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EP0607388B1 - Use of graft polymers for stuffing and fulling leathers and fur pelts - Google Patents

Use of graft polymers for stuffing and fulling leathers and fur pelts Download PDF

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Publication number
EP0607388B1
EP0607388B1 EP93915893A EP93915893A EP0607388B1 EP 0607388 B1 EP0607388 B1 EP 0607388B1 EP 93915893 A EP93915893 A EP 93915893A EP 93915893 A EP93915893 A EP 93915893A EP 0607388 B1 EP0607388 B1 EP 0607388B1
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EP
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Prior art keywords
monomers
acid
monoethylenically unsaturated
weight
leather
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EP93915893A
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German (de)
French (fr)
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EP0607388A1 (en
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Hermann Birkhofer
Peter Danisch
Walter Denzinger
Heinrich Hartmann
Michael Kneip
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BASF SE
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BASF SE
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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

  • Greasing is a quality-determining process in the production of leather and is particularly important for very soft types of leather.
  • aqueous fat emulsions (licker) are used, which generally based on petrochemical products and natural oils and fats and made water-emulsifiable by partial sulphonation or with the help of emulsifiers.
  • DE-A 42 05 839 describes polymeric leather greasing agents based on esterified or amidated homo- or copolymers of monoethylenically unsaturated dicarboxylic acid anhydrides, which, depending on the degree of derivatization of the carboxyl groups and the polarity of the monomers in hydrophobicized leather, lead to a certain deterioration in the water-repellent properties of the leather can.
  • This application also describes further prior art.
  • EP-A 024 886 describes leather tanning agents based on polymers of (meth) acrylic acid, optionally (meth) acrylates and partially sulfated unsaturated fatty oils such as castor oil.
  • DE-AS 18 00 244 relates to the greasing and impregnation of leather with a mixture of an essentially hydrophobic synthetic resin and preferably sulfonated or sulfated animal or vegetable oils.
  • the synthetic resin has a maximum of 2% by weight of monomers containing carboxylate groups.
  • the post-published DE-A 41 42 318 relates to the use of copolymers and / or adducts of maleic anhydride with unsaturated fatty acids and / or their carboxyl group derivatives as neutral oil components in leather and fur greasing agents.
  • the invention was based on the object of providing improved means for greasing and filling leather and fur skins which no longer have the disadvantages of the prior art.
  • Monomers (a) are e.g. monoethylenically unsaturated mono- and dicarboxylic acids with preferably 3 to 12 carbon atoms in the molecule, such as acrylic acid, methacrylic acid, dimethylacrylic acid, ethyl acrylic acid, allylacetic acid, vinyl acetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid or methylene malonic acid and the corresponding anhydrides.
  • monoethylenically unsaturated mono- and dicarboxylic acids with preferably 3 to 12 carbon atoms in the molecule, such as acrylic acid, methacrylic acid, dimethylacrylic acid, ethyl acrylic acid, allylacetic acid, vinyl acetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid or methylene malonic acid and the corresponding anhydrides.
  • Examples of monomers containing sulfo groups include Vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, styrenesulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid.
  • Monomers with phosphonic acid groups are, for example, vinylphosphonic acid, allylphosphonic acid, phosphonomethylated allylamine and acrylamido-2-methylpropanephosphonic acid.
  • Preferred monomers of group (a) are acrylic acid, methacrylic acid and maleic acid. It can also be advantageous to use mixtures of the monomers (a).
  • the acids are preferably used as such or as anhydrides; in addition, alkali metal, alkaline earth metal or ammonium salts, such as the sodium, potassium, calcium, ammonium or substituted ammonium salts, can of course also be used, the acids in whole or in part as salts can be present.
  • olefins having 2 to 30 carbon atoms and vinyl alkyl ethers are also used as monomers (b) with 1 to 30 carbon atoms in the alkyl radical are particularly suitable.
  • olefins having 2 to 30 carbon atoms and vinyl alkyl ethers are also used as monomers (b) with 1 to 30 carbon atoms in the alkyl radical are particularly suitable.
  • a further modification of the graft copolymers can be achieved by carrying out the graft polymerization in the presence of monomers from group (c).
  • the monomer mixtures contain up to 5% by weight of a monomer having at least two ethylenically unsaturated non-conjugated double bonds in the molecule.
  • These compounds are usually used as crosslinkers in copolymerizations. They can be added to the monomers of group (a) used for the copolymerization or to the monomer mixtures from (a) and (b). If they are used, the amount of monomers (c) used is preferably 0.05 to 2% by weight.
  • Suitable compounds of this type are, for example, methylene bisacrylamide, esters of acrylic acid and methacrylic acid with polyhydric alcohols, e.g. Glycol diacrylate, glycerol triacrylate, glycol dimethacrylate, glycerol trimethacrylate, as well as polyols esterified at least twice with acrylic acid or methacrylic acid, such as pentaerythritol and glucose.
  • Suitable crosslinkers are also divinylbenzene, divinyldioxane, pentaerythritol triallyl ether and pentaallylsucrose. From this group of compounds, preference is given to using water-soluble monomers, such as glycol diacrylate or glycol diacrylates of polyethylene glycols having a molecular weight of up to 3,000.
  • component B includes all vegetable and animal oils. There are, for example, olive oil, rapeseed oil, soybean oil, sunflower oil, safflower oil, linseed oil, capelan oil or sperm oil.
  • the monomers (a) and optionally (b) and / or (c) are polymerized by free radicals in the presence of component B. It may be favorable for the effect of the graft polymer formed to use two or more of the oils specified under B.
  • the polymerization can be carried out in the presence or in the absence of inert solvents or diluents, with the absence of diluents being preferred.
  • Inert solvents are, for example, aromatic hydrocarbons such as toluene, xylene, o-, m-, p-xylene and isomer mixtures of xylene or ethylbenzene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, dodecane, cyclohexane, cyclooctane, methylcyclohexane or mixtures of the hydrocarbons mentioned and gasoline fractions which contain no polymerizable monomers.
  • Chlorinated hydrocarbons such as chloroform, carbon tetrachloride, hexachloroethane, dichloroethane or tetrachloroethane, alcohols such as methanol, ethanol, isopropanol, n-propanol, n-butanol or sec-butanol as well as tetrahydrofuran, dioxane and mixtures of the inert solvents mentioned are also suitable.
  • chloroform such as chloroform, carbon tetrachloride, hexachloroethane, dichloroethane or tetrachloroethane
  • alcohols such as methanol, ethanol, isopropanol, n-propanol, n-butanol or sec-butanol as well as tetrahydrofuran, dioxane and mixtures of the inert solvents mentioned are also suitable.
  • the graft polymerization can be carried out continuously or batchwise, generally using free-radical initiators.
  • Suitable free radical initiators are preferably those which have a half-life of less than 3 hours at the polymerization temperature chosen in each case. If the polymerization is initially started at a lower temperature and ends at a higher temperature, it is expedient to work with at least two initiators which decompose at different temperatures, namely firstly using an initiator which already decomposes at a lower temperature for the start of the polymerization and then the Complete the main polymerization with an initiator that decomposes at a higher temperature. For example, the following initiators can be used.
  • a redox system such as salts or complexes of heavy metals, for example copper, cobalt, manganese, iron, vanadium, cerium, nickel and chromium salts, or organic compounds such as benzoin, dimethylaniline or ascorbic acid are used , the half-lives of the radical initiators indicated can be reduced.
  • heavy metals for example copper, cobalt, manganese, iron, vanadium, cerium, nickel and chromium salts, or organic compounds such as benzoin, dimethylaniline or ascorbic acid
  • tert-butyl hydroperoxide with the addition of 5 ppm copper (II) acetylacetonate can be activated in such a way that polymerisation can take place at 100 ° C.
  • the reducing component of redox catalysts can also be formed, for example, from compounds such as sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxylate and hydrazine. Based on the monomers used in the polymerization, 0.01 to 20, preferably 0.05 to 10,% by weight of a polymerization initiator or a mixture of several polymerization initiators is used. 0.01 to 5% of the reducing compounds are added as redox components. Heavy metals are used in the range of 0.1 to 100 ppm, preferably 0.5 to 10 ppm. It is often beneficial to use a combination of peroxide, and Use reducing agent and heavy metal as a redox catalyst.
  • the polymerization of the monomers (a) and the monomers (b) and / or (c) which may also be used can also be carried out by the action of ultraviolet radiation, if appropriate in the presence of UV initiators.
  • the photoinitiators or sensitizers that are normally used are used. These are, for example, compounds such as benzoin and benzoin ether, ⁇ -methylbenzoin or ⁇ -phenylbenzoin. So-called triplet sensitizers, such as benzene diketals, can also be used.
  • UV-low light sources such as fluorescent tubes with a high proportion of blue, also serve as UV radiation sources.
  • Suitable regulators are, for example, mercapto compounds, such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid, butyl mercaptan and dodecyl mercaptan.
  • allyl compounds such as allyl alcohol, aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and isobutyraldehyde, formic acid, ammonium formate, propionic acid, hydrazine sulfate and butenols. If the polymerization is carried out in the presence of regulators, 0.05 to 20% by weight, based on the monomers used in the polymerization, are required.
  • the polymerization is carried out in the presence of water-soluble phosphorus compounds in which the phosphorus has an oxidation number of 1 to 4, the water-soluble alkali metal or ammonium salts, water-soluble Compounds containing PO (OH) "groups and / or their water-soluble salts.
  • Phosphorous acid is preferably used.
  • the phosphorus compounds in question are used to reduce the discoloration of the graft copolymers in amounts of from 0.01 to 5% by weight, based on the used monomers (A) Possible phosphorus compounds are described in EP-A-0 175 317.
  • the copolymerization of components (A) and (B) is usually carried out in an inert gas atmosphere with the exclusion of atmospheric oxygen. Good mixing of the reactants is generally ensured during the polymerization. In the case of smaller batches in which a reliable removal of the heat of polymerization is ensured, the reactants, which are preferably present in an inert diluent, can be copolymerized discontinuously by heating the reaction mixture to the polymerization temperature. These temperatures are in the range of 40 to 150 ° C. In order to be able to better control the course of the polymerization reaction, the monomers (A) are therefore added continuously or batchwise to the polymerizing mixture to the extent that the graft polymerization can be easily controlled in the desired temperature range.
  • a type of addition of the monomers of component (A) is preferred in which the compounds of component (B) or at least some of the compounds of component (B) are initially introduced into the reactor together with at least one monomer of group (a) in the polymerization reactor and heated therein to the desired polymerization temperature with stirring. As soon as this temperature is reached, the remaining monomers of group (a) and optionally the monomers (b) and optionally (c) and the initiator and optionally are added over a period of about 1 to 10, preferably 2 to 8 hours a controller too.
  • capelan oil with 1% ditertiary butyl peroxide can be heated to 150 ° C. in a weak stream of N 2 for 2 hours and then acrylic acid is metered in at 150 ° C. in the course of 3 hours.
  • the grafted vegetable or animal oil is converted into an aqueous dispersion.
  • the dispersion can be carried out using conventional emulsifiers such as fatty alcohol ethoxylates, dodecylbenzenesulfonates, Dioctyl sulfosuccinate or alkyl sulfonates can be made in suitable apparatus.
  • Emulsifier-free dispersion is particularly preferred by partially or completely neutralizing the carboxyl groups of the graft polymer with alkalis, alkaline earths, ammonia or amines and thus obtaining stable aqueous dispersions.
  • These dispersions have a solids content of 5 to 80% and preferably 20 to 70% and can thus be used directly for the treatment of leather and furskins.
  • the drying residue can be determined, for example, in a drying cabinet (2 h at 120 ° C).
  • graft polymers to be used according to the invention it is possible to produce very soft leather without the addition of conventional liquors.
  • the water-repellent properties of hydrophobized leather are not adversely affected when these products are used.
  • the mechanical properties, such as tensile strength, as well as the light fastness and heat yellowing resistance of such leathers are influenced very positively by the use of these graft polymers.
  • the good fixation in the leather results in great resistance to extractability with solvents or water.
  • washable leathers i.e. leathers that do not lose their properties such as softness, firmness and suppleness after washing; in contrast, this property is not to be expected for leathers that are greased with conventional licker.
  • aqueous dispersion to be used according to the invention preferably contains no additional emulsifiers. It is known that leather and furs, which are to be made hydrophobic and are treated with products containing emulsifiers, have to undergo complex processes after treatment with these agents, e.g. Post-treatment with polyvalent metal salts, to make the emulsifiers in the leather or in the fur skins ineffective, i.e. to fix.
  • the graft polymer dispersions described above are suitable for the treatment of all conventional tanned hides.
  • the tanned hides are usually deacidified before treatment. They may have been stained before treatment. Coloring can, however, also be carried out only after the lubrication that takes place according to the invention.
  • the tanned skins are expediently mixed with the aqueous dispersions in aqueous liquors, which can be obtained by diluting the graft polymer dispersions with water, at pH values of 4 to 10, preferably 5 to 8 and temperatures of 20 to 60, preferably 30 to 50 ° C. treated for a period of 0.1 to 5, in particular 0.5 to 2 h. This treatment takes place, for example, by drumming in a barrel.
  • the required amount of graft polymer dispersion, based on the shaved weight of the leather or the wet weight of the fur skins is 0.1 to 30, preferably 1 to 20,% by weight.
  • the fleet length i.e. the percentage weight ratio of the treatment liquor to the goods, based on the shaved weight of the leather or the wet weight of the fur skins, is usually 10 to 1000, preferably 30 to 150%, for fur skins 50 to 500%.
  • the pH of the treatment liquor is adjusted to a value of 3 to 5, preferably 3.5 to 4, by adding acids, preferably an organic acid such as formic acid.
  • the treatment with the aqueous dispersions to be used according to the invention can be used before or after the retanning step.
  • Example 2 Similar to Example 1, 100 g of capelan oil and 1 g of tert-butyl perethylhexanoate are heated to 150 ° and stirred for 1 hour. Then 10 g of maleic anhydride and 1 g of tert-butyl perethylhexanoate are added and the mixture is heated at 150 ° C. for 6 hours. After cooling, the mixture is diluted with 310 g of water and 7.2 g of 50% sodium hydroxide solution and the mixture is intensively dispersed for 10 minutes with the Ultra-Turrax. The dispersion obtained has a pH of 8.9, a drying residue of 25% and a Brookfield viscosity of 16 mPa ⁇ s at 23 ° C.
  • rapeseed oil are heated to 150 ° C under a weak stream of N2. Then 20 g of acrylic acid (100%) and the solution of 1 g of tert-butyl perethylhexanoate in 10 g of rapeseed oil are metered in uniformly at 150 ° C. within 1 h. The mixture is then stirred at 150 ° for 2 h, a further 1 g of tert-butyl perethylhexanoate is added and the mixture is heated again at 150 ° C. for 2 h.
  • 100 g of the graft polymer thus obtained are diluted with 76 g of water and dispersed intensively for 10 minutes.
  • the white viscous dispersion has a pH of 3.5 and a drying residue of 55.9%.
  • methacrylic acid is used instead of acrylic acid, a dispersion with comparable properties is obtained.
  • Example 1 100 g of rapeseed oil and 1 g of tert-butyl perethylhexanoate are heated at 150 ° C. for 1 hour under a weak stream of N 2 . 18 g of maleic anhydride and 1 g of tert-butyl perethylhexanoate are then added and the mixture is heated at 150 ° C. for 6 h. Then it is cooled and 105 g of the product are mixed with 90 g of water and 8 g of 50% sodium hydroxide solution and intensively dispersed for 10 minutes with the Ultra-Turrax. A homogeneous viscous dispersion is formed with a drying residue of 52.7% and a pH of 5.5.
  • Example 1 100 g of capelan oil are heated to 150 ° in a weak N2 stream and then 20 g of acrylic acid and a solution of 1 g of tert-butyl perethylhexanoate in 10 g of capelan oil are uniformly added at 150 ° C. in the course of 1 h. The mixture is then heated for a further 1 h, another 1 g of tert-butyl perethylhexanoate is added and the mixture is heated for a further 1 h. The mixture is then cooled and 103 g of the product, after adding 90 g of water and 9 g of 50% sodium hydroxide solution, are dispersed intensively for 10 minutes using Ultra-Turrax. The viscous homogeneous dispersion has a pH of 7.0 and the drying residue is 49.1%.
  • Example 6 20 g of methacrylic acid are used instead of acrylic acid. 115 g of the graft polymer obtained, 95 g of water and 14 g of 50% sodium hydroxide solution are dispersed intensively for 10 minutes with the Ultra-Turrax. The viscous dispersion has a pH of 7.1 and a drying residue of 51.2%.
  • Example 4 The product from Example 4 was used analogously to the procedure given in Example 3.
  • the leather thus obtained showed soft and round grip properties.
  • Example 5 The product from Example 5 was used analogously to the procedure given in Example 1.
  • the leather thus obtained was characterized by a round, soft handle.
  • Example 6 The product from Example 6 was used analogously to the procedure given in Example 1. The result was similarly advantageous as in the previous examples.
  • Example 7 The product from Example 7 was used analogously to the procedure given in Example 3. The result was a soft leather with a comfortable grip.

