC, manufacturer Stockhausen GmbH & Co. KG) used.
  • V1 commercial product "Magnopal®” SOF, manufacturer Stockhausen GmbH & Co. KG
  • V2 commercial product "Chromopol®” LFC, manufacturer Stockhausen GmbH & Co. KG
  • Softness grading according to the school grade principle (1: very good; 6: insufficient).
  • Fogging gravimetric data in mg / 50 cm 2
  • Lightfastness according to DIN 54004, assessment against blue scale under daylight lamp, lower numbers correspond to stronger yellowing.
  • the table shows that the products according to the invention are the products of the prior art are superior in at least one criterion.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Description

Die Erfindung betrifft neue Lederbehandlungsmittel für die Herstellung von Ledern mit geringen Gehalten an flüchtigen Bestandteilen, insbesondere für hochwertige Autopolsterleder, ein Verfahren zur Herstellung dieser Mittel und ihre Verwendung bei der Herstellung foggingarmer Leder. Autopolsterleder müssen bestimmte Kriterien erfüllen. Wesentlich ist einerseits die Weichheit, andererseits die Echtheit gegenüber Licht und Wärmeeinflüssen und schließlich das sogenannte Foggingverhalten. Die DIN 75201 definiert Fogging als Kondensation von verdampften flüchtigen Bestandteilen aus der Fahrzeuginnenausstattung an den Glasscheiben, insbesondere an der Windschutzscheibe. In derselben Norm werden auch ein gravimetrisches und ein reflektometrisches Verfahren zur Charakterisierung des Fogging-Verhaltens von Leder beschrieben.The invention relates to new leather treatment agents for the production of leather with low Contained in volatile components, especially for high-quality car upholstery leather, a process for the preparation of these agents and their use in the manufacture low-fogging leather. Car upholstery leather has to meet certain criteria. Is essential on the one hand the softness, on the other hand the authenticity to light and heat influences and finally the so-called fogging behavior. DIN 75201 defines fogging as condensation of evaporated volatile components from the vehicle interior to the Glass panes, especially on the windshield. In the same standard are also a gravimetric and a reflectometric method to characterize the fogging behavior described by leather.

In der EP 498 634 A2 werden spezielle Polymere für die Herstellung von low-fogging Leder empfohlen, wobei die wäßrigen Dispersionen im wesentlichen frei von organischen Lösungsmitteln sind und ein amphiphiles Copolymer enthalten, welches aus einem überwiegenden Anteil von mindestens einem hydrophoben Monomeren und einem geringeren Anteil von mindestens einem hydrophilen Monomeren besteht. Die Behandlung der Leder mit diesen Dispersionen führt bei einem gravimetrischen Test nach DIN 75201 zu guten Resultaten. Reflektometrische Untersuchungen wurden nicht offenbart.EP 498 634 A2 describes special polymers for the production of low-fogging leather recommended, the aqueous dispersions being essentially free of organic solvents are and contain an amphiphilic copolymer, which consists of a predominant Proportion of at least one hydrophobic monomer and a minor proportion of at least one hydrophilic monomer. Treating the leather with these Dispersions give good results in a gravimetric test according to DIN 75201. Reflectometric Investigations have not been disclosed.

Die Herstellung dieser amphiphilen Copolymere erfolgt vorzugsweise in einer wäßrigen Emulsionspolymerisation. Dies führt jedoch aufgrund der unterschiedlichen Hydrophilie der einzusetzenden Monomere naturgemäß zu Problemen beim Copolymerisationsverhalten, was im Extremfall dazu führen kann, daß die Monomere in unerwünschter Weise jeweils für sich Homopolymerisate bilden. Eine weitere Folge der an sich ungünstigen Lösungsverhältnisse ist eine aufwendige Nachbearbeitung zur Zerstörung von Restmonomeren. Zur Erzielung einer guten Emulsionsstabilität ist es außerdem erforderlich, eine ausreichende Menge eines Emulgators (in den angeführten Beispielen wurde Laurylsulfat verwendet) hinzuzufügen, was bei der Lederbearbeitung zu Abwasserproblemen führen kann.These amphiphilic copolymers are preferably prepared in an aqueous one Emulsion polymerization. However, this leads to the different hydrophilicity of the Monomers to be used naturally lead to problems in the copolymerization behavior, what in extreme cases can lead to the monomers being undesirable in each case Form homopolymers. Another consequence of the inherently unfavorable solution conditions is a complex post-processing to destroy residual monomers. To achieve a Good emulsion stability also requires a sufficient amount of an emulsifier (Lauryl sulfate was used in the examples given) to add what leather processing can lead to wastewater problems.

Es ist weiterhin bekannt, durch polymeranaloge Umsetzung mit Fettalkoholen fettchemische Rohstoffe herzustellen. Grundlegende Prinzipien werden in Fat Sci. Technol. 92, Nr. 10, S.397-400 beschrieben. Obwohl auch denkbare Einsatzgebiete diskutiert werden, ist eine Anwendung in der Lederherstellung nicht beschrieben.It is also known to be oleochemical by polymer-analogous reaction with fatty alcohols To produce raw materials. Basic principles are described in Fat Sci. Technol. 92, No. 10, S.397-400. Although conceivable areas of application are also discussed, one application is not described in leather production.

Die DE 42 05 839 A1 beschreibt die Umsetzung von Polymerisaten aus a) 30-100 mol% ungesättigten Dicarbonsäureanhydriden, b) 0 bis 70 mol% eines oder mehrerer Vinylaromaten, c) 0-70 mol% Vinylestern von C1-C8-Carbonsäuren, d) 0-50 mol% C2-C6-Olefinen, e) 0-30 mol% ungesättigter C3-C5-Carbonsäuren und bis zu 10% weiteren copolymerisierbaren Monomeren mit hydrophoben Aminen oder Alkoholen. Die resultierenden Produkte verleihen damit behandelten Ledern besondere Weichheit.DE 42 05 839 A1 describes the reaction of polymers from a) 30-100 mol% of unsaturated dicarboxylic acid anhydrides, b) 0 to 70 mol% of one or more vinyl aromatics, c) 0-70 mol% of vinyl esters of C 1 -C 8 -carboxylic acids , d) 0-50 mol% of C 2 -C 6 olefins, e) 0-30 mol% of unsaturated C 3 -C 5 carboxylic acids and up to 10% of other copolymerizable monomers with hydrophobic amines or alcohols. The resulting products give treated leather special softness.

