EP0739425B1 - Fatty treatment agent for leather - Google Patents

Fatty treatment agent for leather Download PDF

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Publication number
EP0739425B1
EP0739425B1 EP95904545A EP95904545A EP0739425B1 EP 0739425 B1 EP0739425 B1 EP 0739425B1 EP 95904545 A EP95904545 A EP 95904545A EP 95904545 A EP95904545 A EP 95904545A EP 0739425 B1 EP0739425 B1 EP 0739425B1
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EP
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Prior art keywords
acid
preparations
group
carbon atoms
oligomers
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EP95904545A
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German (de)
French (fr)
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EP0739425A1 (en
Inventor
Rudolf Zauns-Huber
Fredi Wolter
Günter Uphues
Gilbert Schenker
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes

Definitions

  • the invention relates to agents for greasing leather.
  • the leather treated with these agents is characterized by good Fastness to washing and cleaning as well as good water resistance.
  • the Agents according to the invention are aqueous dispersions with a content based on special aminopropionic acid derivatives and co-oligomers of fat crotonates.
  • the greasing of vegetable and / or mineral tanned leather respectively Fur skins is an essential process step in the Ready-to-use equipment.
  • the form of fat distribution in the skin substance and the extent of the integration of the fat components in the skin substance affect the properties and the usability of the finished products is crucial. It exists extensive knowledge of possible interactions between the fat components on the one hand and the tanned, as well as residual tannins containing skin substance on the other hand.
  • the special structure the fatliquor - for example the extent of their lipophilic Groups and any reactive groups present for the reaction with suitable reactive components in the tanned leather - determine among other things, the durability and effectiveness of the greasing equipment in the practical use of leather and fur products.
  • EP 193 832 relates to a method for producing watertight Leather or furs using sulfosuccinic acid monoesters in combination with impregnating and / or hydrophobic Greasing agents.
  • amphiphilic agents of this kind can in the form of aqueous dispersions, emulsions and / or solutions after completion of the main tanning in the leather to be finished or Skins are worked in - for example rolled in.
  • these can Amphiphilic agents simultaneously take on the function of retanning.
  • there can be a final fixation of the amphiphiles Means with in particular mineral tanning agents can be provided.
  • amphiphilic copolymers from one predominant proportion of at least one hydrophobic monomer and one minor portion of at least one copolymerizable hydrophilic Monomers are formed.
  • hydrophobic monomers long chain alkyl (meth) acrylates, long chain alkoxy or Alkylphenoxy (polyethylene oxide) - (meth) acrylates, primary alkenes, vinyl esters of long-chain alkyl carboxylic acids and their mixtures.
  • the Hydrophilic comonomers present to a lesser extent are ethylenic unsaturated water-soluble acids or hydrophilic basic ones Comonomers.
  • the weight average molecular weight of the copolymers is in the range of 2,000 to 100,000.
  • EP 412 389 describes the use of copolymers as agents for hydrophobicizing leather and fur skins, which are obtained by radical copolymerization of (a) C 8-40 monoolefins with (b) ethylenically unsaturated C 4-8 dicarboxylic acid anhydrides in the manner of bulk polymerization at temperatures from 80 to 300 ° C to copolymers with molecular weights of 500 to 20,000 g / mol, subsequent solvolysis of the anhydride groups of the copolymers and at least partial neutralization of the carboxyl groups formed in the solvolysis have been prepared in an aqueous medium with bases and which are in the form of aqueous dispersions or There are solutions.
  • EP 418 661 describes the use of copolymers which contain (a) 50 to 90% by weight of C 8-40 alkyl (meth) acrylates, vinyl esters of C 8-40 carboxylic acids or mixtures thereof and ( b) 10 to 50% by weight of monoethylenically unsaturated C 3-12 carboxylic acids, monoethylenically unsaturated dicarboxylic acid anhydrides, half esters or half amides of monoethylenically unsaturated C 4-12 dicarboxylic acids, amides of C 3-12 monocarboxylic acids or mixtures thereof, and copolymerized, and molecular weights possess from 500 to 30,000 g / mol.
  • the copolymers are in at least partially neutralized form in aqueous solution or in aqueous dispersion for the intended use.
  • aqueous dispersions of co-oligomers from the radically triggered aqueous emulsion copolymerization in weakly acidic to neutral pH range as amphiphiles Means for greasing and washable finishing of leather and Fur skins;
  • the main components are half esters of maleic acid with oleophilic alcohols and / or their lower alkylene oxide adducts as well as acrylic acid and / or methacrylic acid; in addition can also minor amounts of other hydrophilic and / or oleophilic Co-monomers can be contained in the oligomer molecule.
  • the object of the present invention was to provide means for the above Field of application, i.e. for the greasing equipment of To provide leather.
  • Fat crotonates are esters of crotonic acid (trans-2-butenoic acid) with C 10-40 fatty alcohols.
  • the radical R 1 in the formula for the aminopropionic acid derivatives (I) is a saturated alkyl radical with predominantly 12 to 18 carbon atoms.
  • the radical Y in the formula for the aminopropionic acid derivatives (I) is an alkylene group, in particular a group -CH 2 -CH 2 -, and the radical R 2 is a carboxyl group (-CO 2 H).
  • the teaching according to the invention thus provides for the application area specified here the greasing equipment of leather and fur Combination of special aminopropionic acid derivatives with co-oligomers based on fat crotonates, their use as the main oleophilic component in amphiphilic dressings of the type concerned in The prior art has not been described so far.
  • the agents according to the invention are for rapid and penetrating impregnating finish of leather and / or fur particularly suitable, so that genuine and cleanable leather and fur skins become accessible.
  • the so obtained leather due to the hydrophobic properties of the invention Good water resistance.
  • those fatty crotonate building blocks (a) are preferred which contain C 12-24 fatty alcohols as the alcohol component.
  • Straight-chain fatty alcohols or their mixtures are preferred.
  • the use of branched-chain fatty alcohols in the fat crotonate component (a) can also lead to interesting results in individual cases. For example, by using such branched-chain alcohols to a limited extent, the penetrability of the co-oligomer (II) into the fiber structure of the skin material to be treated can be promoted.
  • branched alcohols with a shorter carbon number, suitable alcohols having at least 6 carbon atoms, preferably having at least 8 carbon atoms.
  • An important branched chain alcohol that can be used in connection with the fatty crotonate building blocks (a) is 2-ethylhexanol.
  • the amount of branched-chain, in particular shorter, alcohols to be used will always be comparatively small.
  • no more than 50% by weight, preferably no more than 30 or no more than 20% by weight, of the alcohol residues present in (a) are formed by such branched-chain, in particular lower, alcohols.
  • hydrophilic used in the amphiphilic co-oligomers (II) Components (b) can consist of the corresponding building blocks the co-oligomers of EP 372 746, EP 412 389 and Correspond to EP 418 661.
  • the last-mentioned publication provides detailed information on suitable classes of substances and numerous special representatives.
  • Particularly important building blocks (b) for the co-oligomers (II) are in According to the present invention, ethylenically unsaturated monocarboxylic acids and / or ethylenically unsaturated dicarboxylic acids and / or their anhydrides each with preferably up to 12 carbon atoms.
  • the dicarboxylic acids can also at least partially in the form of their partial derivatives with a carboxyl group and a derivatized carboxylic acid group for example as dicarboxylic acid half esters.
  • Particularly interesting representatives from the class of monoethylenically unsaturated C 3-12 monocarboxylic acids are, for example, acrylic acid, methacrylic acid and crotonic acid.
  • Particularly suitable building blocks (b) can also be dicarboxylic acids or their derivatives, in particular their anhydrides. Typical representatives are maleic acid, fumaric acid, itaconic acid, glutaconic acid and corresponding anhydrides.
  • Maleic anhydride is of particular importance. Fat crotonates (a) and maleic anhydride can be satisfactory Way with or without the use of auxiliary solvents to co-oligomers (II) implement an easily adjustable low molecular weight. It is particularly possible to use approximately the same molar amounts Maleic anhydride and fat crotonate with each other for implementation bring so that after solvolysis, especially hydrolysis of the maleic anhydride building blocks on the one hand, sufficiently high concentrations on carboxyl groups for fixing the oligomers in the skin or Fiber structure are available, on the other hand also reliably high levels of oleophilic and therefore greasy and water-repellent fat crotonate building block.
  • hydrophilic building blocks (b) are also other copolymerizable, hydrophilic Connections can be used.
  • Sulfoic acid groups in particular come into consideration here containing ethylenically unsaturated monomers.
  • Known Representatives of this type are, in particular, corresponding aliphatic ones and / or aromatic sulfonic acids, such as styrene sulfonic acid also compounds such as vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid and the same.
  • the block can (b) of the co-oligomer (II) wholly or partly from those of the copolymerization or co-oligomerization accessible sulfonic acid compounds be educated.
  • Preferred ranges for the mixing ratios are about 35 to 80% by weight (a) to 65 to 20% by weight (b).
  • amphiphilic co-oligomers can (II) also minor amounts of other copolymerizable Contain comonomers, which are in the above definition as building blocks (c) are designated.
  • Any of the co-oligomerization can be suitable here accessible ethylenically unsaturated compounds as they are are described in the relevant prior art, cf. here for example EP 418 661 Al, column 3, 49 to column 4, 27. In the As a rule, these are comonomers that are neither pronounced Hydrophobing effect also have hydrophilizing groups in the Sense of the carboxyl groups or sulfonic acid groups of the invention have used components (b).
  • Such comonomers (c) in the amphiphilic co-oligomers described according to the invention used their share is preferably no longer than about 30% by weight and in particular not more than about 15% by weight - % by weight - refers to the sum of (a), (b) and (c).
  • co-oligomers (II) particularly preferred which are free from those according to the above Definition of optional building blocks (c), that is, the exclusive ones are built up from building blocks (a) and (b).
  • These preferred Co-oligomers (II) contain building blocks (a) and (b) in mixing ratios from about 40 to 70% by weight (a) to 60 to 30 % By weight (b); the percentages by weight relate to the sum again of (a) and (b).
  • the co-oligomers (II) based on the fat crotonates preferably have average molecular weights in the range from about 500 to 30,000 g / mole. Molar masses in the range can be particularly suitable from about 1,000 to 15,000 g / mol. It has been shown that within of these comparatively broad areas the lower values - average molecular weights or molecular weights in the range of about 1,000 to 4,000 or 5,000 g / mol and expediently in the range from about 1,000 to 3,000 g / mol - can be of particular importance.
  • those co-oligomers (II) are within the scope of the invention
  • Lessons preferred from the implementation of fat crotonates and maleic anhydride result and their maleic anhydride building blocks by hydrolysis and / or solvolysis with H-active components in the corresponding form with free carboxyl groups have been converted.
  • solvolysis of maleic anhydride building blocks with H-active components alcohols are particularly suitable but also other compounds such as carboxylic acids, reactive hydrogen containing amino compounds and the like.
  • Such targeted solvolysis can be influenced in a targeted manner a strengthening of the greasy or water-repellent Properties of the co-oligomers (II).
  • the ratio from oleophilic to hydrophilic groups towards the water-repellent oleophilic elements are moved.
  • co-oligomers (II) access to the co-oligomers (II) is also, for example possible in the following way: In a first process stage, the free crotonic acid and maleic anhydride with each other to the corresponding Implemented oligomer compound. Then is excluded of water and rapid discharge of the condensation water Esterification of the crotonic acid components with the desired fatty alcohols or fatty alcohol mixtures. Below then the hydrolysis or solvolysis of the anhydride rings carried out.
  • the agents according to the invention are preferably weak acidic to weakly alkaline range.
  • it may be appropriate to offer forms provide the aqueous phase by adding inorganic and / or organic bases on neutral to weakly alkaline pH values is set.
  • Suitable for pH regulation all bases described in the relevant prior art.
  • the alkali salts, in particular sodium, are preferred and / or potassium.
  • ammonium salts or salts of alkanolamines such as diethanolamine are suitable representatives.
  • Preferred pH values for products that are stable in storage can be in the range of pH 7 to 8.
  • aqueous pasty masses can be produced be, the valuable content of components (I) and (II) for example is in the range of about 30 to about 75% by weight.
  • Such pasty masses are mixed with water and / or aqueous active ingredients of the type described below at any time and to put it into practical use.
  • the agents according to the invention are used together with selected emulsifiers which, when introduced into mineral-tanned leather and / or furs in particular, cause additional greasing or hydrophobicization and can preferably be fixed simultaneously via acidic groups in the tanned leather or fur.
  • emulsifiers which, when introduced into mineral-tanned leather and / or furs in particular, cause additional greasing or hydrophobicization and can preferably be fixed simultaneously via acidic groups in the tanned leather or fur.
  • emulsifiers are the water-emulsifiable sulfosuccinic acid half-esters mentioned at the outset, which are derived from long-chain fatty alcohols and / or their alkylene oxide adducts.
  • An important example of the emulsifier class of the type concerned here are C 18 sulfosuccinic acid half esters. It has been shown that by using such emulsifier-like auxiliary components - which are known per se as finishing agents for
  • the agents according to the invention can also contain greasing agents or hydrophobizing agents in the sense of the mixtures of materials from EP 193 832 cited at the beginning.
  • the mixtures according to the invention of components (I) and (II) combined with impregnating and / or hydrophobizing fatliquoring agents, such as sulfosuccinic acid monoester salts with C 12-24 fat residues, in combination with other impregnating fatliquoring agents are selected in particular from the group of oxidized or oxidized and partially sulfated C 18-26 hydrocarbons or C 32-40 waxes.
  • additional impregnating fatliquors are phosphoric acid mono-C 12-24 alkyl esters, partial esters of polycarboxylic acids such as citric acid mono-C 16-24 alkyl esters, partial esters of polyalcohols such as sorbitan, glycerol or pentaerythritol C 16-24 fatty acid esters .
  • a particularly suitable class of emulsifiers which can also be used in the context of the teaching according to the invention, are the N-acylamino acids known from the finishing of leather and furs with fatty substances, in particular fatty acid sarcosides, for example N-oleoyl sarcosine, as used, for example, as emulsifiers for introducing silicone oils in leather and furs are described in detail in EP-B-0 213 480.
  • Suitable emulsifiers are accordingly, in particular, salts of N- (C 9-20 -acyl) -amino acids, corresponding salts of an amino acid having 2 to 6 C atoms, which with the acyl residue of a saturated or unsaturated fatty acid having 9 to 20 C atoms Amine nitrogen, which is optionally additionally substituted by methyl, is of particular importance.
  • Suitable salts of these emulsifiers are in particular alkali, ammonium or alkanolamine salts.
  • N- (C 9-20 -acyl) amino acids those with 2 to 4 C atoms and with the amino group in the alpha position to the carboxyl group are particularly preferred, which are also substituted on the amine nitrogen atom by a methyl group.
  • the fatty acid sarcosides of saturated or unsaturated fatty acids with 9 to 20, preferably 16 to 18, carbon atoms have a particularly superior effect.
  • the preferred sarcoside is the oleic acid sarcoside.
  • N-stearoyl sarcosine, N-lauroyl sarcosine and N-isononanoyl sarcosine are particularly suitable, in each case in the form of their alkali metal salts, ammonium salts or the salts of mono-, di- or trialkanolamines with in particular 2 to 4 C- Atoms in the alkanol residue.
  • the amount is Components (I) and (II) compulsory according to the invention preferably at least about 35% by weight of the material mixture and in particular at least about 50% by weight. However, it may be useful at least about 70 to 80 wt .-% of the total to be equipped A mixture of valuable materials to be introduced into leather or fur skins to be provided on the basis of components (I) and (II).
  • the dispersions of the invention are suitable for the treatment of all usual tanned hides, especially appropriate material, that has been tanned with mineral tannins.
  • the tanned Skins are usually deacidified before treatment. You can have been stained before treatment. A coloring can but also only after the treatment carried out according to the invention be made.
  • the treatment takes place, for example by walking in a FaB.
  • the amount of the invention Dispersions are usually 0.1 to 30 wt .-%, in particular 1 to 20% by weight based on the shaved weight of the leather or the wet weight of the fur skins.
  • the fleet length is usually 10 to 1,000%, preferably 30 to 150%, for fur skins 50 to 500%.
  • the addition of organic is particularly suitable Acids, preferably formic acid.
  • Preferred pH values are in the range from 3 to 5, preferably in the range from about 3.5 to 4.
  • fixation with mineral tanning agents in particular downstream, whereby the use of aluminum salts, but also from other multivalent mineral salts, e.g. Chromium or zirconium salts can be particularly preferred.
  • the aminopropionic acid derivatives (I) can be prepared by methods known per se, e.g. B. by addition of acrylic or methacrylic acid to primary Alkylamines and subsequent implementation of the resulting N-alkylaminopropionic acids with carboxylic acid anhydrides, carboxylic acid chlorides, Sulfonic acid chlorides, isocyanates, halocarboxylic acids or acrylic or methacrylic acids (see e.g. the above-cited DE-A-37 17 961).