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

Abstract

The invention relates to the use of water-soluble or dispersible graft polymers of vegetable and animal oils, obtainable by the radically initiated polymerisation A) of a monomer or monomer mixture of (a) 20 to 100 wt % monoethylenically unsaturated carboxylic acids and/or monoethylenically unsaturated sulphonic acids and/or monoethylenically unsaturated phosphonic acids or their alkaline, alkaline earth or ammonium salts, (b) 0 to 80 wt % other monoethylenically unsaturated monomers which can be copolymerised with monomers (a), and (c) 0 to 5 wt % at least double-ethylenic unconjugated unsaturated monomers, in the presence of B) vegetable and/or animal oils, in the weight ratio of A:B of (80 to 1):(20 to 99) to stuff and full leathers and fur pelts. This provides soft leathers with a pleasant feel.

Description

Die Fettung ist ein qualitätsbestimmender Prozeß bei der Herstellung von Ledern und insbesondere bei sehr weichen Ledersorten wichtig. Zur Steuerung der mechanischen Eigenschaften des Leders wie Weichheit, Biegsamkeit, Geschmeidigkeit werden wäßrige Fettemulsionen (Licker) verwendet, die i.a. auf petrochemischen Produkten und natürlichen Ölen und Fetten basieren und durch Teilsulfierung oder mit Hilfe von Emulgatoren wasseremulgierbar gemacht werden.Greasing is a quality-determining process in the production of leather and is particularly important for very soft types of leather. To control the mechanical properties of the leather such as softness, flexibility, suppleness, aqueous fat emulsions (licker) are used, which generally based on petrochemical products and natural oils and fats and made water-emulsifiable by partial sulphonation or with the help of emulsifiers.