Nachteil dieser Verfahrensweise ist die große Menge schlecht polymerisierbarer Dicarbonsäureanhydride, weshalb drastische Polymerisationsbedingungen gewählt werden müssen, um einen für ein gutes Foggingverhalten erforderlichen niedrigen Anteil niedermolekularer Substanzen im Endprodukt zu erhalten. Die Angaben in den Beispielen: Polymerisationstemperatur bei der Siedetemperatur des Lösungsmittels Xylol, ca. 136-140°C, mindestens 3 Stunden, bestätigen diesen Sachverhalt.The disadvantage of this procedure is the large amount of poorly polymerizable dicarboxylic anhydrides, which is why drastic polymerization conditions have to be chosen in order to a low proportion of low molecular weight substances required for good fogging behavior to get in the final product. The information in the examples: polymerization temperature at the boiling point of the solvent xylene, approx. 136-140 ° C, at least 3 hours, confirm this fact.

In der EP 466 392 B1 wird ein Verfahren zur Herstellung von Polymeren beschrieben, die sowohl seitenständige hydrophobe Gruppen als auch seitenständige alkoxylierte Gruppen enthalten und die durch eine Derivatisierung von Polymeren nach dem eigentlichen Polymerisationsprozeß nach üblichen Verfahren erhalten werden. So werden bevorzugt Polymere aus einfachen Monomeren wie Acrylamid und/oder Acrylsäure durch herkömmliche Polymerisation hergestellt und danach mit einer Mischung aus primären bzw. sekundären hydrophoben Aminen und primären bzw. sekundären alkoxylierten Aminen derivatisiert. Derartige derivatisierte Polymere werden als Verdickungsmittel und Schmutzlösemittel eingesetzt. EP 466 392 B1 describes a process for the preparation of polymers which contain both pendant hydrophobic groups and pendant alkoxylated groups and that by derivatizing polymers after the actual polymerization process can be obtained by conventional methods. So polymers are preferred simple monomers such as acrylamide and / or acrylic acid by conventional polymerization prepared and then with a mixture of primary or secondary hydrophobic Amines and primary or secondary alkoxylated amines derivatized. Such derivatized Polymers are used as thickeners and dirt removers.

Aufgabe der Erfindung war es daher, neue, einfach herstellbare, im wesentlichen selbstemulgierende und an Restmonomeren arme Mittel zur Lederbehandlung, ein Verfahren zu ihrer Herstellung und ein Verfahren für die Lederherstellung unter Verwendung dieser Mittel bereitzustellen, bei dem Leder mit sehr niedrigen Gehalten an verdampfenden flüchtigen Bestandteilen (Low-Fogging-Leder), bestimmt sowohl nach gravimetrischen als auch nach reflektometrischen Meßverfahren erhalten werden, wobei die übrigen wichtigen Ledereigenschaften wie Weichheit, Echtheit gegenüber Licht und Wärmeeinflüssen usw. nicht beeinträchtigt werden.The object of the invention was therefore to create new, easy to produce, essentially self-emulsifying and agents for leather treatment poor in residual monomers, a process for their To provide manufacture and a process for leather manufacture using these agents, for the leather with very low levels of volatile volatiles (Low-fogging leather), determined according to both gravimetric and reflectometric Measurement methods are obtained, the other important leather properties such as softness, fastness to light and heat influences etc. are not impaired become.

Gegenstand der Erfindung sind neue Lederbehandlungsmittel, insbesondere für Autopolsterleder, erhältlich durch

  • A)
    Polymerisation von
  • a1) 70-100 Gew% Acrylsäure und/oder Methacrylsäure und/oder deren Säurechloriden und/oder deren Anhydriden mit
  • a2) 0-30 Gew.% weiteren mit a1) copolymerisierbaren wasserlöslichen Monomeren und
  • a3) 0-20 Gew.% mit a1) und a2) copolymerisierbaren wasserunlöslichen Monomeren,
  • B)
    Umsetzung des Polymerisates aus A) mit Aminen der Formel I R1-NH-R2 worin
  • R1 einen C12-C30 Alkyl- oder Alkenylrest
  • und R2 H, einen C1-C4-Alkyl- oder C1-C2-Hydroxyalkylrest bedeuten,
  • gegebenenfalls C)
    Umsetzung der nicht an das Polymerisat aus A) gebundenen Amine mit (Meth-)acrylsäure zu N-substituierten-β-Aminopropionsäuren und gegebenenfalls Acylierung,
  • D)
    Neutralisation und Dispergierung des aus B) bzw. aus C) angefallenen Produktes.
    • The invention relates to new leather treatment agents, in particular for car upholstery leather, available from
  • A)
    Polymerization of
  • a1) 70-100% by weight of acrylic acid and / or methacrylic acid and / or their acid chlorides and / or their anhydrides
  • a2) 0-30% by weight of further water-soluble monomers copolymerizable with a1) and
  • a3) 0-20% by weight of water-insoluble monomers copolymerizable with a1) and a2),
  • B)
    Reaction of the polymer from A) with amines of the formula I. R 1 -NH-R 2 wherein
  • R 1 is a C 12 -C 30 alkyl or alkenyl radical
  • and R 2 is H, a C 1 -C 4 alkyl or C 1 -C 2 hydroxyalkyl radical,
  • optionally C)
    Reaction of the amines not bound to the polymer from A) with (meth) acrylic acid to give N-substituted-β-aminopropionic acids and optionally acylation,
  • D)
    Neutralization and dispersion of the product obtained from B) or from C).