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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)
  • Cosmetics (AREA)

Abstract

Aqueous dispersions containing special aminopropionic acid derivatives and co-oligomers based on fatty crotonates are suitable for the oiling of leather. The leathers thus treated are distinguished by high resistance to washing and cleaning and by impermeability to water.

Description

Gebiet der ErfindungField of the Invention

Die Erfindung betrifft Mittel zur fettenden Ausrüstung von Leder. Die mit diesen Mitteln behandelten Leder zeichnen sich durch gute Wasch- und Reinigungsechtheit sowie gute Wasserdichtigkeit aus. Die erfindungsgemäßen Mittel sind wäßrige Dispersionen mit einem Gehalt an speziellen Aminopropionsäurederivaten und Co-Oligomeren auf Basis von Fettcrotonaten.The invention relates to agents for greasing leather. The leather treated with these agents is characterized by good Fastness to washing and cleaning as well as good water resistance. The Agents according to the invention are aqueous dispersions with a content based on special aminopropionic acid derivatives and co-oligomers of fat crotonates.

Stand der TechnikState of the art

Die Fettung pflanzlich und/oder mineralisch gegerbter Leder beziehungsweise Pelzfelle ist ein essentieller Verfahrensschritt in der Ausrüstung zum gebrauchsfertigen Wertstoff. Die Form der Fettverteilung in der Hautsubstanz und das Ausmaß der Einbindung der Fettkomponenten in die Hautsubstanz beeinflussen die Eigenschaften und die Gebrauchsfähigkeit der Fertigprodukte entscheidend. Es besteht dabei umfangreiches Fachwissen zu möglichen Interaktionen zwischen den Fettkomponenten einerseits und der gegerbten, sowie Restgerbstoffe enthaltenden Hautsubstanz andererseits. Der spezielle Aufbau der Fettungsmittel - beispielsweise das Ausmaß ihrer lipophilen Gruppen und gegebenenfalls vorliegenden Reaktivgruppen zur Umsetzung mit geeigneten Reaktivbestandteilen im gegerbten Leder - bestimmen unter anderem die Dauerhaftigkeit und Wirkung der fettenden Ausrüstung im praktischen Gebrauch der Leder- und Pelzwaren.The greasing of vegetable and / or mineral tanned leather respectively Fur skins is an essential process step in the Ready-to-use equipment. The form of fat distribution in the skin substance and the extent of the integration of the fat components in the skin substance affect the properties and the usability of the finished products is crucial. It exists extensive knowledge of possible interactions between the fat components on the one hand and the tanned, as well as residual tannins containing skin substance on the other hand. The special structure the fatliquor - for example the extent of their lipophilic Groups and any reactive groups present for the reaction with suitable reactive components in the tanned leather - determine among other things, the durability and effectiveness of the greasing equipment in the practical use of leather and fur products.

Ein für die Praxis wichtiger Aspekt liegt in der Schaffung von fettenden Ausrüstungsmitteln, die in der gegerbten Hautsubstanz so zuverlässig gebunden werden können, daß eine für die praktischen Bedürfnisse hinreichende Wasch- und Reinigungsbeständigkeit der Leder- und Pelzwaren sichergestellt ist. Hochwertige Lederwaren, beispielsweise aus der Bekleidungsindustrie, sollen dabei sowohl der wäßrigtensidischen Wäsche als auch gegebenenfalls einer chemischen Reinigung ohne wesentliche Qualitätseinbuße zugänglich sein. Für Sonderfälle wird die weiterführende Bedingung hinreichender Wasserdichtigkeit des fertig ausgerüsteten Leders gewünscht.An important aspect in practice is the creation of greasy ones Finishing agents that are so reliable in the tanned skin substance that can be bound for practical needs sufficient resistance to washing and cleaning of the leather and fur products is ensured. High quality leather goods, for example from the clothing industry, both the water-surfactant Laundry and, if necessary, a dry cleaning be accessible without significant loss of quality. For special cases becomes the further condition of sufficient water resistance of the finished leather.

Zur wasserdichten Ausrüstung von Leder oder Pelzen sind insbesondere drei Verfahrensprinzipien bekannt:

  • 1. Imprägnierung durch Einlagerung wasserunlöslicher Verbindungen, zum Beispiel feste Fette, Wachse oder spezielle Polymere,
  • 2. Imprägnierung durch Einlagerung wasserquellender Verbindungen, die bei Wasseraufnahme hochviskose Emulsionen bilden und die Faserzwischenräume des Leders verstopfen, zum Beispiel spezielle Emulgatoren vom W/0-Typ,
  • 3. Behandlung mit hydrophobierend wirkenden Verbindungen, zum Beispiel Aluminium-, Chrom- und/oder Zirkonkomplexe, Silkone oder organische Fluorverbindungen.
    • In particular, three process principles are known for waterproofing leather or furs:
  • 1. impregnation by storing water-insoluble compounds, for example solid fats, waxes or special polymers,
  • 2. Impregnation by incorporating water-swellable compounds which form highly viscous emulsions when water is absorbed and clog the interstices of the leather, for example special emulsifiers of the W / 0 type,
  • 3. Treatment with compounds having a hydrophobic effect, for example aluminum, chromium and / or zircon complexes, Silkone or organic fluorine compounds.

    • Die DE 1 669 347 beschreibt die Verwendung von wasseremulgierbaren Sulfobernsteinsäure-Halbestern zum Fetten von Leder, wobei jedoch noch keine Wasserdichteffekte erzielt werden.DE 1 669 347 describes the use of water-emulsifiable Sulfosuccinic acid half-esters for greasing leather, however no waterproofing effects can be achieved yet.

    Gegenstand der EP 193 832 ist ein Verfahren zur Herstellung wasserdichter Leder oder Pelze unter Verwendung von Sulfobernsteinsäure-Monoestern in Kombination mit imprägnierenden und/oder hydrophobierenden Fettungsmitteln.EP 193 832 relates to a method for producing watertight Leather or furs using sulfosuccinic acid monoesters in combination with impregnating and / or hydrophobic Greasing agents.

    Die DE 37 17 961 beschreibt ein Verfahren zur Herstellung von N,N-disubstituierten β-Aminopropionsäuren und ihre Verwendung unter anderem zur Hydrophobierung von Leder und Pelzen. Die Herstellung dieser Verbindungen geschieht dabei in zwei Schritten derart, daß zunächst primäre Alkylamine an Acryl- bzw. Methacrylsäure angelagert werden und die dabei entstandenen N-Alkylaminopropionsäuren mit Carbonsäureanhydriden, Carbonsäurechloriden, Sulfonsäurechlorid, Isocyanaten, Halogencarbonsäuren oder Acryl- bzw. Methacylsäuren umgesetzt werden. Die Produkte können gewünschtenfalls anschlieBend noch - wenigstens teilweise - neutralisiert werden.DE 37 17 961 describes a process for the production of N, N-disubstituted β-aminopropionic acids and their use under for the waterproofing of leather and furs. The production these connections are done in two steps such that initially primary alkyl amines attached to acrylic or methacrylic acid and the resulting N-alkylaminopropionic acids with carboxylic anhydrides, Carboxylic acid chlorides, sulfonic acid chloride, isocyanates, Halogen carboxylic acids or acrylic or methacrylic acids implemented will. If desired, the products can then still be used - at least partially - be neutralized.

