EP0628085A1

EP0628085A1 - Use of reaction products of homo- or copolymerisates based on monoethylenically unsaturated dicarboxylic acid anhydrides with amines or alcohols for stuffing and fulling leathers and fur pelts.

Info

Publication number: EP0628085A1
Application number: EP93903970A
Authority: EP
Inventors: Hermann Birkhofer; Peter Danisch; Walter Denzinger; Heinrich Hartmann; Norbert Greif; Knut Oppenlaender
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1992-02-26
Filing date: 1993-02-15
Publication date: 1994-12-14
Anticipated expiration: 2013-02-15
Also published as: US5433752A; JPH07504217A; AU3497393A; WO1993017130A1; DE4205839A1; DE59301646D1; EP0628085B1; ES2083280T3; AU661562B2

Abstract

Utilisation de produits de réaction A) d'homo- ou de copolymérisats à base d'anhydrides d'acide dicarboxylique monoéthyléniquement insaturés, que l'on peut obtenir par polymérisation initiée radicalement a) de 30 à 100 % en moles d'un ou de plusieurs anhydride(s) d'acide dicarboxylique monoéthyléniquement insaturés ayant 4 à 10 atomes de C, b) de 0 à 70 % en moles d'un ou de plusieurs aromate(s) vynilique(s) de la formule générale (I) où R1, R2 et R3 représentent oxygène, méthyle ou éthyle et k vaut 1 ou 2, c) de 0 à 70 % en moles d'un ou de plusieurs ester(s) vynilique(s) d'acides carboxyliques C1 à C8, d) de 0 à 50 % en moles d'une ou de plusieurs oléfine(s) C2 à C6 et e) de 0 à 30 % en moles d'un ou de plusieurs acides carboxyliques C3 à C5 monoéthyléniquement insaturés, B) d'amines ou d'alcools ou de mélanges d'amines et d'alcools pour nourrir et fouler des cuirs et des peaux en poils.Use of reaction products A) of homo- or copolymerizates based on monoethylenically unsaturated dicarboxylic acid anhydrides, which can be obtained by radically initiated polymerization of a) 30 to 100 mol % of one or more several monoethylenically unsaturated dicarboxylic acid anhydride(s) having 4 to 10 C atoms, b) from 0 to 70% by mole of one or more vinyl aromatic(s) of the general formula (I) in which R1, R2 and R3 represent oxygen, methyl or ethyl and k is 1 or 2, c) from 0 to 70% by mole of one or more vinyl ester(s) of C1 to C8 carboxylic acids, d ) from 0 to 50% by mole of one or more C2 to C6 olefin(s) and e) from 0 to 30% by mole of one or more monoethylenically unsaturated C3 to C5 carboxylic acids, B) of amines or alcohols or mixtures of amines and alcohols for nourishing and treading hides and hides.

Description

Use of reaction products of homopolymers or copolymers based on monoethylenically unsaturated dicarboxylic acid anhydrides with amines or alcohols for greasing and filling leather and fur skins

description

The present invention relates to the use of reaction products of homopolymers or copolymers based on monoethylenically unsaturated dicarboxylic acid anhydrides with certain amines and alcohols for greasing and filling leather and fur skins. The invention also relates to leather treatment compositions which contain these conversion products.

To control the mechanical properties of leather such as softness, flexibility or suppleness, aqueous fat emulsions (licker) are used, which are generally based on petrochemically produced or natural oils and fats. These are usually made water-emulsifiable by partial sulfonation or with the help of emulsifiers. Incomplete liquor drainage, relatively easy extraction by solvent or water, the occurrence of migration phenomena and unsatisfactory authenticity profiles all turn out to be disadvantages of this class of fatliquoring agents.

Polymeric products, for example based on unsaturated dicarboxylic acid derivatives and long-chain olefins with greasing properties for leather and fur skins, are known and are used as water repellents for leather and fur skins.