    • Gegenstand der Erfindung ist ferner ein Verfahren zur Herstellung der Lederbehandlungsmittel, das dadurch gekennzeichnet ist, daß man die Monomeren a1), a2) und a3) radikalisch, bevorzugt in Lösung polymerisiert, danach das erhaltene Polymerisat entweder sofort oder nach vorheriger Abtrennung des Lösungsmittels mit den Aminen der Formel R1-NH-R2, worin R1 und R2 die in Anspruch 1 angegebene Bedeutung haben, umsetzt, wobei wenigstens ein Teil der im Polymerisat vorhandenen Säuregruppen in die entsprechenden Amidgruppen umgewandelt werden, worauf mit verdünnter Base, gegebenenfalls unter Zusatz von Wasser, die verbleibenden Carboxylgruppen teilweise oder vollständig neutralisiert werden.The invention further relates to a process for the preparation of the leather treatment agent, which is characterized in that the monomers a1), a2) and a3) are polymerized by free radicals, preferably in solution, then the polymer obtained either immediately or after prior removal of the solvent with the Amines of the formula R 1 -NH-R 2 , in which R 1 and R 2 have the meaning given in claim 1, wherein at least some of the acid groups present in the polymer are converted into the corresponding amide groups, followed by dilute base, optionally with Addition of water, the remaining carboxyl groups are partially or completely neutralized.

    Schritt A: Polymerisation
    Die Polymerisate werden hergestellt durch radikalische Polymerisation von, bezogen auf den Gesamtansatz, 70 - 100 Gew.%, vorzugsweise mehr als 80 Gew% Acrylsäure und/oder Methacrylsäure und/oder deren Säurechloriden und/oder Anhydriden.
    Zur Verbesserung der Polymerisate hinsichtlich der angestrebten Eigenschaften bei der Lederbehandlung, insbesondere im Fogging-Verhalten, werden 0 bis 30 Gew.% weitere copolymerisierbare wasserlösliche Monomere einpolymerisiert.    Step A: polymerization
    The polymers are prepared by radical polymerization of, based on the total batch, 70-100% by weight, preferably more than 80% by weight, of acrylic acid and / or methacrylic acid and / or their acid chlorides and / or anhydrides.
    To improve the polymers with regard to the desired properties in leather treatment, in particular in fogging behavior, 0 to 30% by weight of further copolymerizable water-soluble monomers are copolymerized.

    Beispiele für geeignete Monomere dieser Gruppe sind (Meth)acrylamid, (Meth)allylalkohol, Hydroxyethyl(meth)acrylat, Hydroxypropyl(meth)acrylat, Hydroxyalkylpolyethylenoxy(meth)acrylat, Alkyloxypolyethylenoxy(meth)acrylat, Polyethylenglykolmonoallylether, N-Vinylpyrrolidon oder N-Vinylimidazol. Examples of suitable monomers from this group are (meth) acrylamide, (meth) allyl alcohol, Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyalkylpolyethyleneoxy (meth) acrylate, Alkyloxypolyethyleneoxy (meth) acrylate, polyethylene glycol monoallyl ether, N-vinyl pyrrolidone or N-vinyl imidazole.

    Ebenso verwendbar sind weitere säuregruppenhaltige Monomere wie Maleinsäure, Itaconsäure, Vinylsulfonsäure, Methallylsulfonsäure, 2-Acrylamido-2-methylpropylsulfonsäure, 4-Vinylphenylsulfonsäure, Vinylphosphonsäure sowie deren wasserlösliche Ester, Anhydride, Alkali-, Erdalkali- und/oder Ammoniumsalze.
    Desweiteren kann es sinnvoll sein, basische Monomere, wie beispielsweise Dimethylaminoalkyl(meth)acrylat und/oder Dimethylaminoalkyl(meth)acrylamid und/oder deren quatemierte Formen bei der Polymerisation einzusetzen.    Other monomers containing acid groups, such as maleic acid, itaconic acid, vinylsulfonic acid, methallylsulfonic acid, 2-acrylamido-2-methylpropylsulfonic acid, 4-vinylphenylsulfonic acid, vinylphosphonic acid and their water-soluble esters, anhydrides, alkali metal, alkaline earth metal and / or ammonium salts can also be used.
    Furthermore, it can be useful to use basic monomers, such as dimethylaminoalkyl (meth) acrylate and / or dimethylaminoalkyl (meth) acrylamide and / or their quaternized forms in the polymerization.

    Die Polymerisate aus diesen Monomeren weisen naturgemäß einen sehr hydrophilen Charakter auf. Es kann daher sinnvoll sein, die Hydrophilie durch den Einsatz von 0 bis 20 Gew.%, eines oder mehrerer Monomere aus der Gruppe von hydrophoben Monomeren zu beeinflussen. Diese Gruppe umfasst beispielsweise C1-C30 Alkyl(meth)acrylate, Vinylester von C1-C30 Carbonsäuren, Vinylether von C1-C30 Alkoholen oder ethylenisch ungesättigte aromatische Monomere, wie Styrol.The polymers from these monomers naturally have a very hydrophilic character. It can therefore make sense to influence the hydrophilicity by using 0 to 20% by weight of one or more monomers from the group of hydrophobic monomers. This group includes, for example, C 1 -C 30 alkyl (meth) acrylates, vinyl esters of C 1 -C 30 carboxylic acids, vinyl ethers of C 1 -C 30 alcohols or ethylenically unsaturated aromatic monomers such as styrene.

    Die Polymerisation selbst kann nach dem Verfahren der Masse-, Lösungs-, Suspensions- oder Emulsionspolymerisation erfolgen. Bevorzugt wird das Verfahren der Lösungspolymerisation, wobei das Lösungsmittel die Bedingung erfüllen muß, daß es alle eingesetzten Monomeren zu lösen vermag. Geeignet sind demnach Wasser, C1-C4-Alkohole sowie deren Ethylenoxid-Addukte, Glykole und Ketone wie Aceton oder Methylethylketon, wobei höhersiedende organische Lösungsmittel aufgrund ihres günstigeren Fogging-Verhaltens im Endprodukt bevorzugt werden. Die Verwendung von Butylglykol und Butyldiglykol als Lösungsmittel bei der Polymerisation ist besonders bevorzugt.The polymerization itself can be carried out by the process of bulk, solution, suspension or emulsion polymerization. The process of solution polymerization is preferred, the solvent having to meet the condition that it can dissolve all the monomers used. Accordingly, water, C 1 -C 4 alcohols and their ethylene oxide adducts, glycols and ketones such as acetone or methyl ethyl ketone are suitable, with higher-boiling organic solvents being preferred in the end product because of their more favorable fogging behavior. The use of butyl glycol and butyl diglycol as a solvent in the polymerization is particularly preferred.