    In jüngster Zeit werden für die fettende Ausrüstung von insbesondere mineralisch gegerbten Ledern und Pelzen amphiphile Mittel beschrieben, die bestimmt ausgewählte Co-Oligomere von einerseits hydrophoben beziehungsweise oleophilen Monomeren und andererseits hydrophilen Monomerbestandteilen darstellen. Amphiphile Mittel dieser Art können in Form wäßriger Dispersionen, Emulsionen und/oder Lösungen nach Abschluß der Hauptgerbung in die auszurüstenden Leder oder Felle eingearbeitet - beispielsweise eingewalkt - werden. Insbesondere im Fall mineralisch gegerbter Leder oder Pelzfelle können diese amphiphilen Mittel gleichzeitig die Funktion der Nachgerbung übernehmen. Es kann schließlich eine abschließende Fixierung der amphiphilen Mittel mit insbesondere Mineralgerbstoffen vorgesehen sein. Die jüngere Patentliteratur beschreibt Hilfsstoffe der hier betroffenen Art.Recently, the greasing equipment has been used in particular mineral-tanned leathers and furs described amphiphilic agents, the determined selected co-oligomers from hydrophobic on the one hand or oleophilic monomers and, on the other hand, hydrophilic Represent monomer components. Amphiphilic agents of this kind can in the form of aqueous dispersions, emulsions and / or solutions after completion of the main tanning in the leather to be finished or Skins are worked in - for example rolled in. Especially in the case of mineral-tanned leather or fur skins, these can Amphiphilic agents simultaneously take on the function of retanning. Finally, there can be a final fixation of the amphiphiles Means with in particular mineral tanning agents can be provided. The more recent patent literature describes auxiliaries of those affected Art.

    So sind zum Beispiel in der EP 372 746 entsprechende Mittel und ihre Anwendung beschrieben, wobei die amphiphilen Copolymere aus einem überwiegenden Anteil wenigstens eines hydrophoben Monomeren und einem untergeordneten Anteil wenigstens eines copolymerisierbaren hydrophilen Monomeren gebildet sind. Als hydrophobe Monomere sind aufgezählt: langkettige Alkyl(meth)acrylate, langkettige Alkoxy- oder Alkylphenoxy(polyethylen-oxid)-(meth)acrylate, pimäre Alkene, Vinylester von lankettigen Alkylcarbonsäuren und deren Gemische. Die in geringerem Anteil vorliegenden hydrophilen Comonomeren sind ethylenisch ungesättigte wasserlösliche Säuren oder hydrophile basische Comonomere. Das Molekulargewicht (Gewichtsmittel) der Copolymeren liegt im Bereich von 2.000 bis 100.000.For example, in EP 372 746 corresponding means and their Application described, the amphiphilic copolymers from one predominant proportion of at least one hydrophobic monomer and one minor portion of at least one copolymerizable hydrophilic Monomers are formed. The following are listed as hydrophobic monomers: long chain alkyl (meth) acrylates, long chain alkoxy or Alkylphenoxy (polyethylene oxide) - (meth) acrylates, primary alkenes, vinyl esters of long-chain alkyl carboxylic acids and their mixtures. The Hydrophilic comonomers present to a lesser extent are ethylenic unsaturated water-soluble acids or hydrophilic basic ones Comonomers. The weight average molecular weight of the copolymers is in the range of 2,000 to 100,000.

    Die EP 412 389 beschreibt als Mittel zum Hydrophobieren von Leder und Pelzfellen den Einsatz von Copolymerisaten, die durch radikalische Copolymerisation von (a) C8-40-Monoolefinen mit (b) ethylenisch ungesättigten C4-8-Dicarbonsäureanhydriden nach Art einer Substanzpolymerisation bei Temperaturen von 80 bis 300°C zu Copolymerisaten mit Molmassen von 500 bis 20.000 g/Mol, anschließende Solvolyse der Anhydridgruppen der Copolymerisate und zumindest partielle Neutralisation der bei der Solvolyse entstehenden Carboxylgruppen in wäßrigem Medium mit Basen hergestellt worden sind und die in Form von wäßrigen Dispersionen oder Lösungen vorliegen.EP 412 389 describes the use of copolymers as agents for hydrophobicizing leather and fur skins, which are obtained by radical copolymerization of (a) C 8-40 monoolefins with (b) ethylenically unsaturated C 4-8 dicarboxylic acid anhydrides in the manner of bulk polymerization at temperatures from 80 to 300 ° C to copolymers with molecular weights of 500 to 20,000 g / mol, subsequent solvolysis of the anhydride groups of the copolymers and at least partial neutralization of the carboxyl groups formed in the solvolysis have been prepared in an aqueous medium with bases and which are in the form of aqueous dispersions or There are solutions.

    In der EP 418 661 wird zum gleichen Zweck die Verwendung von Copolymerisaten beschrieben, die (a) 50 bis 90 Gew.-% C8-40-Alkyl(meth)acrylate, Vinylester von C8-40-Carbonsäuren oder deren Mischungen und (b) 10 bis 50 Gew.-% monoethylenisch ungesättigte C3-12-Carbonsäuren, monoethylenisch ungesättigte Dicarbonsäureanhydride, Halbester oder Halbamide von monoethylenisch ungesättigten C4-12-Dicarbonsäuren, Amide von C3-12-Monocarbonsäuren oder Mischungen davon einpolymerisiert enthalten und Molmassen von 500 bis 30.000 g/Mol besitzen. Die Copolymerisate liegen in zumindest partiell neutralisierter Form in wäßriger Lösung oder in wäßriger Dispersion für den angegebenen Einsatzzweck vor.For the same purpose, EP 418 661 describes the use of copolymers which contain (a) 50 to 90% by weight of C 8-40 alkyl (meth) acrylates, vinyl esters of C 8-40 carboxylic acids or mixtures thereof and ( b) 10 to 50% by weight of monoethylenically unsaturated C 3-12 carboxylic acids, monoethylenically unsaturated dicarboxylic acid anhydrides, half esters or half amides of monoethylenically unsaturated C 4-12 dicarboxylic acids, amides of C 3-12 monocarboxylic acids or mixtures thereof, and copolymerized, and molecular weights possess from 500 to 30,000 g / mol. The copolymers are in at least partially neutralized form in aqueous solution or in aqueous dispersion for the intended use.

    Untersuchungen der Anmelderin haben gezeigt, daß für das rasche und gleichmäßige Eindringen von Fettungsmitteln dieser Art vergleichsweise niedere Molmassen von entscheidender Bedeutung sein können. Für den Polymerchemiker finden sich entsprechende mittelbare Hinweise auch in den drei zuletzt genannten Druckschriften bei der Schilderung der Herstellung der dort jeweils beschriebenen Copolymertypen. Die radikalische Copolymerisation der jeweils beanspruchten Komponenten zu (a) und (b) soll zweckmäßigerweise in Gegenwart von Kettenüberträgern wie Mercaptanen (EP 372 746 A2, Seite 6, 20/21) beziehungsweise in Gegenwart von Reglern wie C1-4-Aldehyde, Allylalkohol, Buten-1-ol-3, Ameisensäure oder organische SH-Gruppen enthaltende Verbindungen vorgenommen werden (EP 418 661 Al, Spalte 6, Absatz 2). Auch in der EP 412 389 wird die Mitverwendung entsprechender Regler zur Gewinnung hinreichend niedrig molekularer Polymerisate empfohlen, siehe dort Al, Spalte 4, Absatz 2.Investigations by the applicant have shown that comparatively low molar masses can be of crucial importance for the rapid and uniform penetration of fatliquors of this type. For the polymer chemist, there are also corresponding indirect references in the last three publications mentioned in the description of the production of the types of copolymers described there. The free radical copolymerization of the components claimed in each case to (a) and (b) should advantageously be carried out in the presence of chain transfer agents such as mercaptans (EP 372 746 A2, page 6, 20/21) or in the presence of regulators such as C 1-4 aldehydes, allyl alcohol , Buten-1-ol-3, formic acid or compounds containing organic SH groups can be carried out (EP 418 661 Al, column 6, paragraph 2). EP 412 389 also recommends the use of appropriate regulators for obtaining sufficiently low molecular weight polymers, see Al, column 4, paragraph 2.

    Gegenstand der älteren Patentanmeldung DE-A-P 41 29 244.8 der Anmelderin ist die Verwendung wäßriger Dispersionen von Co-Oligomeren aus der radikalisch ausgelösten wäßrigen Emulsionscopolymersation im schwach sauren bis neutral eingestellten pH-Bereich als amphiphiles Mittel zur fettenden und auswaschfesten Ausrüstung von Leder und Pelzfellen; Hauptktkomponenten sind dabei Halbester der Maleinsäure mit oleophilen Alkoholen und/oder deren niederen Alkylenoxidaddukten sowie Acrylsäure und/oder Methacrylsäure; zusätzlich können auch untergeordnete Mengen von weiteren hydrophilen und/oder oleophilen Co-Monomeren im Oligomeren-Molekül enthalten sein.Subject of the earlier patent application DE-A-P 41 29 244.8 of the applicant is the use of aqueous dispersions of co-oligomers from the radically triggered aqueous emulsion copolymerization in weakly acidic to neutral pH range as amphiphiles Means for greasing and washable finishing of leather and Fur skins; The main components are half esters of maleic acid with oleophilic alcohols and / or their lower alkylene oxide adducts as well as acrylic acid and / or methacrylic acid; in addition can also minor amounts of other hydrophilic and / or oleophilic Co-monomers can be contained in the oligomer molecule.

    Beschreibung der ErfindungDescription of the invention

    Aufgabe der vorliegenden Erfindung war es, Mittel für das oben geschilderte Anwendungsgebiet, d.h. für die fettende Ausrüstung von Leder zur Verfügung zu stellen.The object of the present invention was to provide means for the above Field of application, i.e. for the greasing equipment of To provide leather.

    Diese Aufgabe wurde erfindungsgemäß gelöst durch wäBrige Dispersionen mit einem Gehalt an speziellen Aminopropionsäurederivaten und Co-Oligomeren auf Basis von Fettcrotonaten. Unter Fettcrotonaten sind dabei Ester der Crotonsäure (trans-2-Butensäure) mit C10-40-Fettalkoholen zu verstehen.This object was achieved according to the invention by aqueous dispersions containing special aminopropionic acid derivatives and co-oligomers based on fat crotonates. Fat crotonates are esters of crotonic acid (trans-2-butenoic acid) with C 10-40 fatty alcohols.

    Gegenstand der vorliegenden Erfindung sind wäßrige Dispersionen enthaltend

  • i) mindestens ein Aminopropionsäurederivat der allgemeinen Formel (I)
    Figure 00060001
    worin
    • der Rest R1 eine gesättigte oder ungesättigte, geradkettige oder verzweigte Alkyl- oder Alkoxyalkylgruppe mit 8 bis 22 C-Atomen,
    • der Rest R2 eine Alkylgruppe mit 1 bis 18 C-Atomen, einen gesättigten oder ungesättigten Carboxyalkylrest mit 3 bis 4 C-Atomen, einen Carboxyphenylrest oder einen Carboxylrest
    • der Rest R3 Wasserstoff oder eine Methylgruppe,
    • der Rest X Wasserstoff, Alkalimetall, Erdalkalimetall, Ammonium, Alkylammonium oder Alkanolammonium und
    • der Rest Y eine Gruppe -CO-, -SO2-, -CONH oder eine Alkylengruppe mit bis zu drei C-Atomen
    bedeuten, und
  • ii) mindestens ein wasserdispergierbares und/oder wasseremulgierbares Co-Oligomer (II) aus
  • a) Fettcrotonaten und
  • b) radikalisch copolymerisierbaren hydrophilen ethylenisch ungesättigen Säuren und/oder deren Anhydriden, die auch
  • c) untergeordnete Mengen weiterer copolymerisierbarer Comonomere enthalten können.
    • The present invention relates to aqueous dispersions containing
  • i) at least one aminopropionic acid derivative of the general formula (I)
    Figure 00060001
    wherein
    • the radical R 1 is a saturated or unsaturated, straight-chain or branched alkyl or alkoxyalkyl group with 8 to 22 C atoms,
    • the radical R 2 is an alkyl group having 1 to 18 carbon atoms, a saturated or unsaturated carboxyalkyl radical having 3 to 4 carbon atoms, a carboxyphenyl radical or a carboxyl radical
    • the radical R 3 is hydrogen or a methyl group,
    • the radical X is hydrogen, alkali metal, alkaline earth metal, ammonium, alkylammonium or alkanolammonium and
    • the radical Y is a group -CO-, -SO 2 -, -CONH or an alkylene group with up to three C atoms
    mean and
  • ii) at least one water-dispersible and / or water-emulsifiable co-oligomer (II)
  • a) fat crotonates and
  • b) free-radically copolymerizable hydrophilic ethylenically unsaturated acids and / or their anhydrides, which also
  • c) may contain minor amounts of further copolymerizable comonomers.