Nachteile solcher Produkte sind neben einer unvollständigen Flottenauszehrung, einer relativ leichten Extraktion durch Lösungsmittel oder Wasser, dem Auftreten von Migrationsphänomenen und unbefriedigenden Echtheitsprofilen, daß sie nur sehr eingeschränkt zum Fetten von hydrophobierten Ledern geeignet sind; der hohe Anteil an polaren Gruppen bzw. Emulgatoren bewirkt nämlich, daß die wasserabstoßenden Eigenschaften eines hydrophobierten Leders zerstört werden und Wasser, angelagert an die polaren Gruppen, in das Leder eindringen kann.Disadvantages of such products are, in addition to incomplete liquor depletion, relatively easy extraction by solvent or water, the occurrence of migration phenomena and unsatisfactory authenticity profiles, that they are only suitable to a very limited extent for greasing hydrophobized leathers; The high proportion of polar groups or emulsifiers namely has the effect that the water-repellent properties of a hydrophobized leather are destroyed and water, attached to the polar groups, can penetrate into the leather.

So werden z.B. in der DE-A 42 05 839 polymere Lederfettungsmittel auf der Basis von veresterten oder amidierten Homo- oder Copolymerisaten monoethylenisch ungesättigter Dicarbonsäureanhydride beschrieben, die je nach Derivatisierungsgrad der Carboxylgruppen und der Polarität der Monomeren bei hydrophobierten Ledern zu einer gewissen Verschlechterung der wasserabstoßenden Eigenschaften des Leders führen können. In dieser Anmeldung ist auch weiterer Stand der Technik beschrieben.For example, DE-A 42 05 839 describes polymeric leather greasing agents based on esterified or amidated homo- or copolymers of monoethylenically unsaturated dicarboxylic acid anhydrides, which, depending on the degree of derivatization of the carboxyl groups and the polarity of the monomers in hydrophobicized leather, lead to a certain deterioration in the water-repellent properties of the leather can. This application also describes further prior art.

Der Derwent Publ. Abstract AN 83-59741 ≙ JP-OS 1983/079061 offenbart Pfropfpolymerisate von Glycidylestern ungesättigter Fettsäuren mit Copolymeren aus α,β-ethylenisch ungesättigten Säuren wie Acryl- oder Methacrylsäure und Comonomeren wie Acrylaten, Methacrylaten, Styrol oder α-Methylsytrol als äußerliche Beschichtungszusammensetzungen für Metall-, Holz- und Kunststoffoberflächen; Leder als Substrat wird nicht erwähnt.Derwent Publ. Abstract AN 83-59741 ≙ JP-OS 1983/079061 discloses graft polymers of glycidyl esters of unsaturated fatty acids with copolymers of α, β-ethylenically unsaturated acids such as acrylic or methacrylic acid and comonomers such as acrylates, methacrylates, styrene or α-methylsytrol external coating compositions for Metal, wood and plastic surfaces; Leather as a substrate is not mentioned.

Die EP-A 024 886 beschreibt Ledergerbstoffe auf Basis von Polymerisaten aus (Meth)Acrylsäure, gegebenenfalls (Meth)Acrylaten und teilsulfatierten ungesättigten fetten Ölen wie Ricinusöl.EP-A 024 886 describes leather tanning agents based on polymers of (meth) acrylic acid, optionally (meth) acrylates and partially sulfated unsaturated fatty oils such as castor oil.

Die DE-AS 18 00 244 betrifft das Fetten und Imprägnieren von Leder mit einer Mischung aus einem im wesentlichen hydrophoben Kunstharz und vorzugsweise sulfonierten oder sulfatierten tierischen oder pflanzlichen Ölen. Das Kunstharz weist maximal 2 Gew.-% carboxylatgruppenhaltige Monomere auf.DE-AS 18 00 244 relates to the greasing and impregnation of leather with a mixture of an essentially hydrophobic synthetic resin and preferably sulfonated or sulfated animal or vegetable oils. The synthetic resin has a maximum of 2% by weight of monomers containing carboxylate groups.

Die nachveröffentlichte DE-A 41 42 318 betrifft die Verwendung von Copolymerisaten und/oder Addukten des Maleinsäureanhydrids mit ungesättigten Fettsäuren und/oder deren Carboxylgruppenderivaten als Neutralölkomponente in Leder- und Pelzfettungsmitteln.The post-published DE-A 41 42 318 relates to the use of copolymers and / or adducts of maleic anhydride with unsaturated fatty acids and / or their carboxyl group derivatives as neutral oil components in leather and fur greasing agents.

Der Erfindung lag nun die Aufgabe zugrunde, verbesserte Mittel zum Fetten und Füllen von Ledern und Pelzfellen bereitzustellen, die die Nachteile des Standes der Technik nicht mehr aufweisen.The invention was based on the object of providing improved means for greasing and filling leather and fur skins which no longer have the disadvantages of the prior art.

Die Aufgabe wird erfindungsgemäß gelöst durch die Verwendung von wasserlöslichen oder wasserdispergierbaren Pfropfcopolymeren von pflanzlichen und tierischen Ölen, erhältlich durch radikalisch initiierte Polymerisation

  • A) eines Monomeren oder einer Monomermischung aus
    • (a) 20 bis 100 Gew.-% monoethylenisch ungesättigter Carbonsäuren und/oder monoethylenisch ungesättigter Sulfonsäuren und/oder monoethylenisch ungesättigter Phosphonsäuren oder von deren Alkali-, Erdalkalioder Ammoniumsalzen,
    • (b) 0 bis 80 Gew.-% anderer monoethylenisch ungesättigter Monomere, die mit den Monomeren (a) copolymerisierbar sind und
    • (c) 0 bis 5 Gew.-% mindestens doppelt ethylenisch nicht konjugiert ungesättigter Monomerer
    in Gegenwart von
  • B) pflanzlichen und/oder tierischen Ölen
    im Gewichtsverhältnis A:B von (80 bis 1) : (20 bis 99), vorzugsweise (60 bis 5) : (40 bis 95), zum Fetten und Füllen von Leder und Pelzfellen.
The object is achieved according to the invention by using water-soluble or water-dispersible graft copolymers of vegetable and animal oils, obtainable by free-radically initiated polymerization
  • A) a monomer or a monomer mixture
    • (a) 20 to 100% by weight of monoethylenically unsaturated carboxylic acids and / or monoethylenically unsaturated sulfonic acids and / or monoethylenically unsaturated phosphonic acids or their alkali metal, alkaline earth metal or ammonium salts,
    • (b) 0 to 80% by weight of other monoethylenically unsaturated monomers which are copolymerizable with the monomers (a) and
    • (c) 0 to 5% by weight of at least double ethylenically non-conjugated unsaturated monomers
    in the presence of
  • B) vegetable and / or animal oils
    in the A: B weight ratio of (80 to 1): (20 to 99), preferably (60 to 5): (40 to 95), for greasing and filling leather and fur skins.

Monomere (a) sind z.B. monoethylenisch ungesättigte Mono- und Dicarbonsäuren mit vorzugsweise 3 bis 12 C-Atomen im Molekül, wie Acrylsäure, Methacrylsäure, Dimethylacrylsäure, Ethylacrylsäure, Allylessigsäure, Vinylessigsäure, Crotonsäure, Maleinsäure, Fumarsäure, Itakonsäure, Citrakonsäure oder Methylenmalonsäure sowie die entsprechenden Anhydride. Als sulfogruppenhaltige Monomere kommen z.B. Vinylsulfonsäure, Allylsulfonsäure, Methallylsulfonsäure, Acrylsäure-3-sulfopropylester, Methacrylsäure-3-sulfopropylester, Styrolsulfonsäure oder 2-Acrylamido-2-methylpropansulfonsäure in Betracht.Monomers (a) are e.g. monoethylenically unsaturated mono- and dicarboxylic acids with preferably 3 to 12 carbon atoms in the molecule, such as acrylic acid, methacrylic acid, dimethylacrylic acid, ethyl acrylic acid, allylacetic acid, vinyl acetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid or methylene malonic acid and the corresponding anhydrides. Examples of monomers containing sulfo groups include Vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, styrenesulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid.

Monomere mit Phosphonsäuregruppen sind beispielsweise Vinylphosphonsäure, Allylphosphonsäure, phosphonomethyliertes Allylamin und Acrylamido-2-methylpropanphosphonsäure. Bevorzugte Monomere der Gruppe (a) sind Acrylsäure, Methacrylsäure und Maleinsäure. Es kann auch vorteilhaft sein, Mischungen der Monomeren (a) einzusetzen.Monomers with phosphonic acid groups are, for example, vinylphosphonic acid, allylphosphonic acid, phosphonomethylated allylamine and acrylamido-2-methylpropanephosphonic acid. Preferred monomers of group (a) are acrylic acid, methacrylic acid and maleic acid. It can also be advantageous to use mixtures of the monomers (a).

Die Säuren werden vorzugsweise als solche oder als Anhydride verwendet, daneben können natürlich auch Alkali-, Erdalkali- oder Ammoniumsalze, wie die Natrium-, Kalium-, Kalzium-, Ammonium- oder substituierten Ammoniumsalze Verwendung finden, wobei die Säuren ganz oder teilweise als Salze vorliegen können.The acids are preferably used as such or as anhydrides; in addition, alkali metal, alkaline earth metal or ammonium salts, such as the sodium, potassium, calcium, ammonium or substituted ammonium salts, can of course also be used, the acids in whole or in part as salts can be present.