    Die Polymerisation kann sowohl diskontinuierlich als auch in kontinuierlicher Fahrweise, beispielsweise in einer Reaktionskesselkaskade durchgeführt werden. Wird die Reaktion absatzweise durchgeführt, so ist ein Zulaufverfahren bevorzugt, bei welchem über einen Zeitraum von mehreren Stunden Monomere und Initiator bei gleichbleibender Temperatur in die Vorlage dosiert werden. Daneben ist jedoch auch eine adiabatische Fahrweise möglich, bei welcher die Monomeren ganz oder teilweise vorgelegt werden und die entstehende Polymerisationswärme zur Temperaturerhöhung und zur beschleunigten Umsetzung der Monomeren des Ansatzes führt.The polymerization can be carried out batchwise or continuously, can be carried out, for example, in a cascade of reaction vessels. The reaction becomes batch carried out, a feed process is preferred, in which over a period of time of several hours monomers and initiator at constant temperature in the Template be dosed. Adiabatic driving is also possible, however which all or part of the monomers are introduced and the heat of polymerization that arises to increase the temperature and accelerate the conversion of the monomers of the approach leads.

    Die Initiierung der radikalischen Polymerisation wird durch übliche Starter, beispielsweise durch den thermisch oder photochemisch induzierten Zerfall von radikalbildenen Peroxid- und/oder Azoverbindungen und/oder durch geeignete Redoxsysteme ausgelöst, wobei sich die Auswahl des geeigneten Systems nach der vorgesehenen Reaktionstemperatur und der Umsatzgeschwindigkeit richtet. Bei der adiabatischen Polymerisation der Monomeren kann es sinnvoll sein, mehrere Starter, beispielsweise mit unterschiedlichen Zerfallstemperaturen, einzusetzen. In der Regel werden solche Systeme bevorzugt, die im Reaktionsmedium eine ausreichende Löslichkeit aufweisen. Die Initiatormengen liegen bevorzugt im Bereich von 0,01 bis 1 Gew.-%, bezogen auf die Summe der Monomeren.The radical polymerization is initiated by conventional starters, for example through the thermally or photochemically induced decay of radical-forming peroxide and / or azo compounds and / or triggered by suitable redox systems, the Selection of the suitable system according to the intended reaction temperature and the conversion rate judges. The adiabatic polymerization of the monomers can it makes sense to use several starters, for example with different decomposition temperatures. As a rule, those systems are preferred which are adequate in the reaction medium Have solubility. The initiator amounts are preferably in the range of 0.01 up to 1 wt .-%, based on the sum of the monomers.

    Die Regelung der Molmasse der Polymerisate erfolgt über die Reaktionsbedingungen und/oder durch den Einsatz von Reglern, wie beispielsweise Mercaptanen. Die Reglermenge liegt bevorzugt im Bereich von 0 bis 5 Gew.-%, bezogen auf die Summe der Monomeren.The molecular weight of the polymers is regulated via the reaction conditions and / or by using regulators such as mercaptans. The regulator set is preferably in the range from 0 to 5% by weight, based on the sum of the monomers.

    Die mittels Gelpermeationschromatographie bestimmten Zahlenmittel der Molmassen der erhaltenen Polymerisate liegen zwischen 1000 und 100.000 g/mol.The number average molecular weights determined by means of gel permeation chromatography The polymers obtained are between 1000 and 100,000 g / mol.

    Es werden Reaktionstemperaturen im Bereich von 20 - 200 °C bevorzugt, wobei gegebenenfalls die Polymerisation auch unter Druck vorgenommen werden kann. Die Polymerisationsdauer betragen vorteilhaft 0,5 - 8 Stunden.Reaction temperatures in the range from 20 to 200 ° C. are preferred, where appropriate the polymerization can also be carried out under pressure. The polymerization time are advantageously 0.5 - 8 hours.

    Nach der Polymerisation wird entweder sofort mit der polymeranalogen Umsetzung des Polymerisates gemäß Schritt B) fortgefahren oder aber man trennt zunächst das Lösungsmittel vom Polymerisat, beispielsweise destillativ, ab. Letzteres ist bei Polymerisation in wäßrigem
    Medium notwendig, um bei der nachfolgenden Umsetzung des Polymerisats einen ausreichenden Umsatz zu erzielen.    After the polymerization, either the polymer-analogous reaction of the polymer according to step B) is continued immediately or else the solvent is first separated from the polymer, for example by distillation. The latter is in aqueous polymerization
    Medium necessary to achieve sufficient conversion in the subsequent reaction of the polymer.

    Schritt B: Umsetzung mit Fettaminen
    In diesem erfindungsgemäßen Reaktionschritt wird ein Teil der vorhandenen Säuregruppen des Polymerisates durch Umsetzung mit Fettaminen der Formel I R1-NH-R2 mit R1=C12-C30 Alkyl- oder Alkenylrest
    und R2 = H, C1-C4-Alkylrest oder C1-C2-Hydroxyalkylrest
    in die entsprechenden Amidgruppen umgewandelt.    Step B: implementation with fatty amines
    In this reaction step according to the invention, part of the acid groups present in the polymer is reacted with fatty amines of the formula I. R 1 -NH-R 2 with R 1 = C 12 -C 30 alkyl or alkenyl radical
    and R 2 = H, C 1 -C 4 alkyl or C 1 -C 2 hydroxyalkyl
    converted into the corresponding amide groups.

    Im Gegensatz zur Verwendung von Fettalkoholen nach DE 42 05 839 A1 wurde bei der erfindungsgemäßen Verwendung von Fettaminen eine deutlich verbesserte Produktstabilität beobachtet.In contrast to the use of fatty alcohols according to DE 42 05 839 A1, in the case of the invention Use of fatty amines observed a significantly improved product stability.

    Die erfindungsgemäß eingesetzte Menge des Fettamins bestimmt den Weichheitsgrad des Leders. Je mehr Säuregruppen des Polymerisates durch die Umsetzung mit einem oder mehreren Fettaminen modifiziert werden, desto weicher wird das damit behandelte Leder. Da die Selbstemulgierbarkeit des entstehenden Polymers beeinflußt wird, sollten jedoch nicht alle Carboxylgruppen des Polymerisats auf diese Weise umgesetzt werden. In Versuchen hat sich die Umsetzung einer Menge von 20 bis 80 mol%, bezogen auf die im Polymerisat vorhandenen Carboxylgruppen, als vorteilhaft erwiesen.The amount of fatty amine used according to the invention determines the degree of softness of the Leather. The more acid groups of the polymer through the reaction with one or more Fatty amines are modified, the softer the leather treated with them. Since the Self-emulsifiability of the resulting polymer is not affected, however Carboxyl groups of the polymer are implemented in this way. In trials the conversion of an amount of 20 to 80 mol%, based on those present in the polymer Carboxyl groups, proven to be advantageous.