    • In einer bevorzugten Ausführungsform bedeutet der Rest R1 in der Formel für die Aminopropionsäurederivate (I) einen gesättigten Alkylrest mit überwiegend 12 bis 18 C-Atomen. In einer weiteren bevorzugten Ausführungsform bedeutet der Rest Y in der Formel für die Aminopropionsäurederivate (I) eine Alkylengruppe, insbesondere eine Gruppe -CH2-CH2-, und der Rest R2 eine Carboxylgruppe (-CO2H). In a preferred embodiment, the radical R 1 in the formula for the aminopropionic acid derivatives (I) is a saturated alkyl radical with predominantly 12 to 18 carbon atoms. In a further preferred embodiment, the radical Y in the formula for the aminopropionic acid derivatives (I) is an alkylene group, in particular a group -CH 2 -CH 2 -, and the radical R 2 is a carboxyl group (-CO 2 H).

    Die erfindungsgemäße Lehre sieht somit für das hier vorgegebene Anwendungsgebiet der fettenden Ausrüstung von Ledern und Pelzen eine Kombination spezieller Aminopropionsäurederivate mit Co-Oligomeren auf Basis von Fettcrotonaten, deren Verwendung als oleophile Hauptkomponente in amphiphilen Zurichtungsmitteln der betroffenen Art im Stand der Technik bisher nicht beschrieben ist, vor.The teaching according to the invention thus provides for the application area specified here the greasing equipment of leather and fur Combination of special aminopropionic acid derivatives with co-oligomers based on fat crotonates, their use as the main oleophilic component in amphiphilic dressings of the type concerned in The prior art has not been described so far.

    Die erfindungsgemäßen Mittel sind zur raschen und durchdringenden imprägnierenden Ausrüstung von Leder und/oder Pelzen besonders geeignet, so daB waschechte und auch reinigungsfeste Leder und Pelzfelle zugänglich werden. Darüber hinaus weisen die so erhaltenen Leder aufgrund der hydrophobierenden Eigenschaften der erfindungsgemäßen Mittel eine gute Wasserfestigkeit auf.The agents according to the invention are for rapid and penetrating impregnating finish of leather and / or fur particularly suitable, so that genuine and cleanable leather and fur skins become accessible. In addition, the so obtained Leather due to the hydrophobic properties of the invention Good water resistance.

    In Bezug auf die Co-Oligomeren (II) gilt, daß diejenigen Fettcrotonat-Bausteine (a) bevorzugt sind, die als Alkohol-Komponente C12-24-Fettalkohole enthalten. Geradkettige Fettalkohole bzw. deren Mischungen sind dabei bevorzugt. Es hat sich allerdings gezeigt, daß auch die Mitverwendung von verzweigtkettigen Fettalkoholen im Fettcrotonat-Baustein (a) im Einzelfall zu interessanten Ergebnissen führen kann. So kann beispielsweise durch Mitverwendung von solchen verzweigtkettigen Alkoholen in beschränktem Ausmaß die Penetrationsfähigkeit des Co-Oligomeren (II) in die Faserstruktur des auszurüstenden Hautmaterials gefördert werden. Dabei ist es auch möglich, entsprechende verzweigte Alkohole einer kürzeren C-Zahl einzusetzen, wobei entsprechende Alkohole mit wenigstens 6 C-Atomen, vorzugsweise mit wenigstens 8 C-Atomen, in Betracht kommen. Ein wichtiger verzweigtkettiger Alkohol, der im Zusammenhang mit den Fettcrotonat-Bausteinen (a) zum Einsatz kommen kann, ist das 2-Ethylhexanol. Die Menge der mitzuverwendenden verzweigtkettigen insbesondere kürzeren Alkohole wird allerdings immer vergleichsweise gering sein. So werden in der Regel nicht mehr als 50 Gew.-%, vorzugsweise nicht mehrals 30 oder nicht mehr als 20 Gew.-% der in (a) vorliegenden Alkoholreste durch solche verzweigtkettigen insbesondere niederen Alkohole gebildet. Für das praktische Arbeiten haben sich - bezogen auf das oleophile Fettcrotonat (a) - Mengenverhältnisse von wenigstens etwa 90-95 Gew.-% der ausgeprägt oleophilen langkettigen Fettalkohole, insbesondere des Bereichs C12-18, als besonders geeignete Komponenten zur Ausbildung der Crotonatester erwiesen.With regard to the co-oligomers (II) it is true that those fatty crotonate building blocks (a) are preferred which contain C 12-24 fatty alcohols as the alcohol component. Straight-chain fatty alcohols or their mixtures are preferred. However, it has been shown that the use of branched-chain fatty alcohols in the fat crotonate component (a) can also lead to interesting results in individual cases. For example, by using such branched-chain alcohols to a limited extent, the penetrability of the co-oligomer (II) into the fiber structure of the skin material to be treated can be promoted. It is also possible to use corresponding branched alcohols with a shorter carbon number, suitable alcohols having at least 6 carbon atoms, preferably having at least 8 carbon atoms. An important branched chain alcohol that can be used in connection with the fatty crotonate building blocks (a) is 2-ethylhexanol. However, the amount of branched-chain, in particular shorter, alcohols to be used will always be comparatively small. As a rule, no more than 50% by weight, preferably no more than 30 or no more than 20% by weight, of the alcohol residues present in (a) are formed by such branched-chain, in particular lower, alcohols. For practical work - based on the oleophilic fat crotonate (a) - quantitative ratios of at least about 90-95% by weight of the pronounced oleophilic long-chain fatty alcohols, especially in the range C 12-18 , have proven to be particularly suitable components for the formation of the crotonate esters .

    Die in den amphiphilen Co-Oligomeren (II) zum Einsatz kommenden hydrophilen Komponenten (b) können den entsprechenden Bausteinen aus den Co-Oligomeren der zitierten EP 372 746, EP 412 389 und EP 418 661 entsprechen. Insbesondere die zuletzt genannte Druckschrift bringt hier ausführliche Angaben zu geeigneten Stoffklassen und zahlreichen speziellen Vertretern.The hydrophilic used in the amphiphilic co-oligomers (II) Components (b) can consist of the corresponding building blocks the co-oligomers of EP 372 746, EP 412 389 and Correspond to EP 418 661. In particular the last-mentioned publication provides detailed information on suitable classes of substances and numerous special representatives.

    Besonders wichtige Bausteine (b) für die Co-Oligomeren (II) sind im Sinne der vorliegenden Erfindung ethylenisch ungesättigte Monocarbonsäuren und/oder ethylenisch ungesättigte Dicarbonsäuren und/oder deren Anhydride mit bevorzugt jeweils bis zu 12 C-Atomen. Die Dicarbonsäuren können auch wenigstens anteilsweise in Form ihrer Partialderivate mit einer Carboxylgruppe und einer derivatisierten Carbonsäuregruppe zum Beispiel als Dicarbonsäure-Halbester vorliegen.Particularly important building blocks (b) for the co-oligomers (II) are in According to the present invention, ethylenically unsaturated monocarboxylic acids and / or ethylenically unsaturated dicarboxylic acids and / or their anhydrides each with preferably up to 12 carbon atoms. The dicarboxylic acids can also at least partially in the form of their partial derivatives with a carboxyl group and a derivatized carboxylic acid group for example as dicarboxylic acid half esters.

    Besonders interessante Vertreter aus der Klasse monoethylenisch ungesättigter C3-12-Monocarbonsäuren sind beispielsweise Acrylsäure, Methacrylsäure und die Crotonsäure. Besonders geeignete Bausteine (b) können aber auch Dicarbonsäuren beziehungsweise deren Derivate, insbesondere deren Anhydride sein. Typische Vertreter sind die Maleinsäure, Fumarsäure, Itaconsäure, Glutaconsäure und entsprechende Anhydride.Particularly interesting representatives from the class of monoethylenically unsaturated C 3-12 monocarboxylic acids are, for example, acrylic acid, methacrylic acid and crotonic acid. Particularly suitable building blocks (b) can also be dicarboxylic acids or their derivatives, in particular their anhydrides. Typical representatives are maleic acid, fumaric acid, itaconic acid, glutaconic acid and corresponding anhydrides.

    Besondere Bedeutung kommt dabei dem Maleinsäureanhydrid zu. Fettcrotonate (a) und Maleinsäureanhydrid lassen sich in befriedigender Weise mit oder ohne Verwendung von Hilfslösungsmitteln zu Co-Oligomeren (II) eines leicht einstellbar niedrigen Molgewichtes umsetzen. Es ist dabei insbesondere möglich, etwa gleiche Molmengen an Maleinsäureanhydrid und Fettcrotonat miteinander zur Umsetzung zu bringen, so daß nach Solvolyse, insbesondere Hydrolyse der Maleinsäureanhydrid-Bausteine einerseits hinreichend hohe Konzentrationen an Carboxylgruppen für die Fixierung der Oligomeren in der Haut- beziehungsweise Faserstruktur zur Verfügung stehen, andererseits aber auch zuverlässig hohe Gehalte des oleophilen und damit fettenden und wasserabweisenden Fettcrotonat-Baustein eingebunden sind.Maleic anhydride is of particular importance. Fat crotonates (a) and maleic anhydride can be satisfactory Way with or without the use of auxiliary solvents to co-oligomers (II) implement an easily adjustable low molecular weight. It is particularly possible to use approximately the same molar amounts Maleic anhydride and fat crotonate with each other for implementation bring so that after solvolysis, especially hydrolysis of the maleic anhydride building blocks on the one hand, sufficiently high concentrations on carboxyl groups for fixing the oligomers in the skin or Fiber structure are available, on the other hand also reliably high levels of oleophilic and therefore greasy and water-repellent fat crotonate building block.

    Neben oder anstelle dieser hydrophilen Bausteine (b) auf Basis von Carbonsäuren sind aber auch andere copolymerisierbare hydrophile Verbindungen verwendbar. In Betracht kommen hier insbesondere Sulfosäuregruppen enthaltende ethylenisch ungesättigte Monomere. Bekannte Vertreter dieser Art sind insbesondere entsprechende aliphatische und/oder aromatische Sulfonsäuren, wie Styrolsulfonsäure aber auch Verbindungen wie Vinylsulfonsäure, Allylsulfonsäure, Methallylsulfonsäure und dergleichen. Wie bereits angegeben kann der Baustein (b) des Co-Oligomeren (II) ganz oder teilweise aus solchen der Copolymerisation beziehungsweise Co-Oligomerisation zugänglichen Sulfosäureverbindungen gebildet sein.In addition to or instead of these hydrophilic building blocks (b) based on However, carboxylic acids are also other copolymerizable, hydrophilic Connections can be used. Sulfoic acid groups in particular come into consideration here containing ethylenically unsaturated monomers. Known Representatives of this type are, in particular, corresponding aliphatic ones and / or aromatic sulfonic acids, such as styrene sulfonic acid also compounds such as vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid and the same. As already stated, the block can (b) of the co-oligomer (II) wholly or partly from those of the copolymerization or co-oligomerization accessible sulfonic acid compounds be educated.