For example, EP-A 412 389 describes copolymers of C $ to C ₄₀ mono-olefins and ethylenically unsaturated C to Cβ-dicarboxylic acid anhydrides which, following their preparation, by solvolysis of the anhydride groups, for example with bases such as amines or partial esterification of the anhydride groups with alcohols and at least partial neutralization of the carboxyl groups formed with bases in an aqueous medium can be converted to aqueous solutions or dispersions which are recommended as water repellents for leather and fur files.

Such polymeric leather greasing agents do have a certain greasing effect, but this is still not entirely satisfactory, especially for soft types of leather. In these cases, an additional fatliquor based on a native or synthetic see Lickers are used, which complements the effect with the polyer fatty agent.

The invention was therefore based on the object of providing an improved means for greasing and filling leather and fur files which no longer puts the disadvantages of the prior art on ice.

Accordingly, the use of reaction products from

A) Homopolymers or copolymers based on monoethylenically unsaturated dicarboxylic acid anhydrides, obtainable by free-radically initiated polymerization of

(a) 30 to 100 mol% of one or more monoethylenically unsaturated dicarboxylic acid anhydrides having 4 to 10 carbon atoms,

(b) 0 to 70 mol% of one or more vinyl aromatics of the general formula I

in which R ¹ , R ² and R ^{3 are} hydrogen, methyl or ethyl and k is 1 or 2,

(c) 0 to 70 mol% of one or more vinyl esters from CT _. - up to Cβ-carboxylic acids,

(d) 0 to 50 mol% of one or more C ₂ to Cg olefins and

(e) 0 to 30 mol% of one or more monoethylenically unsaturated C ₃ to Cs carboxylic acids,

up to 10% by weight of further copolymerizable monomers can be added to the monomer mixture of (a) to (e) with

B) amines of the general formula R ⁴ R ⁵ NH, in which R ^{4 is} hydrogen,

C ~ to C ₂ c - alkyl, C ₅ - to Ca-cycloalkyl or C ₂ - to C ₄ -hydroxyalkyl and R ⁵ Cζ- to C ₃ ^' o-alkyl, C ₆ ~ to C o-alkenyl _r C5 to Cg cycloalkyl or C ₂ to C ₄ hydroxyalkyl, or

Alcohols of the general formula R ⁶ -O- (CmH _2ιr ) _p - (C _n H _2n 0) qH- in the R ⁶ C: ~ to C ₃ c-alkyl, C ₂ - to C ₃ o-alkenyl, C ₅ - up to C ₈ -Cy- cloalkyl or in the case p + q> 0 is hydrogen, m and n each represent a number from 2 to 4 and p and q each denote a number from 0 to 50, or mixtures of such amines and alcohols

found for greasing and filling leather and fur skins.

Maleic anhydride, itaconic anhydride, citraconic anhydride, mesaconic anhydride, methylene malonic anhydride and mixtures thereof are particularly suitable as monoethylenically unsaturated dicarboxylic acid anhydrides having 4 to 10 carbon atoms (a). Maleic anhydride is particularly preferred.

In the general formula I for the vinyl aromatics (b), the radical R ¹ preferably represents hydrogen or methyl, the radicals R ² and R ³ . preferably denote hydrogen and k preferably denotes 1. If R ³ in the case k = 1 is methyl or ethyl, there is an ortho, meta or preferably para substitution on the phenyl nucleus. If R ³ in the case k = 2 is methyl or ethyl, the substitution pattern on the phenyl nucleus is preferably 2.4.

Suitable vinyl aromatics (b) are, in particular, styrene or α-methylstyrene or a mixture thereof.

Suitable vinyl esters (c) are, in particular, vinyl esters of C 1 -C ₄ -carboxylic acids, for example vinyl formate, vinyl propionate, vinyl butyrate or, in particular, vinyl acetate. Mixtures of such vinyl esters can also be used.

Suitable C ₂ -C 6 -olefins (d) are, in particular, straight-chain or branched monoolefins, in particular α-olefins, for example ethylene, propylene, 1-butene, isobutene, 1-pentene or 1-hexene, and also 2-butene, 2-pentene, 2-hexene or 3-hexene. Isobutene is particularly preferred. In addition, conjugated dienes such as butadiene or isoprene can also be used. Mixtures of the olefins mentioned can also be used.