    Neben der Menge des eingesetzten Fettamins übt die Länge der Alkylkette einen Einfluß auf die erzielbare Weichheit aus. Generell ergeben Alkylketten mit 12-30 C-Atomen eine gute Verwendbarkeit der Mittel. Für besonders weiche Ledertypen werden Fettamine mit einer Kohlenstoffzahl zwischen 16 und 22 bevorzugt. Besonders bevorzugt ist die Verwendung von Oleylamin und Stearylamin zur polymeranalogen Umsetzung.In addition to the amount of fatty amine used, the length of the alkyl chain has an influence the achievable softness. Generally, alkyl chains with 12-30 C atoms give a good one Availability of funds. For particularly soft leather types, fatty amines with a Carbon number between 16 and 22 preferred. The use of is particularly preferred Oleylamine and stearylamine for polymer-analogous implementation.

    Die Umsetzung der Polymerisate mit den Fettaminen geschieht vorzugsweise in Gegenwart saurer Katalysatoren, beispielsweise mit p-Toluolsulfonsäure. Die Menge an Katalysator soll 1 mol%, bezogen auf vorhandene Carboxylgruppen, nicht übersteigen.The reaction of the polymers with the fatty amines is preferably carried out in the presence acidic catalysts, for example with p-toluenesulfonic acid. The amount of catalyst should Do not exceed 1 mol%, based on the carboxyl groups present.

    Die Dauer der Reaktion richtet sich nach dem gewünschten Umsatz, der sich beispielsweise dünnschichtchromatographisch verfolgen läßt und größer als 90% sein sollte.The duration of the reaction depends on the desired conversion, for example can be followed by thin layer chromatography and should be greater than 90%.

    Die Reaktionstemperatur liegt zwischen 60 und 200°C, wobei insbesondere bei niedrigerer Reaktionstemperatur eine Reaktion unter vermindertem Druck vorteilhaft ist. Zur Erzielung von Umsätzen von mehr als 99% ist es unter Umständen erforderlich, das entstehende Reaktionswasser azeotrop zu entfernen.The reaction temperature is between 60 and 200 ° C, especially lower Reaction temperature a reaction under reduced pressure is advantageous. To achieve For sales of more than 99%, the water of reaction formed may be necessary to remove azeotropically.

    Schritt C: Umsetzung von restlichem Fettamin zu N-substituierten-β-Aminopropionsäuren Dieser optionale Schritt wird durchgeführt, falls ein besonders niedriger Restamingehalt im Endprodukt erforderlich ist. Hierbei werden die verbliebenen Amine mit (Meth)acrylsäure umgesetzt und ggf. die nicht an das Polymerisat aus A) gebundenen Amine bzw. die gebildeten N-substituierten Aminopropionsäuren acyliert. Die Einzelheiten dieser Reaktion sind in der DE 37 17 961 C2 beschrieben. Ein Vorteil dieses Schrittes ist, daß es auf diese Weise nicht unbedingt erforderlich ist, während des Schrittes B niedrige Restaminmengen zu erzielen, weshalb auch mit dem Fettamin im Überschuß, das heißt mit mehr als 80 mol%, bezogen auf Carboxylgruppen, gearbeitet werden kann.Step C: Conversion of residual fatty amine to N-substituted-β-aminopropionic acids This optional step is carried out if a particularly low residual amine content in the Final product is required. The remaining amines with (meth) acrylic acid implemented and, if appropriate, the amines not bound to the polymer from A) or the amines formed Acylated N-substituted aminopropionic acids. The details of this reaction are in described in DE 37 17 961 C2. One advantage of this step is that it does this it is not absolutely necessary to achieve low amounts of residual amine during step B, which is why with the fatty amine in excess, that is, with more than 80 mol%, based on carboxyl groups.

    Schritt D: Neutralisation und DispergierungStep D: neutralization and dispersion

    Im Anschluß an die polymeranaloge Umsetzung werden die verbleibenden Carboxylgruppen mit verdünnter Base, ggf. unter Zusatz von Wasser teilweise oder vollständig neutralisiert, wobei das Polymerisat dispergiert bzw. gelöst wird. Als Neutralisationsmittel geeignet sind Alkali- und Erdalkalihydroxide, Ammoniak, Amine oder Aminoalkohole. Die Basenmenge wird so gewählt, daß sich ein pH-Wert zwischen 5 und 9 einstellt. Die erfindungsgemäßen wässrigen Emulsionen werden auf einen Festsubstanzgehalt von 20 bis 80 Gew.-% eingestellt.Following the polymer-analogous reaction, the remaining carboxyl groups partially or completely neutralized with dilute base, if necessary with the addition of water, wherein the polymer is dispersed or dissolved. Are suitable as neutralizing agents Alkali and alkaline earth hydroxides, ammonia, amines or amino alcohols. The amount of base is chosen so that a pH value between 5 and 9 is established. The invention aqueous emulsions are adjusted to a solids content of 20 to 80 wt .-%.

    Die Erfindung betrifft ferner die Verwendung der erfindungsgemäßen Mittel zur Herstellung von Oberledern mit einem geringem Gehalt an verdampfenden flüchtigen Bestandteilen, insbesondere Autopolsterledern.The invention further relates to the use of the compositions according to the invention for the production upper leather with a low content of volatile volatiles, especially car upholstery leather.

    Die erfindungsgemäßen Mittel, welche die modifizierten Polymerisate enthalten, können entweder als solche oder in Kombination mit anderen Fettungsmitteln bei der Herstellung von Autopolsterledern eingesetzt werden.The agents according to the invention, which contain the modified polymers, can either as such or in combination with other fatliquoring agents in the manufacture of Car upholstery leather can be used.