    Besonders bevorzugt sind solche Co-Oligomere (II) in denen die Bausteine (a) und (b) in Verhältnissen von 30 bis 90 Gew% (a) auf 70 bis 10 Gew.-% (b) vorliegen - Gew.-% hier bezogen auf die Summe von (a) und (b). Bevorzugte Bereiche für die Mischungsverhältnisse sind etwa 35 bis 80 Gew.-% (a) auf 65 bis 20 Gew.-% (b).Co-oligomers (II) in which the building blocks are particularly preferred (a) and (b) in ratios of 30 to 90% by weight (a) to 70 up to 10% by weight (b) are present -% by weight here based on the sum of (a) and (b). Preferred ranges for the mixing ratios are about 35 to 80% by weight (a) to 65 to 20% by weight (b).

    Neben den Bausteinen (a) und (b) können die amphiphilen Co-Oligomeren (II) auch untergeordnete Mengen weiterer copolymerisierbarer Comonomere enthalten, die in der obigen Definition als Bausteine (c) bezeichnet sind. Geeignet können hier beliebige der Co-Oligomerisation zugängliche ethylenisch ungesättigte Verbindungen sein, wie sie im einschlägigen Stand der Technik beschrieben sind, vgl. hier beispielsweise EP 418 661 Al, Spalte 3, 49 bis Spalte 4, 27. In der Regel handelt es sich hier um Comonomere, die weder eine ausgeprägte hydrophobierende Wirkung aufweisen noch hydrophilierende Gruppen im Sinne der Carboxylgruppen oder Sulfonsäuregruppen der erfindungsgemäß mitverwendeten Komponenten (b) besitzen. Werden solche Comonomere (c) in den erfindungsgemäß beschriebenen amphiphilen Co-Oligomeren mitverwendet, so beträgt ihr Anteil vorzugsweise nicht mehr als etwa 30 Gew.-% und insbesondere nicht mehr als etwa 15 Gew.-%- die Angabe Gew.-% - bezieht sich dabei auf die Summe von (a), (b) und (c).In addition to building blocks (a) and (b), the amphiphilic co-oligomers can (II) also minor amounts of other copolymerizable Contain comonomers, which are in the above definition as building blocks (c) are designated. Any of the co-oligomerization can be suitable here accessible ethylenically unsaturated compounds as they are are described in the relevant prior art, cf. here for example EP 418 661 Al, column 3, 49 to column 4, 27. In the As a rule, these are comonomers that are neither pronounced Hydrophobing effect also have hydrophilizing groups in the Sense of the carboxyl groups or sulfonic acid groups of the invention have used components (b). Such comonomers (c) in the amphiphilic co-oligomers described according to the invention used, their share is preferably no longer than about 30% by weight and in particular not more than about 15% by weight - % by weight - refers to the sum of (a), (b) and (c).

    Im Sinne der erfindungsgemäßen Lehre sind diejenigen Co-Oligomere (II) besonders bevorzugt, die frei sind von den gemäß der obigen Definition fakultativen Bausteinen (c), das heißt die ausschließlich aus den Bausteinen (a) und (b) aufgebaut sind. Diese bevorzugten Co-Oligomeren (II) enthalten dabei die Bausteine (a) und (b) in Mischungsverhältnissen von etwa 40 bis 70 Gew.-% (a) auf 60 bis 30 Gew.-% (b); die Gew.-%-Angaben beziehen sich dabei wieder die Summe von (a) und (b).In the sense of the teaching according to the invention, those are co-oligomers (II) particularly preferred which are free from those according to the above Definition of optional building blocks (c), that is, the exclusive ones are built up from building blocks (a) and (b). These preferred Co-oligomers (II) contain building blocks (a) and (b) in mixing ratios from about 40 to 70% by weight (a) to 60 to 30 % By weight (b); the percentages by weight relate to the sum again of (a) and (b).

    Die Co-Oligomeren (II) auf Basis der Fettcrotonate weisen bevorzugt mittlere Molgewichte (Molmassen) im Bereich von etwa 500 bis 30.000 g/Mol auf. Geeignet können dabei insbesondere Molmassen im Bereich von etwa 1.000 bis 15.000 g/Mol sein. Es hat sich gezeigt, daß innerhalb dieser vergleichsweise breiten Bereiche den unteren Werten - mittlere Molgewichte beziehungsweise Molmassen im Bereich von etwa 1.000 bis 4.000 oder 5.000 g/Mol und zweckmäßigerweise im Bereich von etwa 1.000 bis 3.000 g/Mol - besondere Bedeutung zukommen kann.The co-oligomers (II) based on the fat crotonates preferably have average molecular weights in the range from about 500 to 30,000 g / mole. Molar masses in the range can be particularly suitable from about 1,000 to 15,000 g / mol. It has been shown that within of these comparatively broad areas the lower values - average molecular weights or molecular weights in the range of about 1,000 to 4,000 or 5,000 g / mol and expediently in the range from about 1,000 to 3,000 g / mol - can be of particular importance.

    Wie angegeben sind diejenigen Co-Oligomere (II) im Rahmen der erfindungsgemäßen Lehre bevorzugt, die aus der Umsetzung von Fettcrotonaten und Maleinsäureanhydrid resultieren und deren Maleinsäureanhydrid-Bausteine durch Hydrolyse und/oder Solvolyse mit H-aktiven Komponenten in die korrespondierende Form mit freien Carboxylgruppen umgewandelt worden sind. Zur Solvolyse der Maleinsäureanhydrid-Bausteine mit H-aktiven Komponenten eignen sich insbesondere Alkohole aber auch andere Verbindungen wie Carbonsäuren, reaktiven Wasserstoff enthaltende Aminoverbindungen und dergleichen. Durch eine solche gezielte Solvolyse kann gezielt Einfluß genommen werden auf eine Verstärkung der fettenden beziehungsweise wasserabweisenden Eigenschaften der Co-Oligomeren (II). Darüber hinaus kann durch Mitverwendung hinreichend langer Kohlenwasserstoffreste das Verhältnis von oleophilen zu hydrophilen Gruppen in Richtung auf die wasserabweisenden oleophilen Elemente verschoben werden.As indicated, those co-oligomers (II) are within the scope of the invention Lessons preferred from the implementation of fat crotonates and maleic anhydride result and their maleic anhydride building blocks by hydrolysis and / or solvolysis with H-active components in the corresponding form with free carboxyl groups have been converted. For solvolysis of maleic anhydride building blocks with H-active components, alcohols are particularly suitable but also other compounds such as carboxylic acids, reactive hydrogen containing amino compounds and the like. By a Such targeted solvolysis can be influenced in a targeted manner a strengthening of the greasy or water-repellent Properties of the co-oligomers (II). In addition, by sharing sufficiently long hydrocarbon residues the ratio from oleophilic to hydrophilic groups towards the water-repellent oleophilic elements are moved.

    Der Zugang zu den Co-Oligomeren (II) ist aber auch beispielsweise auf folgende Art möglich: In einer ersten Verfahrensstufe werden die freie Crotonsäure und Maleinsäureanhydrid miteinander zur entsprechenden Oligomerverbindung umgesetzt. Anschließend wird unter Ausschluß von Wasser und raschem Austrag des Kondensationswassers eine Veresterung der Crotonsäurebestandteile mit den gewünschten Fettalkoholen beziehungsweise Fettalkoholgemischen vorgenommen. Nachfolgend wird dann die Hydrolyse beziehungsweise Solvolyse der Anhydridringe durchgeführt.However, access to the co-oligomers (II) is also, for example possible in the following way: In a first process stage, the free crotonic acid and maleic anhydride with each other to the corresponding Implemented oligomer compound. Then is excluded of water and rapid discharge of the condensation water Esterification of the crotonic acid components with the desired fatty alcohols or fatty alcohol mixtures. Below then the hydrolysis or solvolysis of the anhydride rings carried out.

    Die erfindungsgemäßen Mittel werden bevorzugt auf einen schwach sauren bis schwach alkalischen Bereich eingestellt. Zur Sicherstellung der Lagerstabilität kann es dabei zweckmäßig sein, Anbietungsformen vorzusehen, deren wäßrige Phase durch Zugabe von anorganischen und/oder organischen Basen auf neutrale bis schwach alkalische pH-Werte eingestellt ist. Zur pH-Regulierung eignen sich an sich alle im einschlägigen Stand der Technik beschriebenen Basen. Besonders bevorzugt sind die Alkalisalze, insbesondere des Natriums und/oder Kaliums. Aber auch Ammoniumsalze oder Salze von Alkanolaminen wie Diethanolamin sind geeignete Vertreter. Bevorzugte pH-Werte für lagerstabile Produkte können im Bereich um pH 7 bis 8 liegen. Es können auf diese Weise wäßrig-pastöse Massen hergestellt werden, deren Wertstoffgehalt an den Komponenten (I) und (II) beispielsweise im Bereich von etwa 30 bis ca.75 Gew.-% liegt. Solche pastösen Massen sind mit Wasser und/oder wäßrigen Wirkstoffabmischungen der im nachfolgenden geschilderten Art jederzeit aufzumischen und zum praktischen Einsatz zu bringen.The agents according to the invention are preferably weak acidic to weakly alkaline range. To make sure Storage stability, it may be appropriate to offer forms provide the aqueous phase by adding inorganic and / or organic bases on neutral to weakly alkaline pH values is set. Suitable for pH regulation all bases described in the relevant prior art. Especially the alkali salts, in particular sodium, are preferred and / or potassium. But also ammonium salts or salts of alkanolamines such as diethanolamine are suitable representatives. Preferred pH values for products that are stable in storage can be in the range of pH 7 to 8. In this way, aqueous pasty masses can be produced be, the valuable content of components (I) and (II) for example is in the range of about 30 to about 75% by weight. Such pasty masses are mixed with water and / or aqueous active ingredients of the type described below at any time and to put it into practical use.

    In einer wichtigen Ausführungsform werden die erfindungsgemäßen Mittel zusammen mit ausgewählten Emulgatoren eingesetzt, die beim Eintrag in insbesondere mineralgegerbte Leder und/oder Felle eine zusätzliche Fettung beziehungsweise Hydrophobierung bewirken und bevorzugt gleichzeitig über saure Gruppen im gegerbten Leder beziehungsweise Fell fixiert werden können. Ein wichtiges Beispiel für Verbindungen dieser Art sind die eingangs genannten in Wasser emulgierbaren Sulfobernsteinsäure-Halbester, die von langkettigen Fettalkoholen und/oder ihren Alkylenoxidaddukten abstammen. Ein wichtiges Beispiel für die Emulgatorenklasse der hier betroffenen Art sind C18-Sulfobernsteinsäure-Halbester. Es hat sich gezeigt, daß durch die Mitverwendung solcher emulgatorartiger Hilfskomponenten - die an sich als Ausrüstungsmittel für die Lederfettung vorbekannt sind - im Sinne der erfindungsgemäßen Zielsetzung vorteilhafte Wirkungen erreicht werden können. Als Beispiele für Verbindungstypen dieser Art seien im einzelnen hier benannt:In an important embodiment, the agents according to the invention are used together with selected emulsifiers which, when introduced into mineral-tanned leather and / or furs in particular, cause additional greasing or hydrophobicization and can preferably be fixed simultaneously via acidic groups in the tanned leather or fur. An important example of compounds of this type are the water-emulsifiable sulfosuccinic acid half-esters mentioned at the outset, which are derived from long-chain fatty alcohols and / or their alkylene oxide adducts. An important example of the emulsifier class of the type concerned here are C 18 sulfosuccinic acid half esters. It has been shown that by using such emulsifier-like auxiliary components - which are known per se as finishing agents for leather greasing - advantageous effects can be achieved in the sense of the objective according to the invention. The following are examples of connection types of this type:

    Sulfobernsteinsäure-Halbester langkettiger Fettalkohole mit insbesondere 12 bis 24 C-Atomen und/oder deren Alkylenoxidaddukten mit bevorzugt bis zu 6 Alkylenoxidresten, entsprechende Sulfobernsteinsäure-Halbester von Fettsäuremono- und/oder -diglyceriden beziehungsweise deren Alkylenoxidaddukten mit bevorzugt bis zu 6 Alkylenoxidresten bei weiterhin bevorzugter Kettenlänge der Fettsäure(n) im Bereich C12-24, langkettige Sulfofettsäuren, insbesondere entsprechende alpha-Sulfofettsäuren mit vorzugsweise 12 bis 24, insbesondere 16 bis 18 C-Atomen, wobei im Falle dieser alpha-substituierten Sulfofettsäuren die Kohlenwasserstoffreste üblicherweise gesättigt sind, sowie innenständige Sulfofettsäuren von olefinisch 1- und/oder mehrfach ungesättigten Carbonsäuren wie Ölsäure, Linolsäure, Linolensäure und dergleichen.Sulfosuccinic acid half-esters of long-chain fatty alcohols with in particular 12 to 24 C atoms and / or their alkylene oxide adducts with preferably up to 6 alkylene oxide residues, corresponding sulfosuccinic acid half-esters of fatty acid mono- and / or diglycerides or their alkylene oxide adducts with preferably up to 6 alkylene oxide residues with a further preferred chain length the fatty acid (s) in the range C 12-24 , long-chain sulfofatty acids, in particular corresponding alpha-sulfofatty acids with preferably 12 to 24, in particular 16 to 18, carbon atoms, in the case of which alpha-substituted sulfofatty acids the hydrocarbon radicals are usually saturated, and internal Sulfofatty acids of olefinically 1- and / or polyunsaturated carboxylic acids such as oleic acid, linoleic acid, linolenic acid and the like.