Als Monomere (b), die mit den Monomeren (a) copolymerisierbar sind, können insbesondere N-Vinylpyrrolidon, N-Vinylcaprolactam, N-Vinylimidazol, 1-Vinyl-2-methylimidazol, N-Vinylformamid, N-Vinyl-N-methylformamid, Vinylacetat, Vinylpropionat, Styrol, Acrylsäure- und Methacrylsäureester mit C1- bis C30-Alkoholen, Hydroxi-C2- bis C6-alkylester der Acrylsäure oder Methacrylsäure, Acrylamid, Methacrylamid oder Mono- und Dialkylamide der Acrylsäure und Methacrylsäure mit 1 bis 20 C-Atomen in den Alkylresten genannt werden. Bei der Verwendung von monoethylenisch ungesättigten Dicarbonsäureanhydriden als Monomere (a) sind als Monomere (b) zudem Olefine mit 2 bis 30 C-Atomen und Vinylalkylether mit 1 bis 30 C-Atomen im Alkylrest besonders gut geeignet. Auch hier kann es vorteilhaft sein, Mischungen der Komponenten (b) einzusetzen.As monomers (b) which are copolymerizable with the monomers (a), in particular N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, 1-vinyl-2-methylimidazole, N-vinylformamide, N-vinyl-N-methylformamide, Vinyl acetate, vinyl propionate, styrene, acrylic and methacrylic esters with C 1 - to C 30 alcohols, hydroxy-C 2 - to C 6 -alkyl esters Acrylic acid or methacrylic acid, acrylamide, methacrylamide or mono- and dialkylamides of acrylic acid and methacrylic acid with 1 to 20 carbon atoms in the alkyl radicals. When monoethylenically unsaturated dicarboxylic anhydrides are used as monomers (a), olefins having 2 to 30 carbon atoms and vinyl alkyl ethers are also used as monomers (b) with 1 to 30 carbon atoms in the alkyl radical are particularly suitable. Here, too, it can be advantageous to use mixtures of components (b).

Eine weitere Modifizierung der Pfropfcopolymerisate kann dadurch erreicht werden, daß man die Pfropfpolymerisation in Gegenwart von Monomeren der Gruppe (c) durchführt. Die Monomermischungen enthalten in diesem Fall bis zu 5 Gew.-% eines mindestens zwei ethylenisch ungesättigte nicht-konjugierte Doppelbindungen im Molekül aufweisenden Monomers. Diese Verbindungen werden üblicherweise bei Copolymerisationen als Vernetzer verwendet. Sie können den zur Copolymerisation eingesetzten Monomeren der Gruppe (a) oder den Monomermischungen aus (a) und (b) zugesetzt werden. Im Falle ihres Einsatzes beträgt die bevorzugt verwendete Menge an Monomeren (c) 0,05 bis 2 Gew.-%. Die Mitverwendung der Monomeren der Gruppe (c) während der Copolymerisation bewirkt eine Erhöhung der K-Werte der Copolymerisate. Geeignete Verbindungen dieser Art sind beispielsweise Methylenbisacrylamid, Ester von Acrylsäure und Methacrylsaure mit mehrwertigen Alkoholen, z.B. Glykoldiacrylat, Glycerintriacrylat, Glykoldimethacrylat, Glycerintrimethacrylat, sowie mindestens zweifach mit Acrylsäure oder Methacrylsäure veresterte Polyole, wie Pentaerythrit und Glucose. Geeignete Vernetzer sind außerdem Divinylbenzol, Divinyldioxan, Pentaerythrittriallylether und Pentaallylsucrose. Vorzugsweise verwendet man aus dieser Gruppe von Verbindungen wasserlösliche Monomere, wie Glykoldiacrylat oder Glykoldiacrylate von Polyethylenglykolen eines Molekulargewichts bis zu 3.000.A further modification of the graft copolymers can be achieved by carrying out the graft polymerization in the presence of monomers from group (c). In this case, the monomer mixtures contain up to 5% by weight of a monomer having at least two ethylenically unsaturated non-conjugated double bonds in the molecule. These compounds are usually used as crosslinkers in copolymerizations. They can be added to the monomers of group (a) used for the copolymerization or to the monomer mixtures from (a) and (b). If they are used, the amount of monomers (c) used is preferably 0.05 to 2% by weight. The use of the monomers of group (c) during the copolymerization causes an increase in the K values of the copolymers. Suitable compounds of this type are, for example, methylene bisacrylamide, esters of acrylic acid and methacrylic acid with polyhydric alcohols, e.g. Glycol diacrylate, glycerol triacrylate, glycol dimethacrylate, glycerol trimethacrylate, as well as polyols esterified at least twice with acrylic acid or methacrylic acid, such as pentaerythritol and glucose. Suitable crosslinkers are also divinylbenzene, divinyldioxane, pentaerythritol triallyl ether and pentaallylsucrose. From this group of compounds, preference is given to using water-soluble monomers, such as glycol diacrylate or glycol diacrylates of polyethylene glycols having a molecular weight of up to 3,000.

Die Polymerisation der Monomeren (a) sowie gegebenenfalls noch (b) und (c) erfolgt in Gegenwart der Komponente B. Als Komponente B kommen alle pflanzlichen und tierischen Öle in Betracht. Es sind beispielsweise Olivenöl, Rapsöl, Sojaöl, Sonnenblumenöl, Safloröl, Leinöl, Capelanöl oder Spermöl.The polymerization of the monomers (a) and, if appropriate, also (b) and (c) takes place in the presence of component B. Component B includes all vegetable and animal oils. There are, for example, olive oil, rapeseed oil, soybean oil, sunflower oil, safflower oil, linseed oil, capelan oil or sperm oil.

Zur Herstellung der Pfropfcopolymerisate werden die Monomeren (a) und gegebenenfalls (b) und/oder (c) in Gegenwart der Komponente B radikalisch polymerisiert. Dabei kann es für die Wirkung des entstehenden Pfropfpolymerisates günstig sein, zwei oder mehrere der unter B angegebenen Öle einzusetzen.To prepare the graft copolymers, the monomers (a) and optionally (b) and / or (c) are polymerized by free radicals in the presence of component B. It may be favorable for the effect of the graft polymer formed to use two or more of the oils specified under B.

Die Polymerisation kann in Gegenwart oder in Abwesenheit von inerten Löse- oder Verdünnungsmitteln durchgeführt werden, wobei die Abwesenheit von Verdünnungsmitteln bevorzugt ist. Inerte Lösungsmittel sind bespielsweise aromatische Kohlenwasserstoffe wie Toluol, Xylol, o-, m-, p-Xylol und Isomerengemische des Xylols oder Ethylbenzol, aliphatische Kohlenwasserstoffe, wie Pentan, Hexan, Heptan, Octan, Nonan, Dodecan, Cylohexan, Cyclooctan, Methylcyclohexan oder Mischungen der genannten Kohlenwasserstoffe sowie Benzinfraktionen, die keine polymerisierbaren Monomeren enthalten. Außerdem eignen sich Chlorkohlenwasserstoffe wie Chloroform, Tetrachlorkohlenstoff, Hexachlorethan, Dichlorethan oder Tetrachlorethan, Alkohole wie Methanol, Ethanol, Isopropanol, n-Propanol, n-Butanol oder sek.-Butanol sowie Tetrahydrofuran, Dioxan und Mischungen der genannten inerten Lösemittel.The polymerization can be carried out in the presence or in the absence of inert solvents or diluents, with the absence of diluents being preferred. Inert solvents are, for example, aromatic hydrocarbons such as toluene, xylene, o-, m-, p-xylene and isomer mixtures of xylene or ethylbenzene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, dodecane, cyclohexane, cyclooctane, methylcyclohexane or mixtures of the hydrocarbons mentioned and gasoline fractions which contain no polymerizable monomers. Chlorinated hydrocarbons such as chloroform, carbon tetrachloride, hexachloroethane, dichloroethane or tetrachloroethane, alcohols such as methanol, ethanol, isopropanol, n-propanol, n-butanol or sec-butanol as well as tetrahydrofuran, dioxane and mixtures of the inert solvents mentioned are also suitable.

Es kann auch vorteilhaft sein, pflanzliche oder tierische Öle mit einem Emulgator in Wasser zu emulgieren und dann die Pfropfung durchzuführen.It may also be advantageous to emulsify vegetable or animal oils with an emulsifier in water and then to carry out the grafting.

Die Pfropfpolymerisation kann kontinuierlich oder diskontinuierlich durchgeführt werden, wobei im allgemeinen radikalbildende Initiatoren mitverwendet werden.The graft polymerization can be carried out continuously or batchwise, generally using free-radical initiators.

Als radikalbildende Initiatoren sind vorzugsweise diejenigen geeignet, die bei der jeweils gewählten Polymerisationstemperatur eine Halbwertszeit von weniger als 3 Stunden aufweisen. Falls man die Polymerisation zunächst bei niedrigerer Temperatur startet und bei höherer Temperatur zu Ende führt, ist es zweckmaßig, mit mindestens zwei bei verschiedenen Temperaturen zerfallenden Initiatoren zu arbeiten, nämlich zunächst einen bereits bei niedrigerer Temperatur zerfallenden Initiator für den Start der Polymerisation einzusetzen und dann die Hauptpolymerisation mit einem Initiator zu Ende zu führen, der bei höherer Temperatur zerfällt. Man kann beispielsweise die folgenden Initiatoren verwenden.Suitable free radical initiators are preferably those which have a half-life of less than 3 hours at the polymerization temperature chosen in each case. If the polymerization is initially started at a lower temperature and ends at a higher temperature, it is expedient to work with at least two initiators which decompose at different temperatures, namely firstly using an initiator which already decomposes at a lower temperature for the start of the polymerization and then the Complete the main polymerization with an initiator that decomposes at a higher temperature. For example, the following initiators can be used.