    Neben der Herstellung von Autopolsterledern eignen sich die erfindungsgemäßen Produkte auch für die Herstellung von hydrophobierten Oberledern oder von waschbaren Bekleidungsledern. Die Einsatzmenge der Produkte beträgt 2 bis 20Gew.%, vorzugsweise 5 - 15Gew.%, bezogen auf das Falzgewicht des Leders. Der Einsatz erfolgt üblicherweise in der Fettungsstufe der Lederbearbeitung.In addition to the production of car upholstery leather, the products according to the invention are suitable also for the production of waterproof leather or washable clothing leathers. The amount of use of the products is 2 to 20% by weight, preferably 5 to 15% by weight, based on the fold weight of the leather. They are usually used in the fat level of leather processing.

    Die folgenden Ausführungsbeispiele sollen die Erfindung erläutern, ohne den Erfindungsgedanken einzuschränken. Alle in den Beispielen genannten Zahlenangaben beziehen sich, sofern nicht anders erwähnt, auf Gewichtsmengen.The following exemplary embodiments are intended to explain the invention without the inventive concept restrict. All of the numerical data mentioned in the examples relate, if not mentioned otherwise, on quantities by weight.

    Beispiel 1:Example 1:

    In einem Reaktor mit Ankerrührer, Dosiereinrichtungen, Innenthermometer und Destillationskolonne werden 45,0 g Butylglykol vorgelegt und auf ca. 80°C aufgeheizt. Anschließend werden folgende Zuläufe gestartet:

    Zulauf 1:
    72,0 g (1,0 mol) Acrylsäure
    Zulauf 2:
    9,0 g (0,1 mol) Mercaptoethanol
    Zulauf 3:
    0,5 g (3,0 mmol) Azo-bis-isobutyronitril in 15 g Butylglykol
    45.0 g of butyl glycol are placed in a reactor with anchor stirrer, metering devices, internal thermometer and distillation column and heated to approx. 80 ° C. The following inlets are then started:
    Inlet 1:
    72.0 g (1.0 mol) acrylic acid
    Inlet 2:
    9.0 g (0.1 mol) mercaptoethanol
    Inlet 3:
    0.5 g (3.0 mmol) azo-bis-isobutyronitrile in 15 g butyl glycol

    Die Dosierdauer beträgt etwa eine Stunde. Es wird weitere 30 Minuten bei 80°C gerührt und anschließend 58 g (0,22 mol) Oleylamin sowie 0,4 g p-Toluolsulfonsäure zugegeben. Die Temperatur wird auf 150°C erhöht und der Ansatz 4 Stunden gerührt und dabei 15 g Destillat abgenommen. Nach vier Stunden wurde der Ansatz dünnschichtchromatographisch untersucht. Es ergab sich ein Restamingehalt von 5 % bezogen auf Gesamtprodukt entsprechend einem Umsatz von ca. 85%. Es wurde auf ca. 95°C abgekühlt. Anschließend erfolgte die Zugabe von 2,0 g Acrylsäure, gefolgt von der Zugabe von 1,8 g Maleinsäureanhydrid. Es wurde eine weitere Stunde gerührt und das Produkt schließlich mit 50 g Natronlauge (50%) und 350 g Wasser neutralisiert und dispergiert. Erhalten wurde ein klares gelbes Produkt mit ca. 35 % Trockensubstanz, in der kein Restamin mehr nachweisbar war. Der pH-Wert betrug 6,8.The dosing time is approximately one hour. The mixture is stirred at 80 ° C. for a further 30 minutes and then 58 g (0.22 mol) of oleylamine and 0.4 g of p-toluenesulfonic acid were added. The The temperature is raised to 150 ° C. and the mixture is stirred for 4 hours, with 15 g of distillate decreased. After four hours, the mixture was examined by thin layer chromatography. There was a residual amine content of 5% based on the total product accordingly a turnover of approx. 85%. It was cooled to approx. 95 ° C. The addition was then carried out 2.0 g of acrylic acid followed by the addition of 1.8 g of maleic anhydride. It was stirred for a further hour and the product finally with 50 g of sodium hydroxide solution (50%) and 350 g neutralizes and disperses water. A clear yellow product was obtained with approx. 35% Dry substance in which no residual amine was detectable. The pH was 6.8.

    Beispiel 2:Example 2:

    Beispiel 1 wurde wiederholt, jedoch wurden als Katalysator für die Amidierung 0,5 g hypophosphorige Säure zugesetzt. Es ergab sich nach der polymeranalogen Amidierung ein Restamingehalt von 0,8 %, weshalb auf die Umsetzung mit Acrylsäure und MSA verzichtet wurde. Es wurde ein klares gelbes Produkt mit einer Wirksubstanz von 40 Gew.% und einem pH-Wert von 6,6 erhalten.Example 1 was repeated, but 0.5 g hypophosphorous were used as the catalyst for the amidation Acid added. There was a residual amine content after the polymer-analogous amidation of 0.8%, which is why the reaction with acrylic acid and MSA is dispensed with has been. It became a clear yellow product with an active substance of 40% by weight and one Obtained pH of 6.6.

    Beispiel 3:Example 3:

    Beispiel 1 wurde wiederholt, jedoch wurden 110 g Oleylamin (0,42 mol) eingesetzt. Es resultierte eine gelbe Emulsion mit einem pH-Wert von 7,5 und einer Wirksubstanz von 40 Gew.%. Example 1 was repeated, but 110 g of oleylamine (0.42 mol) were used. It resulted a yellow emulsion with a pH of 7.5 and an active substance of 40 % By weight.

    Beispiel 4:Example 4:

    Dieses Beispiel entspricht Beispiel 1, jedoch wurden am Ende der Reaktion 60 g eines foggingarmen Fischölsulfitats hinzugefügt. Es resultierte eine hellbraune klare Lösung mit einer Wirksubstanz von ca. 40% und einem pH-Wert von 6,6.This example corresponds to example 1, but at the end of the reaction 60 g became one low-fogging fish oil sulfite added. A light brown clear solution resulted an active substance of approx. 40% and a pH of 6.6.