Suitable monoethylenically unsaturated carboxylic acids (C) are, in particular, C - to C ₄ -carboxylic acids, for example crotonic acid or, in particular, acrylic acid and methacrylic acid.

Homopolymers A from one monomer (a), copolymers A from two or more monomers (a) and copolymers A from monomers (a) to (e) are used, the copolymer, however, at least 30 mol% must contain monoethylenically unsaturated dicarboxylic anhydride (a). For example, a copolymer of 60 mol% styrene, 30 mol% maleic anhydride and 10 mol% of acrylic acid or another copolymer

50 mol maleic anhydride, 25 mol% styrene and 25 mol% vinyl acetate can be used.

In a preferred embodiment, a homopolymer of a monoethylenically unsaturated dicarboxylic anhydride having 4 to 10 carbon atoms (a) is used as component A in the preparation of the reaction products used according to the invention.

In a further preferred embodiment, a copolymer is formed as component A in the preparation of the reaction products used according to the invention

(a) 30 to 99 mol% of a monoethylenically unsaturated dicarboxylic acid anhydride with 4 to 10 carbon atoms and

(b) 1 to 70 mol% of one or more vinyl aromatics I

used.

(c) 1 to 70 mol% of one or more vinyl esters of -C ~ to Cβ-carboxylic acids

used.

(a) 50 to 99 mol% of a monoethylenically unsaturated dicarboxylic acid anhydride with 4 to 10 carbon atoms and

(d) 1 to 50 mol% of one or more C ₂ - to C _ß- olefins

used.

To further modify the properties of the polymers A, small amounts of further monomers copolymerizable with the monomers (a) to (e), in particular monoethylenically and polyethylenically unsaturated compounds, can also be used. long. These are, for example, hydroxyalkyl esters with 2 to 6 carbon atoms in the alkyl radical and the corresponding nitriles of the mono- and dicarboxylic acids already mentioned, N-vinylamides such as N-vinylacetamide, N-vinylpyrrolidone, N-vinylpiperidine, N-vinylcaprolactam, N -Vinyl-succinimide, N-vinylphthalimide, N-vinyloxazolone, N-vinylformamide and N-vinylimidazole and alkyl vinyl ether with 1 to 18 carbon atoms in the alkyl radical, for example methyl vinyl ether, ethyl vinyl ether or stearyl vinyl ether, and CΘ ~ to C o- 01efine, in particular Cio to C ₂ 0 ~ α-olefins, for example 1-dodecene, 1-hexadecene or 1-octadecene. Also suitable are methylenebisacrylamide, esters of acrylic acid, methacrylic acid and maleic acid with polyhydric alcohols, such as, for example, glycol diacrylate, glycerol triacrylate, glycol dimethacrylate, glycerol trimethacrylate, and at least polyols esterified with acrylic acid or methacrylic acid, such as pentaerythritol and glucose. Also suitable are divinylbenzene, divinyldioxane, pentaerythritol triallyl ether and pentaallylsucrose, and glycol diacrylates of polyethylene glycols with molecular weights of up to 3000. These monomers which can be used to modify the polymers A are added to the monomer mixture from (a) to (e) in amounts of up to 10% by weight .-%, preferably up to 5 wt .-% added.

The polymers A can be prepared by conventional methods of radical polymerization. The techniques of suspension, solution and bulk polymerization can be used in particular. Organic solvents such as toluene, xylene, ethylbenzene, isopropylbenzene, tetrahydrofuran, dioxane, cyclohexane, petroleum ether or ligroin can be used, for example, as diluents or solvents for the polymerization. One works at normal pressure or under increased pressure. Suitable radical initiator systems are all which form free radicals under the desired polymerization conditions, for example di-tert-butyl peroxide, tert-butyl perbenzoate or tert-butyl perethyl hexanoate. Protective colloids, such as polyethyleneyl ether, can be added, particularly in the case of suspension polymerization.