Temperatur: 40 bis 60°C:
Acetylcyclohexansulfonylperoxid, Diacetylperoxidicarbonat, Dicyclohexylperoxidicarbonat, Di-2-ethylhexylperoxidicarbonat, tert.-Butylperneodecanoat, 2,2'-Azobis-(4-methoxy-2,4-dimethylvaleronitril), 2,2'-Azobis-(2-methylN-phenylpropionamidin)dihydrochlorid, 2,2'-Azobis-(2-methylpropionamidin)dihydrochlorid.Temperature: 40 to 60 ° C:
Acetylcyclohexanesulfonyl peroxide, diacetyl peroxidicarbonate, dicyclohexyl peroxidicarbonate, di-2-ethylhexyl peroxidicarbonate, tert-butyl perneodecanoate, 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis- (2-methylionamidine) phenyl dihydrochloride, 2,2'-azobis (2-methylpropionamidine) dihydrochloride.

Temperatur: 60 bis 80°C:
tert.-Butylperpivalat, Dioctanoylperoxid, Dilauroylperoxid, 2,2'-Azobis-(2,4-dimethylvaleronitril).Temperature: 60 to 80 ° C:
tert-butyl perpivalate, dioctanoyl peroxide, dilauroyl peroxide, 2,2'-azobis (2,4-dimethylvaleronitrile).

Temperatur: 80 bis 100°C:
Dibenzoylperoxid, tert.-Butylpermaleinat, 2,2'-Azobis-(isobutyronitril), Dimethyl-2,2'-azobisisobutyrat, Natriumpersulfat, Kaliumpersulfat, Ammoniumpersulfat.Temperature: 80 to 100 ° C:
Dibenzoyl peroxide, tert-butyl permaleinate, 2,2'-azobis (isobutyronitrile), dimethyl 2,2'-azobisisobutyrate, sodium persulfate, potassium persulfate, ammonium persulfate.

Temperatur: 100 bis 120°C:
Bis-(tert.-butylperoxy)-cyclohexan, tert.-Butylperoxiisopropylcarbonat, tert.-Butylperacetat, Wasserstoffperoxid.Temperature: 100 to 120 ° C:
Bis- (tert-butylperoxy) cyclohexane, tert-butylperoxyisopropyl carbonate, tert-butylperacetate, hydrogen peroxide.

Temperatur: > 120°C:
2,2-Bis-(tert.-butylperoxi)-butan, Dicumylperoxid, Di-tert.-amylperoxid, Di-tert.-butylperoxid, p-Menthanhydroperoxid, Pinanhydroperoxid, Cumolhydroperoxid und tert.-Butylhydroperoxid oder tert.Butylperethylhexanoat.Temperature:> 120 ° C:
2,2-bis (tert-butyl peroxy) butane, dicumyl peroxide, di-tert-amyl peroxide, di-tert-butyl peroxide, p-menthane hydroperoxide, pinane hydroperoxide, cumene hydroperoxide and tert-butyl hydroperoxide or tert-butyl perethyl hexanoate.

Verwendet man zusätzlich zu den genannten Initiatoren noch ein Redoxsystem wie Salze oder Komplexe von Schwermetallen, z.B. Kupfer-, Kobalt-, Mangan-, Eisen-, Vanadium-, Cer-, Nickel- und Chromsalze oder organische Verbindungen, wie Benzoin, Dimethylanilin oder Ascorbinsaure, so können die Halbwertszeiten der angegebenen radikalbildenden Initiatoren verringert werden. So kann man beispielsweise tert.-Butylhydroperoxid unter Zusatz von 5 ppm Kupfer-II-acetylacetonat so aktivieren, daß bereits bei 100°C polymerisiert werden kann. Die reduzierende Komponente von Redoxkatalysatoren kann auch beispielsweise von Verbindungen wie Natriumsulfit, Natriumbisulfit, Natriumformaldehydsulfoxylat und Hydrazin gebildet werden. Bezogen auf die bei der Polymerisation eingesetzten Monomeren verwendet man 0,01 bis 20, vorzugsweise 0,05 bis 10 Gew.-% eines Polymerisationsinitiators oder einer Mischung mehrerer Polymerisationsinitiatoren. Als Redoxkomponenten setzt man 0,01 bis 5 % der reduzierend wirkenden Verbindungen zu. Schwermetalle werden im Bereich von 0,1 bis 100 ppm, vorzugsweise 0,5 bis 10 ppm eingesetzt. Oft ist es von Vorteil, eine Kombination aus Peroxid, und Reduktionsmittel und Schwermetall als Redoxkatalysator einzusetzen.In addition to the initiators mentioned, a redox system such as salts or complexes of heavy metals, for example copper, cobalt, manganese, iron, vanadium, cerium, nickel and chromium salts, or organic compounds such as benzoin, dimethylaniline or ascorbic acid are used , the half-lives of the radical initiators indicated can be reduced. For example, tert-butyl hydroperoxide with the addition of 5 ppm copper (II) acetylacetonate can be activated in such a way that polymerisation can take place at 100 ° C. The reducing component of redox catalysts can also be formed, for example, from compounds such as sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxylate and hydrazine. Based on the monomers used in the polymerization, 0.01 to 20, preferably 0.05 to 10,% by weight of a polymerization initiator or a mixture of several polymerization initiators is used. 0.01 to 5% of the reducing compounds are added as redox components. Heavy metals are used in the range of 0.1 to 100 ppm, preferably 0.5 to 10 ppm. It is often beneficial to use a combination of peroxide, and Use reducing agent and heavy metal as a redox catalyst.

Die Polymerisation der Monomeren (a) und der gegebenenfalls mitzuverwendenden Monomeren (b) und/oder (c) kann auch durch Einwirkung von ultravioletter Strahlung, gegebenenfalls in Gegenwart von UV-Initiatoren, durchgeführt werden. Für das Polymerisieren unter Einwirkung von UV-Strahlen setzt man die dafür üblicherweise in Betracht kommenden Fotoinitiatoren bzw. Sensibilisatoren ein. Hierbei handelt es sich beispielsweise um Verbindungen wie Benzoin und Benzoinether, α-Methylbenzoin oder α-Phenylbenzoin. Auch sogenannte Triplett-Sensibilisatoren, wie Benzildiketale, können verwendet werden. Als UV-Strahlungsquellen dienen beispielsweise neben energiereichen UV-Lampen, wie Kohlenbogenlampen, Quecksilberdampflampen oder Xenonlampen auch UV-arme Lichtquellen, wie Leuchtstoffröhren mit hohem Blauanteil.The polymerization of the monomers (a) and the monomers (b) and / or (c) which may also be used can also be carried out by the action of ultraviolet radiation, if appropriate in the presence of UV initiators. For the polymerization under the action of UV rays, the photoinitiators or sensitizers that are normally used are used. These are, for example, compounds such as benzoin and benzoin ether, α-methylbenzoin or α-phenylbenzoin. So-called triplet sensitizers, such as benzene diketals, can also be used. In addition to high-energy UV lamps, such as carbon arc lamps, mercury vapor lamps or xenon lamps, UV-low light sources, such as fluorescent tubes with a high proportion of blue, also serve as UV radiation sources.

Um Polymerisate mit niedrigem K-Wert herzustellen, wird die Pfropfpolymerisation zweckmäßigerweise in Gegenwart von Reglern durchgeführt. Geeignete Regler sind beispielsweise Mercaptoverbindungen, wie Mercaptoethanol, Mercaptopropanol, Mercaptobutanol, Mercaptoessigsäure, Mercaptopropionsäure, Butylmercaptan und Dodecylmercaptan. Als Regler eignen sich außerdem Allylverbindungen, wie Allylalkohol, Aldehyde, wie Formaldehyd, Acetaldehyd, Propionaldehyd, n-Butyraldehyd und Isobutyraldehyd, Ameisensäure, Ammoniumformiat, Propionsäure, Hydrazinsulfat und Butenole. Falls die Polymerisation in Gegenwart von Reglern durchgeführt wird, benötigt man davon 0,05 bis 20 Gew.-%, bezogen auf die bei der Polymerisation eingesetzten Monomeren.In order to produce polymers with a low K value, the graft polymerization is advantageously carried out in the presence of regulators. Suitable regulators are, for example, mercapto compounds, such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid, butyl mercaptan and dodecyl mercaptan. Also suitable as regulators are allyl compounds, such as allyl alcohol, aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and isobutyraldehyde, formic acid, ammonium formate, propionic acid, hydrazine sulfate and butenols. If the polymerization is carried out in the presence of regulators, 0.05 to 20% by weight, based on the monomers used in the polymerization, are required.

Um farblose oder nur wenig gefärbte Pfropfpolymerisate aus den Komponenten (A) und (B) herzustellen, wird die Polymerisation in Gegenwart von wasserlöslichen Phosphorverbindungen durchgeführt, in denen der Phosphor eine Oxidationszahl von 1 bis 4 hat, deren wasserlöslichen Alkali- oder Ammoniumsalzen, wasserlöslichen -PO(OH)"-Gruppen enthaltenden Verbindungen und/oder deren wasserlöslichen Salzen. Vorzugsweise verwendet man phosphorige Säure. Die in Betracht kommenden Phosphorverbindungen werden zur Verringerung der Verfärbung der Propfcopolymerisate in Mengen von 0,01 bis 5 Gew.-%, bezogen auf die eingesetzten Monomeren (A) angewendet. Die in Betracht kommenden Phosphorverbindungen sind in der EP-A-0 175 317 beschrieben.In order to produce colorless or only slightly colored graft polymers from components (A) and (B), the polymerization is carried out in the presence of water-soluble phosphorus compounds in which the phosphorus has an oxidation number of 1 to 4, the water-soluble alkali metal or ammonium salts, water-soluble Compounds containing PO (OH) "groups and / or their water-soluble salts. Phosphorous acid is preferably used. The phosphorus compounds in question are used to reduce the discoloration of the graft copolymers in amounts of from 0.01 to 5% by weight, based on the used monomers (A) Possible phosphorus compounds are described in EP-A-0 175 317.