    Die erfindungsgemäßen Mittel können auch Fettungs- beziehungsweise Hydrophobierungsmittel im Sinne der Wertstoffgemische aus der eingangs zitierten EP 193 832 enthalten. In dieser Ausführungsform der Erfindung werden also die erfindungsgemäßen Mischungen der Komponenten (I) und (II) kombiniert mit imprägnierenden und/oder hydrophobierenden Fettungsmitteln, wie Sulfobernsteinsäuremonoester-Salze mit C12-24-Fettresten, in Kombination mit weiteren imprägnierenden Fettungsmitteln, ausgewählt insbesondere aus der Gruppe der oxidierten oder oxidierten und teilsulfierten C18-26-Kohlenwasserstoffe oder C32-40-Wachse eingesetzt. Andere Beispiele für diese zusätzlichen imprägnierenden Fettungsmittel sind Phosphorsäuremono-C12-24-Alkylester, Partialester von Polycarbonsäuren wie Citronensäure-Mono-C16-24-Alkylester, Partialester von Polyalkoholen wie Sorbitan-, Glycerin- oder Pentaerythrit-C16-24-fettsäureester.The agents according to the invention can also contain greasing agents or hydrophobizing agents in the sense of the mixtures of materials from EP 193 832 cited at the beginning. In this embodiment of the invention, the mixtures according to the invention of components (I) and (II) combined with impregnating and / or hydrophobizing fatliquoring agents, such as sulfosuccinic acid monoester salts with C 12-24 fat residues, in combination with other impregnating fatliquoring agents are selected in particular from the group of oxidized or oxidized and partially sulfated C 18-26 hydrocarbons or C 32-40 waxes. Other examples of these additional impregnating fatliquors are phosphoric acid mono-C 12-24 alkyl esters, partial esters of polycarboxylic acids such as citric acid mono-C 16-24 alkyl esters, partial esters of polyalcohols such as sorbitan, glycerol or pentaerythritol C 16-24 fatty acid esters .

    Eine besonders geeignete Emulgatorklasse, die im Rahmen der erfindungsgemäßen Lehre mitverwendet werden kann, sind die aus der Ausrüstung von Ledern und Pelzen mit Fettstoffen bekannten N-Acylaminosäuren, insbesondere Fettsäuresarkoside, z.B. N-Oleoyl-sarkosin, wie sie beispielsweise als Emulgatoren zum Eintrag von Silikonölen in Leder und Pelze in der EP-B-0 213 480 im einzelnen beschrieben sind. Geeignete Emulgatoren sind demgemäß insbesondere Salze von N-(C9-20-Acyl)-aminosäuren, wobei entsprechenden Salzen einer Aminosäure mit 2 bis 6 C-Atomen, die mit dem Acylrest einer gesättigten oder ungesättigten Fettsäure mit 9 bis 20 C-Atomen am Aminstickstoff, der gegebenenfalls zusätzlich durch Methyl substituiert ist, besondere Bedeutung zukommt. Geeignete Salze dieser Emulgatoren sind wiederum insbesondere Alkali-, Ammonium- oder Alkanolaminsalze.A particularly suitable class of emulsifiers, which can also be used in the context of the teaching according to the invention, are the N-acylamino acids known from the finishing of leather and furs with fatty substances, in particular fatty acid sarcosides, for example N-oleoyl sarcosine, as used, for example, as emulsifiers for introducing silicone oils in leather and furs are described in detail in EP-B-0 213 480. Suitable emulsifiers are accordingly, in particular, salts of N- (C 9-20 -acyl) -amino acids, corresponding salts of an amino acid having 2 to 6 C atoms, which with the acyl residue of a saturated or unsaturated fatty acid having 9 to 20 C atoms Amine nitrogen, which is optionally additionally substituted by methyl, is of particular importance. Suitable salts of these emulsifiers are in particular alkali, ammonium or alkanolamine salts.

    Von den N-(C9-20-Acyl)-aminosäuren sind solche mit 2 bis 4 C-Atomen und mit der Aminogruppe in alpha-Stellung zur Carboxylgruppe besonders bevorzugt, die weiterhin am Aminstickstoffatom zusätzlich durch eine Methylgruppe substituiert sind. Davon weisen eine besonders überlegene Wirkung die Fettsäuresarkoside von gesättigten oder ungesättigten Fettsäuren mit 9 bis 20, bevorzugt 16 bis 18 C-Atomen auf. Das bevorzugte Sarkosid ist das Ölsäuresarkosid. Weiterhin sind insbesondere das N-Stearoyl-sarkosin, N-Lauroyl-sarkosin und N-Isononanoyl-sarkosin besonders geeignet und zwar jeweils in Form ihrer Alkalisalze, Ammoniumsalze oder der Salze von Mono-, Di- oder Trialkanolaminen mit insbesondere 2 bis 4 C-Atomen im Alkanolrest.Of the N- (C 9-20 -acyl) amino acids, those with 2 to 4 C atoms and with the amino group in the alpha position to the carboxyl group are particularly preferred, which are also substituted on the amine nitrogen atom by a methyl group. Of these, the fatty acid sarcosides of saturated or unsaturated fatty acids with 9 to 20, preferably 16 to 18, carbon atoms have a particularly superior effect. The preferred sarcoside is the oleic acid sarcoside. Furthermore, N-stearoyl sarcosine, N-lauroyl sarcosine and N-isononanoyl sarcosine are particularly suitable, in each case in the form of their alkali metal salts, ammonium salts or the salts of mono-, di- or trialkanolamines with in particular 2 to 4 C- Atoms in the alkanol residue.

    Beim Einsatz von solchen Wertstoffgemischen beträgt die Menge der erfindungsgemäß obligatorisch enthaltenen Komponenten (I) und (II) bevorzugt wenigstens etwa 35 Gew.-% des Wertstoffgemisches und insbesondere wenigstens etwa 50 Gew.-%. Es kann jedoch zweckmäßig sein, wenigstens etwa 70 bis 80 Gew.-% des ingesamt in die auszurüstenden Leder beziehungsweise Pelzfelle einzubringenden Wertstoffgemisches auf Basis der Komponenten (I) und (II) vorzusehen.If such mixtures of materials are used, the amount is Components (I) and (II) compulsory according to the invention preferably at least about 35% by weight of the material mixture and in particular at least about 50% by weight. However, it may be useful at least about 70 to 80 wt .-% of the total to be equipped A mixture of valuable materials to be introduced into leather or fur skins to be provided on the basis of components (I) and (II).

    Der Eintrag der erfindungsgemäBen Mittel über ihre Anbietungsform der wäßrigen Dispersion beziehungsweise ihrer Abmischungen mit den genannten weiteren Komponenten erfolgt in an sich bekannter Weise - siehe hierzu insbesondere auch die Angaben der eingangs genannten Druckschriften für vergleichbare Produkte. Nur kurz sei daher zusammenfassend dargestellt:The entry of the agents according to the invention via their form of offer the aqueous dispersion or its mixtures with the the other components mentioned are carried out in a manner known per se - see in particular also the information given at the beginning Publications for comparable products. Therefore, only a brief summary shown:

    Die erfindungsgemäßen Dispersionen eigenen sich zur Behandlung von allen üblichen gegerbten Häuten, insbesondere entsprechendem Material, das mit Mineralgerbstoffen gegerbt worden ist. Die gegerbten Häute werden üblicherweise vor der Behandlung entsäuert. Sie können bereits vor der Behandlung gefärbt worden sein. Eine Färbung kann aber auch erst nach der erfindungsgemäß durchgeführten Behandlung vorgenommen werden.The dispersions of the invention are suitable for the treatment of all usual tanned hides, especially appropriate material, that has been tanned with mineral tannins. The tanned Skins are usually deacidified before treatment. You can have been stained before treatment. A coloring can but also only after the treatment carried out according to the invention be made.

    Das zur imprägnierende Leder wird mit den Dispersionen in wäBriger Flotte zweckmäßig bei pH-Werten von etwa 4 bis 10 und vorzugsweise bei pH 5 bis 8 und bei Temperaturen von etwa 20 bis 60°C, vorzugsweise 30 bis 50°C, während eines Zeitraumes bis zu einigen Stunden gegebenenfalls mehrstufig behandelt. Die Behandlung erfolgt beispielsweise durch Walken in einem FaB. Die Menge an der erfindungsgemäßen Dispersionen beträgt üblicherweise 0,1 bis 30 Gew.-%, insbesondere 1 bis 20 Gew.-% bezogen auf das Falzgewicht des Leders oder das Naßgewicht der Pelzfelle. Die Flottenlänge beträgt üblicherweise 10 bis 1.000 %, vorzugsweise 30 bis 150 %, bei Pelzfellen 50 bis 500 %.The leather to be impregnated with the dispersions in water Brisk expediently at pH values of about 4 to 10 and preferably at pH 5 to 8 and at temperatures of about 20 to 60 ° C, preferably 30 to 50 ° C, for a period of up to a few hours possibly treated in several stages. The treatment takes place, for example by walking in a FaB. The amount of the invention Dispersions are usually 0.1 to 30 wt .-%, in particular 1 to 20% by weight based on the shaved weight of the leather or the wet weight of the fur skins. The fleet length is usually 10 to 1,000%, preferably 30 to 150%, for fur skins 50 to 500%.

    Nach Abschluß der Behandlung mit der wäßrigen Flotte wird der pH-Wert der Behandlungsflotte durch Zusatz von Säuren in den leicht sauren Bereich verschoben. Geeignet ist insbesondere der Zusatz organischer Säuren, bevorzugt Ameisensäure. Bevorzugte pH-Werte liegen im Bereich von 3 bis 5, vorzugsweise im Bereich von etwa 3,5 bis 4. Gewünschtenfalls kann eine Fixierung mit insbesondere Mineralgerbstoffen nachgeschaltet werden, wobei hier der Einsatz von Aluminiumsalzen, aber auch von anderen mehrwertigen Mineralsalzen, z.B. Chrom- oder Zirkonsalzen besonders bevorzugt sein kann. After completion of the treatment with the aqueous liquor, the pH value the treatment liquor by adding acids in the light acidic area shifted. The addition of organic is particularly suitable Acids, preferably formic acid. Preferred pH values are in the range from 3 to 5, preferably in the range from about 3.5 to 4. If desired, fixation with mineral tanning agents in particular downstream, whereby the use of aluminum salts, but also from other multivalent mineral salts, e.g. Chromium or zirconium salts can be particularly preferred.