The K values of the polymers A are generally between 6 and 200, in particular between 8 and 100. According to Fikentscher, the K values of the copolymers were determined on 1% by weight solutions in cyclohexanone and the K Values of the homopolymers (a) determined in dimethylformamide as solvent at 25 ° C.

After the polymerization, the polymers A can be isolated in solid form and, if desired, dried and then reacted with component B. However, the polymers A can also be reacted directly with component B in solution. Primary, secondary and tertiary alcohols having 1 to 30 carbon atoms are to be mentioned as suitable alcohols for component B for the reaction with the polymers A. Saturated aliphatic alcohols as well as unsaturated alcohols, such as oleyl alcohol, can be used. Primary or secondary alcohols are preferably used, for example amyl alcohol, n-hexanol, n-octanol, 2-ethylhexanol, n-nonanol, iso-nonanol, n-decanol, n-dodecanol, n-tridecanol, iso -Tridecanol, cyclohexanol, naturally occurring fatty alcohols such as tallow fatty alcohol or stearyl alcohol as well as the alcohols or alcohol mixtures with 9 to 19 C atoms which are technically easily accessible through oxosynthesis, such as Cg _/ io-oxoalcohol, Ci _{3 /} i ₅ - Oxo alcohol and Ziegleral alcohols with 12 to 24 carbon atoms, for example Cj _{.2 /} ι - or Ci _{6 /} i ₈ ~ cuts.

The alcohols of component B can also be oxyalkylated, ie have been reacted with a C ₂ -C ₄ -alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide. One or two different alkylene oxide blocks can be present in the molecule. Tetramethylene can also be present as a polytetrahydrofuran structure as an alkylene building block for such a block.

Also suitable as alcohols of component B are ether alcohols and polyether diols such as ethylene glycol monobutyl ether, di- and triethylene glycol monobutyl ether, polytetrahydrofuran as well as polyethylene glycols and polypropylene glycols.

In a preferred embodiment, as component B in the preparation of the reaction products used according to the invention, alcohols in which the radical R ^{6 is} Cχχ to C ₂₂ alkyl or Cio to C ₂₂ alkenyl, m and n each have a number of 2 to 4 mean and p and q each denote a number from 0 to 35, used.

As suitable for reaction with the polymers A primary or secondary amines of component B are, for example, n-hexylamine, cyclohexylamine, methylcyclohexylamine, 2-ethylhexylamine _r ri-octyl amine, n-tridecylamine, isotridecylamine, tallow fatty amine, stearylamine, oleylamine, di-n -Hexylamine, dicyclohexylamine, di- (methylcyclohexyl) amine _r di- (2-ethylhexyl) amine, di- (n-octyl) amine, di- (isotride-cyl) amine, di-tallow fatty amine, di-stearylamine To name diolelylamine, diethanolamine, di-n-propanolamine or di-iso-propanolamine.

In a preferred embodiment, as components B in the preparation of the reaction products used according to the invention, amines in which the radical R ^{4 is} hydrogen and the radical R ⁵ , Cio- to C ₂ 2-alkyl or Cio- to C ₂ 2-alkenyl referred to.

The polymers A are reacted with the amines or alcohols B by known methods. As a rule, carboxylic acid ester or carboxamide functions are incorporated into the polymers A. Amines are expediently used with the polymers A in bulk or in inert organic solvents such as toluene, xylene, cyclohexane, petroleum ether or ligroin, which usually result from the preparation of the polymers A themselves, under normal pressure or elevated pressure at about 60 to 130 ° C implemented. The reaction of the alcohols with the polymers A is also advantageously carried out in bulk or, preferably, in inert organic solvents, as mentioned above, in the presence of acidic catalysts such as p-toluenesulfonic acid under normal pressure or elevated pressure at about 100 to 150 ° C. .

The ratio of components A and B in the reaction is usually chosen so that 0.2 to 1.0 mol of amine or alcohol B or a mixture thereof is used per mole of monomer a) in polymer A.