Die Copolymerisation der Komponenten (A) und (B) erfolgt üblicherweise in einer Inertgasatmosphäre unter Ausschluß von Luftsauerstoff. Während der Polymerisation wird im allgemeinen für eine gute Durchmischung der Reaktionsteilnehmer gesorgt. Bei kleineren Ansätzen, bei denen eine sichere Abführung der Polymerisationswärme gewährleistet ist, kann man die Reaktionsteilnehmer, die vorzugsweise in einem inerten Verdünnungsmittel vorliegen, diskontinuierlich copolymerisieren, indem man das Reaktionsgemisch auf die Polymerisationstemperatur erhitzt. Diese Temperaturen liegen in dem Bereich von 40 bis 150°C. Um den Verlauf der Polymerisationsreaktion besser kontrollieren zu können, gibt man daher die Monomeren (A) dem polymerisierenden Gemisch kontinuierlich oder absatzweise in dem Maße zu, daß die Propfpolymerisation in dem gewünschten Temperaturbereich gut kontrollierbar ist. Bevorzugt ist eine Art der Zugabe der Monomeren der Komponente (A) bei der man im Polymerisationsreaktor zunächst die Verbindungen der Komponente (B) oder zumindest einen Teil der Verbindungen der Komponente (B) zusammen mit mindestens einem Monomer der Gruppe (a) im Reaktor vorlegt und darin unter Rühren auf die gewünschte Polymerisationstemperatur erhitzt. Sobald diese Temperatur erreicht ist, fügt man dazu über einen Zeitraum von etwa 1 bis 10, vorzugsweise 2 bis 8 Stunden, gegebenenfalls die restlichen Monomeren der Gruppe (a) sowie gegebenenfalls die Monomeren (b) und gegebenenfalls (c) sowie den Initiator und gegebenenfalls einen Regler zu.The copolymerization of components (A) and (B) is usually carried out in an inert gas atmosphere with the exclusion of atmospheric oxygen. Good mixing of the reactants is generally ensured during the polymerization. In the case of smaller batches in which a reliable removal of the heat of polymerization is ensured, the reactants, which are preferably present in an inert diluent, can be copolymerized discontinuously by heating the reaction mixture to the polymerization temperature. These temperatures are in the range of 40 to 150 ° C. In order to be able to better control the course of the polymerization reaction, the monomers (A) are therefore added continuously or batchwise to the polymerizing mixture to the extent that the graft polymerization can be easily controlled in the desired temperature range. A type of addition of the monomers of component (A) is preferred in which the compounds of component (B) or at least some of the compounds of component (B) are initially introduced into the reactor together with at least one monomer of group (a) in the polymerization reactor and heated therein to the desired polymerization temperature with stirring. As soon as this temperature is reached, the remaining monomers of group (a) and optionally the monomers (b) and optionally (c) and the initiator and optionally are added over a period of about 1 to 10, preferably 2 to 8 hours a controller too.

Oftmals ist es vorteilhaft, daß pflanzliche und tierische Öle zunächst mit einem Radikalspender in Mengen von 0,1 bis 10 % vorzubehandeln und dann erst die Monomeren A) zuzusetzen. So kann beispielsweise Capelanöl mit 1 % Ditertiärbutylperoxid 2 h im schwachen N2-Strom auf 150°C erhitzt werden und anschließend wird Acrylsäure innerhalb von 3 h bei 150°C zudosiert.It is often advantageous to pretreat vegetable and animal oils first with a radical dispenser in amounts of 0.1 to 10% and only then to add the monomers A). For example, capelan oil with 1% ditertiary butyl peroxide can be heated to 150 ° C. in a weak stream of N 2 for 2 hours and then acrylic acid is metered in at 150 ° C. in the course of 3 hours.

Nach dem Ende der Pfropfpolymerisation wird das gepfropfte pflanzliche oder tierische Öl in eine wäßrige Dispersion übergeführt. Die Dispergierung kann unter Verwendung üblicher Emulgatoren wie Fettalkoholethoxylaten, Dodecylbenzolsulfonaten, Dioctylsulfosuccinat oder Alkylsulfonaten in geeigneten Apparaten vorgenommen werden. Besonders bevorzugt ist die emulgatorfreie Dispergierung, indem man die Carboxylgruppen des Pfropfpolymeren teilweise oder vollständig mit Alkalien, Erdalkalien, Ammoniak oder Aminen neutralisiert und somit zu stabilen wäßrigen Dispersionen gelangt. Diese Dispersionen haben einen Feststoffgehalt von 5 bis 80 % und vorzugsweise 20 bis 70 % und können so direkt zur Behandlung der Leder und Pelzfelle Verwendung finden. Die Bestimmung des Trocknungsrückstands kann z.B. im Trockenschrank (2 h bei 120°C) erfolgen.After the end of the graft polymerization, the grafted vegetable or animal oil is converted into an aqueous dispersion. The dispersion can be carried out using conventional emulsifiers such as fatty alcohol ethoxylates, dodecylbenzenesulfonates, Dioctyl sulfosuccinate or alkyl sulfonates can be made in suitable apparatus. Emulsifier-free dispersion is particularly preferred by partially or completely neutralizing the carboxyl groups of the graft polymer with alkalis, alkaline earths, ammonia or amines and thus obtaining stable aqueous dispersions. These dispersions have a solids content of 5 to 80% and preferably 20 to 70% and can thus be used directly for the treatment of leather and furskins. The drying residue can be determined, for example, in a drying cabinet (2 h at 120 ° C).

Mit den erfindungsgemäß zu verwendenden Pfropfpolymeren ist es möglich, sehr weiche Leder ohne Zusatz herkömmlicher Likker herzustellen. Die wasserabstoßenden Eigenschaften hydrophobierter Leder werden bei Anwendung dieser Produkte nicht negativ beeinflußt.With the graft polymers to be used according to the invention, it is possible to produce very soft leather without the addition of conventional liquors. The water-repellent properties of hydrophobized leather are not adversely affected when these products are used.

Die mechanischen Eigenschaften, wie Reißfestigkeit, sowie die Lichtechtheit und Wärmevergilbungsresistenz solcher Leder werden durch die Anwendung dieser Pfropfpolymeren sehr positiv beeinflußt. Neben der praktisch quantitativen Flottenauszehrung bewirkt die gute Fixierung im Leder eine große Resistenz gegenüber der Extrahierbarkeit mit Lösungsmitteln oder Wasser. Dies führt zu sogenannten waschbaren Ledern, d.h. Ledern, die nach dem Waschen ihre Eigenschaften wie Weicheit, Festigkeit und Geschmeidigkeit nicht verlieren; im Gegensatz dazu ist diese Eigenschaft bei Ledern, die mit konventionellen Lickern gefettet werden, nicht zu erwarten.The mechanical properties, such as tensile strength, as well as the light fastness and heat yellowing resistance of such leathers are influenced very positively by the use of these graft polymers. In addition to the practically quantitative exhaustion of the liquor, the good fixation in the leather results in great resistance to extractability with solvents or water. This leads to so-called washable leathers, i.e. Leathers that do not lose their properties such as softness, firmness and suppleness after washing; in contrast, this property is not to be expected for leathers that are greased with conventional licker.

Ein weiterer Vorteil der erfindungsgemäß zu verwendenden wäßrigen Dispersion besteht darin, daß sie vorzugsweise keine zusätzlichen Emulgatoren enthalten. So müssen Leder und Pelze, die hydrophobiert werden sollen und mit emulgatorhaltigen Produkten behandelt werden, bekanntlich nach der Behandlung mit diesen Mitteln aufwendigen Prozessen, z.B. Nachbehandlung mit mehrwertigen Metallsalzen, unterworfen werden, um die Emulgatoren im Leder oder in den Pelzfellen unwirksam zu machen, d.h. zu fixieren.Another advantage of the aqueous dispersion to be used according to the invention is that it preferably contains no additional emulsifiers. It is known that leather and furs, which are to be made hydrophobic and are treated with products containing emulsifiers, have to undergo complex processes after treatment with these agents, e.g. Post-treatment with polyvalent metal salts, to make the emulsifiers in the leather or in the fur skins ineffective, i.e. to fix.

Die oben beschriebenen Pfropfpolymerdispersionen eignen sich zur Behandlung von allen üblichen gegerbten Häuten. Die gegerbten Häute werden üblicherweise vor der Behandlung entsäuert. Sie können bereits vor der Behandlung gefärbt worden sein. Eine Färbung kann jedoch auch erst nach der erfindungsgemäß erfolgenden Fettung vorgenommen werden.The graft polymer dispersions described above are suitable for the treatment of all conventional tanned hides. The tanned hides are usually deacidified before treatment. They may have been stained before treatment. Coloring can, however, also be carried out only after the lubrication that takes place according to the invention.