    Beispiel 5: Herstellung eines AutopolsterledersExample 5: Production of a car upholstery leather

    Ausgangmaterial Rind wet-blue, Falzstärke 1,0 bis 1,2mm, %-Angaben beziehen sich auf FalzgewichtStarting material cattle wet-blue, fold thickness 1.0 to 1.2mm,% -specifications refer to fold weight 1) Waschen1) washing 300 % Wasser 40 °C,300% water 40 ° C, 0,3 % Entfettungsmittel,0.3% degreasing agent, 10 Min10 min Flotte ablassenDrain the fleet 2) Nachgerbung 12) Retanning 1 100 % Wasser 40 °C100% water 40 ° C 4 % Chromsyntan4% chromium syntan 1,5% Dispergierhilfsmittel1.5% dispersing aid 30 min30 min +2 % Harznachgerbstoff+ 2% resin retanning agent 45 min45 min Flotte ablassenDrain the fleet 3) Neutralisation3) Neutralization 100 % Wasser 35°C100% water 35 ° C Nachgerbung 2Retanning 2 1 % Harznachgerbstoff1% resin retanning agent 10 min10 min + 1,2% Natriumbicarbonat+ 1.2% sodium bicarbonate 50 min50 min + 3,0% Syntan, lichtecht+ 3.0% syntan, lightfast 1,5% Vegetabilgerbstoff1.5% vegetable tannin 45 min45 min Flotte ablassenDrain the fleet 4) Waschen4) wash 300 % Wasser 60 °C300% water 60 ° C 10 Min10 min Flotte ablassenDrain the fleet 5) Fettung5) Bold + 6,5 % Wirksubstanz Fettungsmittel 1:4+ 6.5% active substance fatliquor 1: 4 60 min60 min + 1,5% Ameisensäure+ 1.5% formic acid 30 min 30 min End pH der Flotte 3,5 bis 3,9Final pH of the liquor 3.5 to 3.9 Flotte ablassenDrain the fleet 7) Waschen7) washing 300% Wasser 20 °C300% water 20 ° C 10 Min10 min

    Die Leder werden über Nacht auf dem Bock nassgespannt, getrocknen, angefeuchtet, gestollt und gemillt.The leathers are wet-stretched on the trestle overnight, dried, moistened, and chugged and grilled.

    Als Vergleichsbeispiele (Stand der Technik) wurden ein foggingarmes Polymerfettungsmittel (V1: Handelsprodukt "Magnopal®" SOF, Hersteller Stockhausen GmbH & Co. KG) sowie ein foggingarmes Fettungsmittel auf Basis von Fischölen (V2: Handelsprodukt "Chromopol®" LFC, Hersteller Stockhausen GmbH & Co. KG) verwendet. Tabelle der Ergebnisse: Beispiel 2 Beispiel4 Vergleich 1 Vergleich 2 Weichheit 2 2+ 2+ 2+ Narbenbild ---------- fein bis mittel, egal---------- Foggingergebnisse nach DIN 75201 B (gravimetrisch) 1,2 1,5 3,9 3,5 nach DIN 75201 A (reflektometrisch) 51% 55% 34% 40% Lichtechtheit nach 8 Std. >3 1-2 >3 1 nach 24 Std. 4-5 2 4 1 Comparative examples (prior art) were a low-fogging polymer lubricant (V1: commercial product "Magnopal®" SOF, manufacturer Stockhausen GmbH & Co. KG) and a low-fogging lubricant based on fish oils (V2: commercial product "Chromopol®" LFC, manufacturer Stockhausen GmbH & Co. KG) used. Results table: Example 2 Example4 Comparison 1 Comparison 2 Softness 2nd 2+ 2+ 2+ Scar image ---------- fine to medium, never mind ---------- Fogging results according to DIN 75201 B (gravimetric) 1.2 1.5 3.9 3.5 according to DIN 75201 A (reflectometric) 51% 55% 34% 40% Lightfastness after 8 hours > 3 1-2 > 3 1 after 24 hours 4-5 2nd 4th 1

    Erläuterung der Werte:Explanation of the values:

    Weichheit: Benotung nach dem Schulnotenprinzip (1: sehr gut; 6: ungenügend) Fogging gravimetrisch: Angaben in mg/50 cm2
    Lichtechtheit: nach DIN 54004, Beurteilung gegen Blaumaßstab unter Tageslichtlampe, niedrigere Zahlen entsprechen stärkeren Vergilbungen.    Softness: grading according to the school grade principle (1: very good; 6: insufficient). Fogging gravimetric: data in mg / 50 cm 2
    Lightfastness: according to DIN 54004, assessment against blue scale under daylight lamp, lower numbers correspond to stronger yellowing.

    Die Tabelle zeigt, daß die erfindungsgemäßen Produkte den Produkten des Standes der Technik in mindestens einem Kriterium überlegen sind.The table shows that the products according to the invention are the products of the prior art are superior in at least one criterion.

    Claims (17)