After the reaction of components A and B, any organic solvent which is present is generally removed, preferably by distillation, and the product is usually dispersed in an aqueous solution of a base, preferably an alkali metal hydroxide such as sodium or potassium hydroxide or ammonia. in order to partially or completely hydrolyze the remaining anhydride functions of the partially esterified or partially amidated polymers and to partially or completely neutralize them.

The polymer dispersions obtainable in this way are suitable for the treatment of all customary tanned hides. The tanned hides are usually deacidified before treatment. They may have been stained before the treatment. Coloring can, however, only be carried out after the greasing according to the invention.

The tanned skins are expediently mixed with the aqueous dispersions in an aqueous liquor at pH values from 4 to 10, preferably from 5 to 8, and temperatures from 20 to 60 ° C., preferably 30 to 50 ° C., during a period of 0.1 to 5 hours, in particular 0.5 to 2 hours, treated. This treatment takes place, for example, by walking in a barrel. The amount of reaction product from A and B required, based on the shaved weight of the leather or the wet weight of the fur skins, is 0.1 to 30% by weight, preferably 1 to 20% by weight. The liquor length, ie 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 IQ to 1000%, preferably 30 to 150%, and 50 to 500% for fur skins. The dispersions of the reaction products from A and B used generally have no additional emulsifiers.

After treatment with the aqueous liquor described, the pH of the treatment liquor is adjusted to a pH of 3 to 5, preferably 3.5 to 4, by adding acids, preferably organic acids such as formic acid.

If conventional retanning agents are also used in the finishing process of the leather and fur skins, treatment with the reaction products from A and B to be used according to the invention can take place before or after the retanning step.

The present invention furthermore relates to leather treatment compositions which are reaction products of

(b) 0 to 70 mol% of one or more vinyl aromatics of the general formula I

in which R ¹ , R ² and R ^{3 are} hydrogen, methyl or ethyl and k is 1 or 2,

(c) 0 to 70 mol% of one or more vinyl esters of Ci to Cβ carboxylic acids,

(d) 0 to 50 mol% of one or more C ₂ to Ce olefins and (e) 0 to 30 mol% of one or more monoethylenically unsaturated C ₃ to Cs carboxylic acids,

wherein up to 10% by weight of further copolymerizable monomers can be added to the monomer mixture from (a) to (e) with

B) amines of the general formula R ⁴ R ⁵ NH, in which R ^{4 is} hydrogen,

CT.- to C ₂ o-alkyl, C ₅ - to C ₈ -cycloalkyl or C ₂ - to C ₄ -hydroxyalkyl and R ⁵ Cζ- to C ₃ o-alkyl, Cζ- to C ₃₀ -alkenyl, C ₅ - to Cβ-Cycloalkyl or C ₂ - to C -hydroxyalkyl, or alcohols of the general formula R ⁶ -0- (C _m H _2m O) _p - (C _n H _2n O) _q -H, in which R ⁶ represents Cj.- to C ₃ o-alkyl, C ₂ - to C ₃ o ~ alkenyl, C ₅ - to Cβ-cycloalkyl or in the case p + q> 0 represents hydrogen, m and n each have a number from 2 to 4 mean and p and q each denote a number from 0 to 50, or mixtures of such amines and alcohols

contain.

With the reaction products to be used according to the invention, it is possible to produce very soft leather without the addition of conventional licker. This advantage is reflected in simple and short application formulations.

In addition to an improvement in the mechanical properties such as tear strength, these polymeric greasing agents bring about a significant increase in the fastness profile of the leather. The light fastness and heat yellowing resistance of such leathers are influenced very positively. In addition to the practically quantitative exhaustion of the liquor, the good fixation in the leather causes great resistance to the extractability with solvent or water. This leads to so-called washable leathers, i.e. Leather that does not lose its properties such as softness, strength and suppleness after washing, in contrast to leather that has been greased with conventional leathers.

The hydrophobic properties of these polymeric greasing agents can be varied so that the leather can also be given a certain water resistance by suitable selection from the special alcohols and amines of component B in the reaction products used according to the invention.