Die gegerbten Häute werden mit den wäßrigen Dispersionen zweckmäßigerweise in wäßriger Flotte, die durch Verdünnen der Pfropfpolymerdispersionen mit Wasser erhältlich sind, bei pH-Werten von 4 bis 10, vorzugsweise von 5 bis 8 und Temperaturen von 20 bis 60, vorzugsweise 30 bis 50°C während eines Zeitraumes von 0,1 bis 5, insbesondere 0,5 bis 2 h, behandelt. Diese Behandlung erfolgt beispielsweise durch Walken in einem Faß. Die benötigte Menge an Pfropfpolymerdispersion beträgt, bezogen auf das Falzgewicht des Leders oder das Naßgewicht der Pelzfelle, 0,1 bis 30, vorzugsweise 1 bis 20 Gew.-%. Die Flottenlänge, d.h. das prozentuale Gewichtsverhältnis der Behandlungsflotte zur Ware, bezogen auf das Falzgewicht des Leders oder das Naßgewicht der Pelzfelle, beträgt üblicherweise 10 bis 1000, vorzugsweise 30 bis 150 %, bei Pelzfellen 50 bis 500 %.The tanned skins are expediently mixed with the aqueous dispersions in aqueous liquors, which can be obtained by diluting the graft polymer dispersions with water, at pH values of 4 to 10, preferably 5 to 8 and temperatures of 20 to 60, preferably 30 to 50 ° C. treated for a period of 0.1 to 5, in particular 0.5 to 2 h. This treatment takes place, for example, by drumming in a barrel. The required amount of graft polymer dispersion, based on the shaved weight of the leather or the wet weight of the fur skins, is 0.1 to 30, preferably 1 to 20,% by weight. The fleet length, i.e. the percentage weight ratio of the treatment liquor to the goods, based on the shaved weight of the leather or the wet weight of the fur skins, is usually 10 to 1000, preferably 30 to 150%, for fur skins 50 to 500%.

Nach der Behandlung mit der wäßrigen Flotte wird der pH-Wert der Behandlungsflotte durch Zusatz von Säuren, vorzugsweise einer organischen Säure wie Ameisensäure, auf einen Wert von 3 bis 5, vorzugsweise 3,5 bis 4, eingestellt.After the treatment with the aqueous liquor, the pH of the treatment liquor is adjusted to a value of 3 to 5, preferably 3.5 to 4, by adding acids, preferably an organic acid such as formic acid.

Bei der Mitverwendung von üblichen Nachgerbstoffen beim Veredlungsprozeß des Leders und der Pelzfelle kann die Behandlung mit den erfindungsgemäß zu verwendenden wäßrigen Dispersionen vor oder nach dem Nachgerbschritt eingesetzt werden.If conventional retanning agents are also used in the finishing process of the leather and the fur skins, the treatment with the aqueous dispersions to be used according to the invention can be used before or after the retanning step.

Die Prozentangaben in den Beispielen sind, falls nicht anders angegeben, in Gewichtsprozent.Unless stated otherwise, the percentages in the examples are in percent by weight.

Beispiele zur HerstellungManufacturing examples Beispiel 1example 1

In einem Rührkolben werden 100 g Capelanöl und 0,5 g tert.Butylperethylhexanoat im schwachen N2-Strom auf 150°C erhitzt und 1,5 h bei 150°C gerührt. Dann werden 5 g Maleinsäureanhydrid und 0,5 g tert.Butylperethylhexanoat zugesetzt und es wird weitere 6 h auf 150°C erhitzt. Anschließend kühlt man ab, gibt 300 g Wasser und 3,8 g 50 %ige Natronlauge zu und dispergiert die Mischung mit einem Ultra-Turrax 10 Minuten lang. Die erhaltene Dispersion hat einen pH-Wert von 10,0, einen Trocknungsrückstand von 25 % und eine Brookfieldviskosität von 22 mPa·s bei 23°C. Sie kann direkt zur Lederbehandlung Verwendung finden.In a stirred flask, 100 g of capelan oil and 0.5 g of tert-butyl perethylhexanoate are heated to 150 ° C. in a gentle stream of N2 and stirred at 150 ° C. for 1.5 hours. Then 5 g of maleic anhydride and 0.5 g of tert-butyl perethylhexanoate are added and the mixture is heated at 150 ° C. for a further 6 h. Subsequently Cool down, add 300 g of water and 3.8 g of 50% sodium hydroxide solution and disperse the mixture with an Ultra-Turrax for 10 minutes. The dispersion obtained has a pH of 10.0, a drying residue of 25% and a Brookfield viscosity of 22 mPa · s at 23 ° C. It can be used directly for leather treatment.

Beispiel 2Example 2

Ähnlich wie bei Beispiel 1 werden 100 g Capelanöl und 1 g tert.Butylperethylhexanoat auf 150° erhitzt und 1 h gerührt. Dann werden 10 g Maleinsäureanhydrid und 1 g tert.Butylperethylhexanoat zugesetzt und es wird 6 h bei 150°C erhitzt. Nach dem Abkühlen wird mit 310 g Wasser und 7,2 g 50 %iger Natronlauge verdünnt und mit dem Ultra-Turrax die Mischung 10 Minuten intensiv dispergiert. Die erhaltene Dispersion hat einen pH-Wert von 8,9, einen Trocknungsrückstand von 25 % und eine Brookfieldviskosität von 16 mPa·s bei 23°C.Similar to Example 1, 100 g of capelan oil and 1 g of tert-butyl perethylhexanoate are heated to 150 ° and stirred for 1 hour. Then 10 g of maleic anhydride and 1 g of tert-butyl perethylhexanoate are added and the mixture is heated at 150 ° C. for 6 hours. After cooling, the mixture is diluted with 310 g of water and 7.2 g of 50% sodium hydroxide solution and the mixture is intensively dispersed for 10 minutes with the Ultra-Turrax. The dispersion obtained has a pH of 8.9, a drying residue of 25% and a Brookfield viscosity of 16 mPa · s at 23 ° C.

Beispiel 4Example 4

Ähnlich Beispiel 1 werden 108 g Rapsöl unter schwachem N2-Strom auf 150°C erhitzt. Dann werden bei 150°C innerhalb von 1 h 20 g Acrylsäure (100 %ig) und die Lösung von 1 g tert.Butylperethylhexanoat in 10 g Rapsöl gleichmäßig zudosiert. Danach wird 2 h bei 150° gerührt, nochmals 1 g tert.Butylperethylhexanoat zugesetzt und nochmals 2 h bei 150°C erhitzt.Similar to Example 1, 108 g of rapeseed oil are heated to 150 ° C under a weak stream of N2. Then 20 g of acrylic acid (100%) and the solution of 1 g of tert-butyl perethylhexanoate in 10 g of rapeseed oil are metered in uniformly at 150 ° C. within 1 h. The mixture is then stirred at 150 ° for 2 h, a further 1 g of tert-butyl perethylhexanoate is added and the mixture is heated again at 150 ° C. for 2 h.

100 g des so erhaltenen Pfropfpolymeren werden mit 76 g Wasser verdünnt und 10 Minuten lang intensiv dispergiert. Die weiße viskose Dispersion hat einen pH-Wert von 3,5 und einen Trocknungsrückstand von 55,9 %.100 g of the graft polymer thus obtained are diluted with 76 g of water and dispersed intensively for 10 minutes. The white viscous dispersion has a pH of 3.5 and a drying residue of 55.9%.

Beispiel 4Example 4

Verwendet man anstelle von Acrylsäure Methacrylsäure, so wird eine Dispersion mit vergleichbaren Eigenschaften erhalten.If methacrylic acid is used instead of acrylic acid, a dispersion with comparable properties is obtained.

Beispiel 5Example 5

Entsprechend Beispiel 1 werden 100 g Rapsöl und 1 g tert.Butylperethylhexanoat 1 h bei 150°C unter einem schwachen N2-Strom erhitzt. Anschließend werden 18 g Maleinsäureanhydrid und 1 g tert.Butylperethylhexanoat zugesetzt und 6 h bei 150°C erhitzt. Dann wird abgekühlt und 105 g des Produkts werden mit 90 g Wasser und 8 g 50 %iger Natronlauge gemischt und 10 Minuten mit dem Ultra-Turrax intensiv dispergiert. Es entsteht eine homogene viskose Dispersion mit einem Trocknungsrückstand von 52,7 % und einem pH-Wert von 5,5.According to Example 1, 100 g of rapeseed oil and 1 g of tert-butyl perethylhexanoate are heated at 150 ° C. for 1 hour under a weak stream of N 2 . 18 g of maleic anhydride and 1 g of tert-butyl perethylhexanoate are then added and the mixture is heated at 150 ° C. for 6 h. Then it is cooled and 105 g of the product are mixed with 90 g of water and 8 g of 50% sodium hydroxide solution and intensively dispersed for 10 minutes with the Ultra-Turrax. A homogeneous viscous dispersion is formed with a drying residue of 52.7% and a pH of 5.5.

Beispiel 6Example 6

Entsprechend Beispiel 1 werden 100 g Capelanöl im schwachen N2-Strom auf 150° erhitzt und anschließend innerhalb von 1 h bei 150°C mit 20 g Acrylsäure und einer Lösung von 1 g tert.Butylperethylhexanoat in 10 g Capelanöl gleichmäßig versetzt. Anschließend wird noch 1 h nacherhitzt, nochmals 1 g tert.Butylperethylhexanoat zugegeben und 1 h weitererhitzt. Danach wird abgekühlt und 103 g des Produkts werden nach Zugabe von 90 g Wasser und 9 g 50 %iger Natronlauge mittels Ultra-Turrax 10 Minuten intensiv dispergiert. Die viskose homogene Dispersion hat einen pH-Wert von 7,0 und der Trocknungsrückstand beträgt 49,1 %.According to Example 1, 100 g of capelan oil are heated to 150 ° in a weak N2 stream and then 20 g of acrylic acid and a solution of 1 g of tert-butyl perethylhexanoate in 10 g of capelan oil are uniformly added at 150 ° C. in the course of 1 h. The mixture is then heated for a further 1 h, another 1 g of tert-butyl perethylhexanoate is added and the mixture is heated for a further 1 h. The mixture is then cooled and 103 g of the product, after adding 90 g of water and 9 g of 50% sodium hydroxide solution, are dispersed intensively for 10 minutes using Ultra-Turrax. The viscous homogeneous dispersion has a pH of 7.0 and the drying residue is 49.1%.