    1. Leather dressing agents, particularly for car upholstery leather, which may be obtained by
      A) polymerization of
      a1) 70-100 wt.-% acrylic acid and/or methacrylic acid and/or the acid chlorides and/or anhydrides thereof with
      a2) 0-30 wt.-% of other water-soluble monomers copolymerizable with a1), and
      a3) 0-20 wt.-% of water-insoluble monomers copolymerizable with a1) and a2),
      B) reaction of the polymer from A) with amines of formula 1 R1-NH-R2 wherein
      R1 represents a C12-C30 alkyl or alkenyl residue, and
      R2 represents H, a C1-C4 alkyl or C1-C2 hydroxyalkyl residue,
      optionally
      C) reaction of the amines not bound to the polymer from A) with (meth)acrylic acid to give N-substituted β-aminopropionic acids and optionally, acylation of the amines not bound to the product A), or the N-substituted aminopropionic acids formed,
      D) neutralization and dispersion of the product obtained from B) and C), respectively.
    2. Leather dressing agents according to claim 1, which may be obtained by A) polymerization of 80-100 wt.-% of monomer a1).
    3. Leather dressing agents according to one of claims 1-2, which may be obtained by A) polymerization of (meth)acrylamide, (meth)allyl alcohol, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxyalkylpolyethyleneoxy (meth)acrylate, alkyloxypolyethyleneoxy (meth)acrylate, polyethylene glycol monoallyl ether, N-vinylpyrrolidone and/or N-vinylimidazole as comonomers a2).
    4. Leather dressing agents according to one of claims 1-2, which may be obtained by polymerization of monomers containing acid groups, preferably maleic acid, itaconic acid, vinylsulfonic acid, methallylsulfonic acid, 2-acrylamido-2-methylpropylsulfonic acid, 4-vinylphenylsulfonic acid, vinylphosphonic acid and/or the water-soluble esters, anhydrides, alkali, alkaline earth and/or ammonium salts of the above acids as comonomers a2).
    5. Leather dressing agents according to one of claims 1-2, which may be obtained by A) polymerization of basic monomers, preferably dimethylaminoalkyl (meth)acrylate and/or dimethylaminoalkyl (meth)acrylamide and/or the quaternary forms thereof as comonomers a2).
    6. Leather dressing agents according to one of claims 1-5, which may be obtained by A) polymerization of C1-C30 alkyl (meth)acrylates, vinyl esters of C1-C30 carboxylic acids, vinyl ethers of C1-C30 alcohols and/or ethylenically unsaturated aromatic monomers, preferably styrene, as comonomers a3).
    7. Leather dressing agents according to one of claims 1-6, which may be obtained by solution polymerization in a solvent wherein all the monomers employed are soluble.
    8. Leather stuffing agents according to one of claims 1-7, which may be obtained by solution polymerization in ethylene glycol butyl ether and/or diethylene glycol butyl ether as solvent.
    9. Leather stuffing agents according to one of claims 1-8, characterized in that 20-80 mole-% of the carboxyl groups present in the polymer are reacted with amines of formula R1-NH-R2.
    10. Leather stuffing agents according to one of claims 1-9, characterized by the form of an aqueous solution or emulsion having a pH value ranging from 5 to 9 and a content of polymer of 20-80 wt.-%, calculated as solid matter.
    11. A process for producing the leather dressing agents according to one of claims 1-10, characterized in that the monomers a1), a2) and a3) are subjected to free-radical polymerization, preferably in solution, the polymer obtained is then reacted either immediately or subsequent to solvent removal with the amines of formula R1-NH-R2, wherein R1 and R2 have the meanings indicated in claim 1, at least part of the acid groups present in the polymer being converted to the corresponding amide groups, followed by partial or complete neutralization of the remaining carboxyl groups using dilute base, optionally with addition of water.
    12. The process according to claim 11, characterized in that prior to neutralization and emulsification, residual fatty amine is reacted with (meth)acrylic acid and subsequently acylated, if necessary.
    13. The process according to one of claims 11-12, characterized in that the polymer-analogous reaction of the polymers with the fatty amines of general formula R1-NH-R2 is performed at temperatures of from 60 to 200°C, optionally under reduced pressure and/or with azeotropic removal of the reaction water produced.
    14. The process according to one of claims 11-13, characterized in that a pH value of from 5 to 9 is finally adjusted using dilute base, preferably alkali and alkaline earth hydroxide, ammonia, amines or aminoalcohols, with dispersion or solution of the product.
    15. Use of the leather dressing agents according to one of claims 1-10 in the manufacture of upper leathers having low contents in evaporating volatiles, particularly car upholstery leathers.
    16. The use according to claim 15 in combination with other well-known stuffing agents.
    17. The use of the leather dressing agents according to one of claims 1-14 at a required amount of from 2 too 20 wt.-%, preferably 5-15 wt.-%, based on the shaving weight of the leather at the stuffing stage of leather manufacturing.
    EP97944848A 1996-09-09 1997-09-08 Novel leather-treatment agents, process for their preparation, and their use for producing low-fogging leathers Expired - Lifetime EP0927271B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    DE19636494A DE19636494C2 (en) 1996-09-09 1996-09-09 Low-monomer, amine-free polymers, processes for their preparation and their use in the production of low-fogging leather
    DE19636494 1996-09-09
    PCT/EP1997/004863 WO1998010103A1 (en) 1996-09-09 1997-09-08 Novel leather-treatment agents, process for their preparation, and their use for producing low-fogging leathers

    Publications (2)

    Publication Number Publication Date
    EP0927271A1 EP0927271A1 (en) 1999-07-07
    EP0927271B1 true EP0927271B1 (en) 2000-03-29

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    EP97944848A Expired - Lifetime EP0927271B1 (en) 1996-09-09 1997-09-08 Novel leather-treatment agents, process for their preparation, and their use for producing low-fogging leathers

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    US (1) US6048467A (en)
    EP (1) EP0927271B1 (en)
    AR (1) AR009525A1 (en)
    AT (1) ATE191239T1 (en)
    DE (2) DE19636494C2 (en)
    ES (1) ES2144881T3 (en)
    TR (1) TR199900511T2 (en)
    WO (1) WO1998010103A1 (en)

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    DE10207277A1 (en) * 2002-02-21 2003-09-04 Basf Ag Low-VOC greasing agents, their use in the production and / or treatment of leather and skins, and processes for the production and / or treatment of leather and skins with these greasing agents
    DE10320110A1 (en) 2003-05-06 2004-11-25 Basf Ag Lubricant for the manufacture and treatment of leather
    US7425595B2 (en) * 2003-12-15 2008-09-16 Absorbent Technologies, Inc. Superabsorbent polymer products including a beneficial additive and methods of making and application
    PT1737907T (en) * 2003-12-15 2019-05-29 Vjs Investments Ltd A superabsorbent polymer product including a bioactive, growth-promoting additive
    EP1781709A4 (en) * 2004-08-27 2011-07-06 Absorbent Technologies Inc Superabsorbent polymers in agricultural applications
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    US7607259B2 (en) * 2006-01-17 2009-10-27 Absorbent Technologies, Inc. Superabsorbent polymer root dip
    US20070167330A1 (en) * 2006-01-17 2007-07-19 Savich Milan H Superabsorbent polymer applicator
    EP1882749A1 (en) 2006-07-25 2008-01-30 Joseph Mellini Leather-surface repair-composition and the method for surface repair of leather surfaces
    US9596801B2 (en) 2010-10-25 2017-03-21 Vjs Investments Limited Superabsorbent polymer seed coatings and associated methods
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    Publication number Publication date
    AR009525A1 (en) 2000-04-26
    DE19636494A1 (en) 1998-03-26
    DE19636494C2 (en) 2000-11-16
    ES2144881T3 (en) 2000-06-16
    DE59701378D1 (en) 2000-05-04
    WO1998010103A1 (en) 1998-03-12
    ATE191239T1 (en) 2000-04-15
    TR199900511T2 (en) 1999-06-21
    US6048467A (en) 2000-04-11
    EP0927271A1 (en) 1999-07-07

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