Another advantage of the reaction products used according to the invention is that dispersions made from them do not require any additional emulsifiers when applied to leather or fur skins. Leather and furs made with emulsifier Products that have been treated in many cases have to be subjected to complex processes, such as aftertreatment with polyvalent metal salts, after treatment with these agents in order to render the emulsifiers in the leather or in the fur skins ineffective.

Examples

The percentages in the examples relate to the weight, unless stated otherwise. The molecular weights of the copolymers were determined by gel permeation chromatography, using tetrahydrofuran as eluent and narrowly distributed fractions of polystyrene for calibration. The K values according to Fikentscher of the copolymers and of the auxiliaries were determined in 1% strength by weight solutions in cyclohexanone at 25 ° C. In the homopolymers of monomers (a), dimethylformamide was used as the solvent instead of cyclohexanone.

Preparation of the polymers A

example 1

In a heatable reactor, which was provided with a stirrer, reflux condenser, thermometer, inlet devices, nitrogen inlet and outlet, 1600 g of technical xylene, 392 g (4.0 mol) of maleic anhydride and 7 g of polyethylvinyl ether with a K value of 50 to Boiling heated and within 2 hours 344 g (4.0 mol) of vinyl acetate and a solution of 4 g of di-tert-butyl peroxide in 200 g of technical xylene were metered in uniformly under boiling conditions. The mixture was then stirred under reflux for a further hour, cooled and the polymer in the form of a fine suspension was filtered off and the filter cake was dried at 80 ° C. in vacuo. The K value of the copolymer in the form of a white powder was 15.9 and the molar mass was 7000.

Example 2

In a reactor as in Example 1, 1960 g of o-xylene, 441 g (4.5 mol) of maleic anhydride and 45 g of polyvinyl vinyl ether with a K value of 50 were heated to boiling and within 3 hours, 468 g (4, 5 mol) of styrene and a solution of 18.2 g of tert-butyl perbenzoate in 162 g of o-xylene were metered in evenly while boiling. The mixture was then heated for a further 2 hours and then cooled. The K value of the polymer obtained was 14.6, the molar mass was 5000. The light brown, fine suspension with With a polymer content of 29.5%, it could be processed directly into a leather greasing agent.

Example 3

The preparation is carried out analogously to Example 2, except that 264.6 g (2.7 mol) of maleic anhydride and 655.2 g (6.3 mol) of styrene were used. The K value of the polymer obtained was 16.0 and the molar mass was 9000. The fine, light brown polymer suspension could be further processed directly to give a leather greasing agent.

Example 4

In a reactor as in Example 1, 1750 g of maleic anhydride and 1165 g of o-xylene were heated to boiling and within

A solution of 262 g of tert-butyl perethylhexanoate in 190 g of o-xylene was metered in uniformly for 5 hours while boiling. Subsequently, the mixture was heated for another hour and then the o-xylene was decanted off over the melt, the melt was applied to an aluminum sheet and cooled. The resin was crushed and the remaining solvent was distilled off in vacuo. The polymer had a K value of 10 and the molar mass was 1000.

Example 5

In a pressure reactor with structures as described in Example 1, 1210 g of o-xylene, 636 g (6.5 mol) of maleic anhydride and

6 g of polyvinyl vinyl ether with a K value of 50 presented. The reactor was tightly sealed, pressed three times with 3 bar of nitrogen each time and relaxed again, evacuated and heated to 120 ° C. 364 g (6.5 mol) of isobutene and a solution of 30 g of tert-butyl perethylhexanoate in 250 g of o-xylene were then metered in uniformly at 120 ° C. in the course of 4 hours. The mixture was then reheated at 120 ° C. for 2 hours. Then the pressure built up of 3 bar was released and the reactor was cooled. The viscous, fine-grained suspension of the copolymer was freed from the solvent in vacuo at 80 ° C. The copolymer obtained was a fine powder with a K value of 25 and its molar mass was 8000.

Preparation of the dispersions of the reaction products from A and B.