    BeispieleExamples 1. Herstellung der erfindungsgemäß einzusetzenden Verbindungen 1.1 Herstellung der Aminopropionsäurederivate (I)1. Preparation of the compounds to be used according to the invention 1.1 Preparation of the aminopropionic acid derivatives (I)

    Die Aminopropionsäurederivate (I) können nach an sich bekannten Methoden, z. B. durch Anlagerung von Acryl- bzw. Methacylsäure an primäre Alkylamine und anschließende Umsetzung der dabei erhaltenen N-Alkylaminopropionsäuren mit Carbonsäureanhydriden, Carbonsäurechloriden, Sulfonsäurechloriden, Isocyanaten, Halogencarbonsäuren oder Acryl- bzw. Methacylsäuren hergestellt werden (vergleiche z. B. die oben zitierte DE-A-37 17 961).The aminopropionic acid derivatives (I) can be prepared by methods known per se, e.g. B. by addition of acrylic or methacrylic acid to primary Alkylamines and subsequent implementation of the resulting N-alkylaminopropionic acids with carboxylic acid anhydrides, carboxylic acid chlorides, Sulfonic acid chlorides, isocyanates, halocarboxylic acids or acrylic or methacrylic acids (see e.g. the above-cited DE-A-37 17 961).

    1.2. Herstellung der (amphiphilen) Co-Oligomeren (II)1.2. Preparation of the (amphiphilic) co-oligomers (II)

    Die Herstellung der erfindungsgemäß einzusetzenden Co-Oligomeren (II) ist nachfolgend für vier ausgewählte Beispiele beschrieben.The preparation of the co-oligomers to be used according to the invention (II) is described below for four selected examples.

    Beispiel 1example 1

    700 g eines C16/18-Fettalkohol-Crotonats (45-55% C16; 45-55% C18-Fettalkohole), 300 g Maleinsäureanhydrid sowie 250 g Xylol wurden in einem 3 1-Reaktor eingewogen. Mit einer konstanten Badtemperatur von 175°C wurde das Reaktionsgemisch bis zum Sieden des Xylols aufgeheizt. Bei einer Innentemperatur von 150°C wurden 47,5 g tert.-Butylperbenzoat in 47,5 g Xylol innerhalb von 2 h zugetropft. Durch die einsetzende Polymerisation stieg die Innentemperatur auf 164°C an. Nach beendeter Initiatordosierung erfolgte eine zweistündige Nachreaktionszeit bei 160°C. Danach wurden nochmals 2,5 g tert.-Butylperbenzoat in 2,5 g Xylol zugegeben. Nach weiteren 2 h Reaktionszeit bei 160°C wurde das Xylol unter Vakuum (50-200 mbar) abgezogen. 700 g of a C 16/18 fatty alcohol crotonate (45-55% C 16 ; 45-55% C 18 fatty alcohols), 300 g maleic anhydride and 250 g xylene were weighed in a 3 1 reactor. With a constant bath temperature of 175 ° C, the reaction mixture was heated until the xylene boiled. At an internal temperature of 150 ° C., 47.5 g of tert-butyl perbenzoate in 47.5 g of xylene were added dropwise over the course of 2 hours. Due to the onset of polymerization, the internal temperature rose to 164 ° C. After the initiator metering had ended, there was a two-hour post-reaction time at 160 ° C. Then another 2.5 g of tert-butyl perbenzoate in 2.5 g of xylene were added. After a further 2 h reaction time at 160 ° C, the xylene was removed under vacuum (50-200 mbar).

    Nach dem Abkühlen auf 80°C wurden 1.500 g Wasser und 30,6 g NaOH zugegeben, so daB sich eine teilneutralisierte stabile Dispersion bildete. Restmonomere: C16-Crotonat 5,1 % C18-Crotonat 6,3 % Maleinsäureanhydrid < 0,1 % Molekulargewichte: Mw 2.100 g/Mol Mn 1.200 g/Mol Feststoffgehalte 40,2 Gew.-% After cooling to 80 ° C, 1,500 g of water and 30.6 g of NaOH were added, so that a partially neutralized stable dispersion was formed. Residual monomers: C 16 crotonate 5.1% C 18 crotonate 6.3% Maleic anhydride <0.1% Molecular weights: Mw 2,100 g / mol Mn 1,200 g / mol Solids contents 40.2% by weight

    Beispiel 2Example 2

    600 g eines C16/18-FettalkoholCrotonats (45-55% C16-; 45-55% C18-Fettalkohol). 400 g Maleinsäureanhydrid sowie 176 g Xylol wurden in einen 3 1-Reaktor eingewogen. Mit einer konstanten Badtemperatur von 160°C wurde das Reaktionsgemisch bis zum Sieden des Xylols aufgeheizt. Bei einer Innentemperatur von 150°C wurden 47,5 g tert.-Butylperbenzoat in 117,8 g Xylol innerhalb von 2 h zugetropft. Durch die einsetzende Polymerisation stieg die Innentemperatur auf 169°C an. Nach beendeter Initiatordosierung erfolgte eine zweistündige Nachreaktionszeit bei 150°C. Danach wurden nochmals 2,5 g tert.-Butylperbenzoat in 6,2 g Xylol zugegeben. Nach Weiteren 2 h Reaktionszeit bei 150°C wurde das Xylol unter Vakuum (50-200 mbar) abgezogen. 600 g of a C 16/18 fatty alcohol cronate (45-55% C 16 -; 45-55% C 18 fatty alcohol). 400 g of maleic anhydride and 176 g of xylene were weighed into a 3 1 reactor. With a constant bath temperature of 160 ° C, the reaction mixture was heated until the xylene boiled. At an internal temperature of 150 ° C., 47.5 g of tert-butyl perbenzoate in 117.8 g of xylene were added dropwise over the course of 2 hours. Due to the onset of polymerization, the internal temperature rose to 169 ° C. After the initiator metering had ended, there was a two-hour post-reaction time at 150 ° C. Then another 2.5 g of tert-butyl perbenzoate in 6.2 g of xylene were added. After a further 2 h reaction time at 150 ° C, the xylene was removed under vacuum (50-200 mbar).

    Nach dem Abkühlen auf 80°C wurden 2.333 g Wasser und 54,4 g NaOH zugegeben, so daß sich eine teilneutralisierte stabile Dispersion bildete. Restmonomere: C16-Crotonat 3,9 % C18-Crotonat 4,3 % Maleinsäureanhydrid < 0,01 % Molekulargewichte: Mw 2.000 g/Mol Mn 1.350 g/Mol Feststoffgehalt 30,1 Gew.-% After cooling to 80 ° C., 2,333 g of water and 54.4 g of NaOH were added, so that a partially neutralized, stable dispersion was formed. Residual monomers: C 16 crotonate 3.9% C 18 crotonate 4.3% Maleic anhydride <0.01% Molecular weights: Mw 2,000 g / mol Mn 1,350 g / mol Solids content 30.1% by weight

    Beispiel 3Example 3

    5.600 g eines C16/18-Fettalkohol-Crotonats (45-55% C16; 45-55% C18--Fettalkohol), 2.400 g Maleinsäureanhydrid sowie 1.800 g Xylol wurden in einem 25 1-Reaktor eingewogen. Mit einer konstanten Badtemperatur von 170°C wurde das Reaktionsgemisch bis zum Sieden des Xylols aufgeheizt. Bei einer Innentemperatur von 150°C wurden 400 g tert.-Butylperbenzoat in 600 g Xylol innerhalb von 2 h zugetropft. Die Innentemperatur wurde während der Reaktion bei 150°C gehalten. Nach beendeter Initiatordosierung erfolgte eine zweistündige Nachreaktionszeit bei 150°C. Danach wurden nochmals 80 g tert.-Butylperbenzoat zugegeben. Nach weiteren 2 h Reaktionszeit bei 150°C wurde das Xylol unter Vakuum (50-200 mbar) abgezogen. 5,600 g of a C 16/18 fatty alcohol crotonate (45-55% C 16 ; 45-55% C 18 fatty alcohol), 2,400 g maleic anhydride and 1,800 g xylene were weighed into a 25 1 reactor. With a constant bath temperature of 170 ° C, the reaction mixture was heated until the xylene boiled. 400 g of tert-butyl perbenzoate in 600 g of xylene were added dropwise at an internal temperature of 150 ° C. in the course of 2 hours. The internal temperature was kept at 150 ° C during the reaction. After the initiator metering had ended, there was a two-hour post-reaction time at 150 ° C. Then another 80 g of tert-butyl perbenzoate were added. After a further 2 h reaction time at 150 ° C., the xylene was drawn off under vacuum (50-200 mbar).

    Nach dem Abkühlen auf 80°C wurden 16.000 g Wasser und 371 g NaOH zugegeben, so daß sich eine teilneutralisierte stabile Dispersion bildete. Restmonomere: C16-Crotonat 5,6 % C18-Crotonat 6,1 % Maleinsäureanhydrid < 0,1 % Molekulargewichte: Mw 2.100 g/Mol Mn 1.300 g/Mol Feststoffgehalt 34,4 Gew.-% After cooling to 80 ° C., 16,000 g of water and 371 g of NaOH were added, so that a partially neutralized, stable dispersion was formed. Residual monomers: C 16 crotonate 5.6% C 18 crotonate 6.1% Maleic anhydride <0.1% Molecular weights: Mw 2,100 g / mol Mn 1,300 g / mol Solids content 34.4% by weight

    Beispiel 4Example 4

    172,2 g Crotonsäure, 206,1 g Maleinsäureanhydrid sowie 100 g Xylol wurden in einem 3 l-Reaktor eingewogen. Mit einer konstanten Badtemperatur von 175°C wurde das Reaktionsgemisch bis zum Sieden des Xylols aufgeheizt. Bei einer Innentempertur von 150°C wurden 18 g tert.-Butylperbenzoat in 64 g Xylol innerhalb von 2 h zugetropft. Die Innentemperatur betrug während der Polymerisation 150°C. Nach beendeter Initiatordosierung erfolgte eine zweistündige Nachreaktionszeit bei 150°C. Danach wurden nochmals 1 g tert.-Butylperbenzoat in 4 g Xylol zugegeben. Nach weiteren 2 h Reaktionszeit wurden 515 g Stenol 1618 (45-55% C16-; 45-55% C18-Fettalkohol) zugegeben. Bei einer Innentemperatur von 160°C erfolgte die azeotrope Veresterung des Polymers mit dem Fettalkohol innerhalb von 7 h. Es wurden 34,1 g Wasser erhalten, was einem Veresterungsumsatz von 95 % entspricht. 172.2 g crotonic acid, 206.1 g maleic anhydride and 100 g xylene were weighed out in a 3 l reactor. With a constant bath temperature of 175 ° C, the reaction mixture was heated until the xylene boiled. At an internal temperature of 150 ° C., 18 g of tert-butyl perbenzoate in 64 g of xylene were added dropwise over the course of 2 hours. The internal temperature was 150 ° C. during the polymerization. After the initiator metering had ended, there was a two-hour post-reaction time at 150 ° C. A further 1 g of tert-butyl perbenzoate in 4 g of xylene were then added. After a further 2 h reaction time, 515 g of Stenol 1618 (45-55% C 16 -; 45-55% C 18 fatty alcohol) were added. At an internal temperature of 160 ° C, the polymer was azeotropically esterified with the fatty alcohol within 7 hours. 34.1 g of water were obtained, which corresponds to an esterification conversion of 95%.

    Nach beendeter Veresterung wurde das Xylol im Vakuum (50-200 mbar) abgetrennt.After the esterification, the xylene was in vacuo (50-200 mbar) severed.