Beispiel 7Example 7

Entsprechend Beispiel 6 verwendet man anstelle von Acrylsäure 20 g Methacrylsäure. 115 g des erhaltenen Pfropfpolymeren, 95 g Wasser und 14 g 50 %ige Natronlauge werden 10 Minuten mit dem Ultra-Turrax intensiv dispergiert. Die viskose Dispersion hat einen pH-Wert von 7,1 und einen Trocknungsrückstand von 51,2 %.According to Example 6, 20 g of methacrylic acid are used instead of acrylic acid. 115 g of the graft polymer obtained, 95 g of water and 14 g of 50% sodium hydroxide solution are dispersed intensively for 10 minutes with the Ultra-Turrax. The viscous dispersion has a pH of 7.1 and a drying residue of 51.2%.

AnwendungsbeispieleExamples of use Beispiel 1example 1

Chromgegerbtes Rindleder mit einer Falzstärke von 1,8 mm, das auf einen pH-Wert von 5,0 entsäuert worden war, wurde mit 15 % des Produktes aus Beispiel 1, bezogen auf das Falzgewicht, 2 h bei 40°C im Gerbfaß gewalkt. Die Gesamtflottenlänge betrug 150 %. Das Leder wurde anschließend mit 1 % eines üblichen anionischen Anilinfarbstoffes gefärbt. Danach wurde es mit Ameisensäure auf einen pH-Wert von 3,8 eingestellt. Es wurde abschließend gewaschen, mechanisch ausgereckt und getrocknet. Das erhaltene Leder war sehr weich, geschmeidig, gut gefüllt und gleichmäßig gefärbt.Chrome-tanned cowhide with a fold thickness of 1.8 mm, which had been deacidified to a pH of 5.0, was treated with 15% of the product from Example 1, based on the fold weight, Tumbled for 2 hours at 40 ° C in a tanning barrel. The total fleet length was 150%. The leather was then dyed with 1% of a common anionic aniline dye. Then it was adjusted to a pH of 3.8 with formic acid. It was then washed, mechanically stretched and dried. The leather obtained was very soft, supple, well filled and evenly colored.

Beispiel 2Example 2

Chromgegerbtes Rindleder mit einer Falzstärke von 1,8 mm, das auf einen pH-Wert von 5,0 entsäuert und mit 0,7 % eines üblichen anionischen Anilinfarbstoffes gefärbt worden war, wurde mit 20 % des Produktes aus Beispiel 2, bezogen auf das Falzgewicht, 1,5 h bei 40°C im Gerbfaß gewalkt. Im Anschluß an diese Behandlung wurde das Leder mit Ameisensäure auf einen pH-Wert von 3,6 gebracht und wie üblich fertiggestellt. Das so erhaltene Leder war sehr weich und griffig.Chrome-tanned cowhide with a fold thickness of 1.8 mm, which had been deacidified to a pH of 5.0 and dyed with 0.7% of a conventional anionic aniline dye, was mixed with 20% of the product from Example 2, based on the fold weight , Tumbled for 1.5 h at 40 ° C in the tanning drum. Following this treatment, the leather was brought to a pH of 3.6 with formic acid and finished as usual. The leather thus obtained was very soft and easy to grip.

Beispiel 3Example 3

Chromgegerbtes Rindleder mit einer Falzstärke von 1,8 mm, das auf einen pH-Wert von 5,0 entsäuert und mit 0,7 % eines üblichen anionischen Anilinfarbstoffes gefärbt worden war, wurde mit 15 % des Produktes aus Beispiel 3, bezogen auf das Falzgewicht, 30 Minuten bei 40°C im Gerbfaß gewalkt und anschließend mit 3 % eines üblichen synthetischen Gerbstoffes 1 h weiterbehandelt. Dann wurde das Leder mit Ameisensäure auf einen pH-Wert von 3,6 gebracht und wie üblich fertiggestellt. Das so erhaltene Leder fühlte sich angenehm weich und griffig an.Chrome-tanned cowhide with a fold thickness of 1.8 mm, which had been deacidified to a pH of 5.0 and dyed with 0.7% of a common anionic aniline dye, was mixed with 15% of the product from Example 3, based on the fold weight , Tumbled for 30 minutes at 40 ° C. in a tanning drum and then further treated with 3% of a conventional synthetic tanning agent for 1 h. Then the leather was brought to a pH of 3.6 with formic acid and finished as usual. The leather thus obtained felt pleasantly soft and easy to grip.

Beispiel 4Example 4

Das Produkt aus Beispiel 4 wurde analog zu der im Beispiel 3 angegebenen Arbeitsweise eingesetzt. Das so erhaltene Leder zeigte weiche und runde Griffeigenschaften.The product from Example 4 was used analogously to the procedure given in Example 3. The leather thus obtained showed soft and round grip properties.

Beispiel 5Example 5

Das Produkt aus Beispiel 5 wurde analog zu der im Beispiel 1 angegebenen Arbeitsweise eingesetzt. Das so erhaltene Leder zeichnete sich durch einen runden, weichen Griff aus.The product from Example 5 was used analogously to the procedure given in Example 1. The leather thus obtained was characterized by a round, soft handle.

Beispiel 6Example 6

Das Produkt aus Beispiel 6 wurde analog zu der im Beispiel 1 angegebenen Arbeitsweise eingesetzt. Das Ergebnis war ähnlich vorteilhaft wie bei den vorhergehenden Beispielen.The product from Example 6 was used analogously to the procedure given in Example 1. The result was similarly advantageous as in the previous examples.

Beispiel 7Example 7

Das Produkt aus Beispiel 7 wurde analog zu der im Beispiel 3 angegebenen Arbeitsweise eingesetzt. Das Ergebnis war ein weiches Leder mit angenehmem Griff.The product from Example 7 was used analogously to the procedure given in Example 3. The result was a soft leather with a comfortable grip.

Claims (7)

  1. The use of water-soluble or water-dispersible vegetable and animal oil graft polymers obtainable by free-radically initiated polymerization
    A) of a monomer or monomer mixture comprising
    (a) from 20 to 100% by weight of monoethylenically unsaturated carboxylic acids and/or monoethylenically unsaturated sulfonic acids and/or monoethylenically unsaturated phosphonic acids or their alkali metal, alkaline earth metal or ammonium salts,
    (b) from 0 to 80% by weight of other monoethylenically unsaturated monomers which are copolymerizable with the monomers (a), and
    (c) from 0 to 5% by weight of at least doubly ethylenically unconjugatedly unsaturated monomers
    in the presence of
    B) vegetable and/or animal oils
    in a weight ratio of A:B of (80-1):(20-99), for fatliquoring and filling leathers and fur skins with the exception of the use of copolymers and/or adducts of maleic anhydride with unsaturated fatty acids and/or their carboxyl group derivatives as neutral oil component in leather and fur fatliquoring compositions.
  2. A use as claimed in claim 1, characterized in that component a) is a carboxylic acid or anhydride.
  3. A use as claimed in claim 1, characterized in that component a) is acrylic acid, methacrylic acid or maleic acid or anhydride.
  4. A use as claimed in claim 1, characterized in that component b) is a (meth)acrylic acid or maleic acid derivative, in particular a C1-C20-alkyl ester, or (meth)acrylamide.
  5. A use as claimed in claim 1, characterized in that only component a) is used.
  6. A use as claimed in claim 1, characterized in that self-emulsifying systems are used.
  7. A use as claimed in claim 1, characterized in that components A and B are used in a weight ratio of (60-5):(40-95).
EP93915893A 1992-07-24 1993-07-13 Use of graft polymers for stuffing and fulling leathers and fur pelts Expired - Lifetime EP0607388B1 (en)

Applications Claiming Priority (3)

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DE4224456 1992-07-24
DE4224456A DE4224456A1 (en) 1992-07-24 1992-07-24 Use of graft polymers for greasing and filling leather and fur skins
PCT/EP1993/001831 WO1994002650A1 (en) 1992-07-24 1993-07-13 Use of graft polymers for stuffing and fulling leathers and fur pelts

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DE4402029A1 (en) * 1994-01-25 1995-07-27 Basf Ag Aqueous solutions or dispersions of copolymers
DE19625984C2 (en) * 1996-06-28 1999-07-29 Stockhausen Chem Fab Gmbh Aqueous polymer dispersions, process for their preparation and their use in leather production
KR100346466B1 (en) * 1999-12-06 2002-07-27 현대자동차주식회사 Sealing materials of paste type for antiacoustic
FR2836485B1 (en) * 2002-02-28 2004-07-30 Coatex Sas USES OF GRAFT ACRYLIC POLYMERS IN THE FIELD OF COLLAGEN-BASED SUBSTRATES. SUBSTRATES, SKINS AND LEATHERS THUS OBTAINED
AU2003298467A1 (en) * 2003-12-25 2005-08-11 Council Of Scientific And Industrial Research A process for making leather
US20060188729A1 (en) * 2005-02-22 2006-08-24 Kai-Volker Schubert Washable leather with repellency
FR2974578B1 (en) * 2011-04-28 2015-10-30 Rhodia Operations COPOLYMERIZED FATTY BODY, PREPARATION METHOD AND APPLICATIONS THEREOF

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DE4142318C2 (en) * 1991-12-20 1999-01-14 Zschimmer & Schwarz Gmbh & Co Use of fatty acid conversion products in leather and fur greasing agents and agents for greasing leather and fur skins

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DE59307502D1 (en) 1997-11-13
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US5620748A (en) 1997-04-15
JPH06511284A (en) 1994-12-15
AU662071B2 (en) 1995-08-17
AU4567993A (en) 1994-02-14
EP0607388A1 (en) 1994-07-27
DE4224456A1 (en) 1994-01-27

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