The reaction products from polymers A and amines B were prepared by adding the amines given in the table to the polymers shown in the table in xylene at 120 to 130 ° C. in the molar ratio A in: maleic anhydride (MA) in the polymer shown in the table . After distilling After the reaction, the product was dispersed in the polymer with an Ultraturax stirrer in aqueous sodium hydroxide solution in the molar ratio NaOHrMSA given in the table, so that a 20 to 25% dispersion with a pH value from 7 to 8 resulted.

The reaction products were prepared from polymers A and alcohols B by reacting the alcohols listed in the table with the polymers listed in the table in xylene at 120 to 130 ° C. in the presence of catalytic amounts of p-toluenesulfonic acid for 3 to 5 Hours in the molar ratio alcohol: MA given in the table in the polymer. After the xylene had been distilled off after the reaction had taken place, the product was dispersed in the polymer using an Ultaturax stirrer in aqueous sodium hydroxide solution in the molar ratio NaOHrMSA given in the table, so that a 20 to 25% dispersion with a pH from 7 to 8 resulted.

table

Dispersions of the reaction products from A and B.

Annotation:

C ₄ H ₈ 0 in Examples 14, 15, 17, 18 and 19 denotes oxybutylene, obtained by reacting methanol with butylene oxide

Examples of use

Example 21

Chrome-tanned cowhide with a fold thickness of 1.8 mm, which had been deacidified to a pH of 5.0, was drummed with 15% of the product from Example 6, based on the fold weight, in a tanning drum at 40 ° C. for 2 hours. The total fleet length was 150%. The leather was then dyed with 1% of a common anionic aniline dye. After that, it was adjusted to pH with formic acid. set from 3.8. It was finally washed, mechanically stretched and dried. The leather obtained was very soft, supple, well filled and evenly colored. Example 22

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 based on 20% of the product from Example 7 the fold weight,

Tumbled for 1.5 hours at 40 ° C in a tanning barrel. Following this treatment, the leather was adjusted to a pH of. With formic acid

3.6 brought and completed as usual. The leather thus obtained was very soft and easy to grip.

Example 23

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 based on 15% of the product from Example 8 the fold weight, drummed for 30 minutes at 40 ° C. in the tanning drum and then treated further with 3% of a conventional synthetic tanning agent for one hour. 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.

Example 24

The product of Example ^"9 was used as per the Example 21 an¬ given operation. The leather thus obtained had soft and round hand properties.

Example 25

The product from Example 10 was used analogously to the procedure given in Example 23. The leather thus obtained was characterized by a round, soft handle.

Examples 26 to 28

The products from Examples 11 to 13 were used analogously to the procedure given in Example 22. The results were similarly advantageous as in the previous examples.

Examples 29-33

The products from Examples 14 to 18 were used analogously to the procedure given in Example 21. The results were similarly advantageous as in the previous examples. Examples 34 and 35

The products from Examples 19 and 20 were used analogously to the procedure given in Example 23. The results were similarly advantageous as in the previous examples.

Claims

1. Use of implementation products from

A) Homopolymers or copolymers based on monoethylenically unsaturated dicarboxylic acid anhydrides, obtainable by radically initiated polymerization of

(a) 30 to 100 mol% of one or more monoethylenically unsaturated dicarboxylic anhydrides having 4 to 10 carbon atoms,

(b) 0 to 70 mol% of one or more vinyl aromatics of the general formula I

in which R ¹ , R ² and R ^{3 are} hydrogen, methyl or ethyl and k is 1 or 2,

(c) 0 to 70 mol% of one or more vinyl esters of Ci to C ₈ carboxylic acids,

(d) 0 to 50 mol% of one or more C ₂ to Cg olefins and

where up to 10% by weight of further copolymerizable monomers can be added to the monomer mixture from (a) to (e) with

B) Amines of the general formula R ⁴ R ⁵ NH, in which R ^{4 is} hydrogen, C 1 to C ₂ o-alkyl, C ₅ to C ₈ cycloalkyl or