    Nach dem Abkühlen auf 80°C wurden 1.340 g Wasser und 40 g NaOH zugegeben, so daß sich eine teilneutralisiete stabile Dispersion bildete. Restmonomere: Stenol 1618 4,7 % Maleinsäureanhydrid 0,15 % Crotonsäure 0,05 % Molekulargewichte: Mw 10.600 g/Mol Mn 1.000 g/Mol Feststoffgehalt 40,1 Gew.-% After cooling to 80 ° C., 1,340 g of water and 40 g of NaOH were added, so that a partially neutralized, stable dispersion was formed. Residual monomers: Stenol 1618 4.7% Maleic anhydride 0.15% Crotonic acid 0.05% Molecular weights: Mw 10,600 g / mol Mn 1,000 g / mol Solids content 40.1% by weight

    Claims (19)

    1. Preparations for the oiling of leather in the form of an aqueous dispersion, characterized in that they contain
      i) at least one aminopropionic acid derivative corresponding to general formula (I):
      Figure 00290001
      in which
      R1 is a saturated or unsaturated, linear or branched alkyl or alkoxyalkyl group containing 8 to 22 carbon atoms,
      R2 is an alkyl group containing 1 to 18 carbon atoms, a saturated or unsaturated carboxyalkyl group containing 3 to 4 carbon atoms, a carboxyphenyl group or a carboxyl group,
      R3 is hydrogen or a methyl group,
      X is hydrogen, alkali metal, alkaline earth metal, ammonium, alkylammonium or alkanolammonium and
      Y is a group -CO-, -SO2-, -CONH or an alkylene group containing up to three carbon atoms,
      and
      ii) at least one water-dispersible and/or water-emulsifiable co-oligomer (II) of
      a) fatty crotonates and
      b) radical-copolymerizable hydrophilic ethylenically unsaturated acids and/or anhydrides thereof which may also contain
      c) small quantities of other copolymerizable monomers.
    2. Preparations as claimed in claim 1, characterized in that the substituent R1 of the aminopropionic acid derivatives (I) is a saturated alkyl radical predominantly containing 12 to 18 carbon atoms.
    3. Preparations as claimed in claim 1 or 2, characterized in that the substituent Y of the aminopropionic acid derivative (I) is an alkylene group, more particularly a group -CH2-CH2-, and the substituent R2 is a carboxyl group (-CO2H).
    4. Preparations as claimed in any of claims 1 to 3, characterized in that co-oligomers (II) containing esters or ester mixtures of crotonic acid and C12-24 fatty alcohols are used as component (a).
    5. Preparations as claimed in any of claims 1 to 4, characterized in that the co-oligomers (II) used contain as components (b) ethylenically unsaturated monocarboxylic acids, ethylenically unsaturated dicarboxylic acids and/or anhydrides thereof preferably containing up to 12 carbon atoms, the dicarboxylic acids optionally being at least partly present in the form of their partial derivatives containing a carboxyl group and a derivatized carboxylic acid group, for example as dicarboxylic acid semiesters.
    6. Preparations as claimed in any of claims 1 to 5, characterized in that the co-oligomers (II) used at least partly contain residues of copolymerizable aliphatic and/or aromatic sulfonic acids as component (b), component (b) optionally being exclusively formed by such sulfonic acids.
    7. Preparations as claimed in any of claims 1 to 6, characterized in that co-oligomers (II) are used in which components (a) and (b) are present in ratios by weight (based on the sum of (a)+(b)) of 30 to 90 parts and preferably 35 to 80 parts (a) to 70 to 10 parts and preferably 65 to 20 parts (b); where comonomers (c) are used, their percentage content is preferably no more than 30% by weight and, more preferably, no more than 15% by weight (% by weight, based on the sum of (a), (b) and (c)).
    8. Preparations as claimed in any of claims 1 to 7, characterized in that co-oligomers (II) from the radical copolymerization of fatty crotonates with acrylic acid, methacrylic acid, maleic anhydride, maleic acid, crotonic acid and/or fumaric acid are used.
    9. Preparations as claimed in any of claims 1 to 8, characterized in that co-oligomers (II) which have been produced without using chain transfer agents or molecular weight regulators are used.
    10. Preparations as claimed in any of claims 1 to 9, characterized in that co-oligomers (II) with average molecular weights of 500 to 30,000 g/mole and preferably from about 1,000 to 15,000 g/mole are used, co-oligomers of low molecular weight, for example with molecular weights in the range from about 1,000 to 4,000 g/mole, being particularly preferred.
    11. Preparations as claimed in any of claims 1 to 10, characterized in that co-oligomers (II) of fatty crotonate and maleic anhydride, in which the maleic anhydride component has been converted into maleic acid or a maleic acid derivative by hydrolysis and/or solvolysis with H-active components, are used.
    12. Preparations as claimed in any of claims 1 to 11, characterized in that the co-oligomers (II) used have been produced by co-oligomerization of crotonic acid and maleic anhydride, subsequent esterification of the crotonic acid components with fatty alcohols and, if desired, subsequent hydrolysis or solvolysis of the anhydride rings.
    13. Preparations as claimed in any of claims 1 to 12, characterized in that they have been adjusted to a mildly acidic to mildly alkaline pH value.
    14. The use of the preparations claimed in any of claims 1 to 13, the compounds (I) and the co-oligomers (II) being used together with emulsifiers which, on introduction into - in particular - mineral-tanned leathers and/or skins, have an additional oiling effect and, at the same time, can preferably be fixed in the tanned leather or skin by acidic groups, for oiling leather.
    15. The use of the preparations claimed in any of claims 1 to 14, the compounds (I) and the co-oligomers (II) - after introduction into the leathers and/or skins to be finished - being fixed therein by an aftertreatment with, in particular, mineral tanning agents, for oiling leather.
    16. Preparations as claimed in any of claims 1 to 13, characterized in that they additionally contain emulsifiers and/or low molecular weight leather oiling components which contain an oleophilic hydrocarbon radical preferably containing at least 8 to 10 carbon atoms, optionally together with at least one acid group in the molecule, and which are preferably assigned to the following classes:
      sulfosuccinic acid semiesters of long-chain fatty alcohols containing in particular 12 to 24 carbon atoms and/or alkylene oxide adducts thereof preferably containing up to 6 alkylene oxide units,
      sulfosuccinic acid semiesters of fatty acid mono- and/or diglycerides or alkylene oxide adducts thereof preferably containing up to 6 alkylene oxide units for a preferred chain length of the fatty acid(s) of C12-24,
      long-chain sulfofatty acids, more particularly alpha-sulfofatty acids preferably containing 12 to 24 carbon atoms,
      intemal sulfonates of mono- and/or polyolefinically unsaturated fatty acids containing at least 12 and preferably 16 to 24 C atoms,
      salts of an amino acid containing 2 to 6 carbon atoms attached at the amine nitrogen atom to the acyl group of a saturated or unsaturated fatty acid containing 9 to 20 carbon atoms, which may be additionally substituted by methyl, more particularly fatty acid sarcosides.
    17. Preparations as claimed in any of claims 1 to 13 and 16, characterized in that they additionally contain other impregnating and/or hydrophobicizing leather oiling agents, a preferred mixture of this type being based on the following components: sulfosuccinic acid esters with C12-24 fatty groups in combination with compounds from the group of oxidized or oxidized and partly sulfonated C18-26, hydrocarbons or C32-40 waxes, phosphoric acid mono-C12-24-alkyl esters, partial esters of polycarboxylic acids, such as citric acid mono-C18-24-alkyl esters, partial esters of polyalcohols, such as sorbitan, glycerol or pentaerythritol C18-24 fatty acid esters.
    18. Preparations as claimed in any of claims 1 to 13, 16 and 17, characterized in that components (I) and (II) together make up at least about 35% by weight and preferably at least the predominant part of the impregnating and/or hydrophobicizing active substances in the corresponding active-substance mixtures of the aqueous dispersions.
    19. The use of mixtures containing
      i) at least one aminopropionic acid derivative corresponding to general formula (I):
      Figure 00330001
      in which
      R1 is a saturated or unsaturated, linear or branched alkyl or alkoxyalkyl group containing 8 to 22 carbon atoms,
      R2 is an alkyl group containing 1 to 18 carbon atoms, a saturated or unsaturated carboxyalkyl group containing 3 to 4 carbon atoms, a carboxyphenyl group or a carboxyl group,
      R3 is hydrogen or a methyl group,
      X is hydrogen, alkali metal, alkaline earth metal, ammonium, alkylammonium or alkanolammonium and
      Y is a group -CO-, -SO2-, -CONH or an alkylene group containing up to three carbon atoms,
      and
      ii) at least one water-dispersible and/or water-emulsifiable co-oligomer (II) of
      a) fatty crotonates and
      b) radical-copolymerizable hydrophilic ethylenically unsaturated acids and/or anhydrides thereof which may also contain
      c) small quantities of other copolymerizable monomers,
      for oiling leather.
    EP95904545A 1994-01-12 1995-01-03 Fatty treatment agent for leather Expired - Lifetime EP0739425B1 (en)

    Applications Claiming Priority (4)

    Application Number Priority Date Filing Date Title
    DE4400507A DE4400507A1 (en) 1994-01-12 1994-01-12 Leather greasing agents
    DE4400507 1994-01-12
    PCT/EP1995/000011 WO1995019451A1 (en) 1994-01-12 1995-01-03 Fatty treatment agent for leather
    US08/679,475 US5683611A (en) 1994-01-12 1996-07-12 Preparations for the oiling of leather

    Publications (2)

    Publication Number Publication Date
    EP0739425A1 EP0739425A1 (en) 1996-10-30
    EP0739425B1 true EP0739425B1 (en) 1998-04-29

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    EP95904545A Expired - Lifetime EP0739425B1 (en) 1994-01-12 1995-01-03 Fatty treatment agent for leather

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    US (1) US5683611A (en)
    EP (1) EP0739425B1 (en)
    JP (1) JPH09507520A (en)
    AT (1) ATE165623T1 (en)
    BR (1) BR9506479A (en)
    CA (1) CA2181081A1 (en)
    DE (2) DE4400507A1 (en)
    ES (1) ES2115355T3 (en)
    WO (1) WO1995019451A1 (en)

    Family Cites Families (10)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE1669347A1 (en) * 1967-03-25 1971-05-06 Henkel & Cie Gmbh Process for greasing leather
    DE3507241A1 (en) * 1985-03-01 1986-09-04 Henkel KGaA, 4000 Düsseldorf METHOD FOR PRODUCING WATERPROOF LEATHER OR FUR
    DE3529869A1 (en) * 1985-08-21 1987-02-26 Basf Ag METHOD FOR HYDROPHOBIZING LEATHER AND FURS
    DE3717961C2 (en) * 1986-10-27 1994-05-26 Stockhausen Chem Fab Gmbh Process for the preparation of mixtures of N, N-disubstituted ß-aminopropionic acid derivatives, certain mixtures of N-alkyl-N (2-carboxyethyl) sulfonamides and N-alkyl-N (2-carboxyethyl) ureas and use of the compounds mentioned
    EP0265818B1 (en) * 1986-10-27 1994-09-28 Chemische Fabrik Stockhausen GmbH Process for the preparation of N,N-disubstituted beta-aminoacids and their use in water-proofing leather and skins
    TNSN89128A1 (en) * 1988-12-02 1991-02-04 Rohn And Haas Company Independance Mall West LEATHER TREATMENT WITH SELECTED AMPHIPHITE COPOLYMERS
    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
    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
    DE4129244A1 (en) * 1991-09-03 1993-03-04 Henkel Kgaa AQUEOUS DISPERSIONS OF NEW AMPHIPHILE CO-OLIGOMERS FOR THE WASHING AND CLEANING-RESISTANT FATTY EQUIPMENT OF LEATHER AND FUR SKINS AND THEIR USE
    DE4223111A1 (en) * 1992-07-14 1994-01-20 Henkel Kgaa New leather greasing agents and their use

    Also Published As

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    ATE165623T1 (en) 1998-05-15
    WO1995019451A1 (en) 1995-07-20
    US5683611A (en) 1997-11-04
    BR9506479A (en) 1997-10-07
    DE4400507A1 (en) 1995-07-13
    ES2115355T3 (en) 1998-06-16
    DE59502052D1 (en) 1998-06-04
    CA2181081A1 (en) 1995-07-20
    EP0739425A1 (en) 1996-10-30
    JPH09507520A (en) 1997-07-29

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