C ₂ - to C -hydroxyalkyl and R ⁵ C _ß - to C ₃ o-alkyl, Cg- to Cjo-alkenyl, C ₅ - to C ₈ -cycloalkyl or C ₂ - to C ₄ -hydroxyalkyl, or alcohols of the general formula R ⁶ -0- (C _m H _2m O) _p - (C _n H _2n O) qH, in which R ^{6 is} for C ₁ -C ₃ -alkyl, C ₂ - to C ₃ o-alkenyl, C ₅ - to C ₈ cycloalkyl or for the

If p + q> 0 represents hydrogen, m and n each represent a number from 2 to 4 and p and q each represent a number denote from 0 to 50, or mixtures of such amines and alcohols

for greasing and filling leather and fur skins.

2. Use of reaction products according to claim 1, in the production of which as component A a homopolymer of a monoethylenically unsaturated dicarboxylic acid anhydride having 4 to 10 carbon atoms (a) was used for the greasing and filling of leather and fur skins.

3. Use of reaction products according to claim 1, in the preparation of which as component A is a copolymer

(b) 1 to 70 mol% of one or more vinyl aromatics I

was used for greasing and filling leather and fur skins.

4. Use of reaction products according to claim 1, in the preparation of which as component A, a copolymer

(c) 1 to 70 mol% of one or more vinyl esters of CT. to C ₈ carboxylic acids

was used for greasing and filling leather and fur skins.

5. Use of reaction products according to claim 1, in the preparation of which as component A is a copolymer

(a) 50 to 99 mol% of a monoethylenically unsaturated dicarboxylic anhydride with 4 to 10 carbon atoms and

(d) 1 to 50 mol% of one or more C ₂ to Ce olefins

was used for greasing and filling leather and fur skins.

6. Use of implementation products according to claims 1 to

5, in whose production maleic anhydride was used as monomer (a) for the polymer A, for greasing and filling leather and fur skins.

7. Use of reaction products according to claims 1 to

6, in the production of which amines were used as component B, in which the radical R ^{4 is} hydrogen and the radical R ^{5 is} Cχo ~ to C ₂₂ -alkyl or Cio- to C ₂₂ ~ alkenyl, for greasing and filling leather and fur files.

8. Use of reaction products according to claims 1 to 6, in the preparation of which, as component B, alcohols have been used in which the radical R ^{6 is} C 1 -C ₂₂ -alkyl or C 1 -C ₂₂ -alkenyl, m and n each represent a number from 2 to 4 and p and q each denote a number from 0 to 35, for greasing and filling leather and fur skins.

9. Process for greasing and filling leather and fur, characterized in that reaction products according to claims 1 to 8 are used for this.

10. Leather treatment agent containing reaction products of

(a) 30 to 100 mol% of one or more monoethylenically unsaturated dicarboxylic acid anhydrides with 4 to 10 carbon atoms

Atoms,

(b) 0 to 70 mol% of one or more vinyl aromatics of the general formula I

, R ² and R ³ is hydrogen, methyl or ethyl and k is 1 or ^2: in which R

(c) 0 to 70 mol% of one or more vinyl esters of

Cι ~ to Cg carboxylic acids, (d) 0 to 50 mol% of one or more C ₂ - to Cβ-olefins and

Amines of the general formula R ⁴ R ⁵ NH, in which R ⁴ is hydrogen, C ₁ -C ₂ -alkyl, C ₅ -C ₈ -cycloalkyl or C ₂ -C ₄ -hydroxyalkyl and R ⁵ Cς-C ₃₀ -alkyl, Cζ- to C ₃ o-alkenyl, C5- to C ₈ -cycloalkyl or C ₂ - to C ₄ -hydroxyalkyl, or alcohols of the general formula R ⁶ -0- (C _m H ₂ mO) p- (C _n H _2rι O) qH, in which R ⁶ for C - to C ₃₀ -alkyl, C ₂ - to C ₃ o-alkenyl, C5- to C ₈ -cycloalkyl or in the case p + q> 0 represents hydrogen, m and n each represent a number from 2 to 4 and p and q each denote a number from 0 to 50, or mixtures of such amines and alcohols.