EP1623047A1

EP1623047A1 - Lubricant for the production and treatment of leather

Info

Publication number: EP1623047A1
Application number: EP04731175A
Authority: EP
Inventors: Ralph Lunkwitz; Andreas Seitz
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2003-05-06
Filing date: 2004-05-05
Publication date: 2006-02-08
Also published as: WO2004099449A1; BRPI0410065A; US7300599B2; DE10320110A1; CN1802442A; US20070021552A1

Abstract

Disclosed is a lubricant for producing and/or treating leather, comprising (A) at least one native lipoid, (B) at least one polymer based on the monomers acrylic acid and/or methacrylic acid, and (C) an emulsifier composition containing a C6 to C17 alkanol that is alkoxylated with up to 12 alkylene oxide units or a mixture of two or more such alkenols and a C12 to C24 fatty alcohol mixture which is alkoxylated with at least 15 alkylene oxide units.

Description

Lubricant for the manufacture and treatment of leather

The present invention relates to a composition which contains native lipoid, synthetic polymer and a specific mixture of various alkoxylated alkanols and can preferably be used both in the production and treatment of leather, and the use of this fatliquor in the production and / or treatment of leather. The present invention also relates to a method for greasing leather using the composition according to the invention. The present invention further describes the use of a special emulsifier composition for the production and / or treatment of leather and for the production of a fatliquor for the production and / or treatment of leather.

Greasing agents are used in leather production to soften the leather, to increase its fullness and strength and to protect it from moisture, dirt and chemical influences from outside (see H. Herfeld, "Library of Leather", Vol. 4, (1985), p. 13 ff.). Commercial greasing agents are products which generally consist of chemically modified native fats, oils, waxes, resins and their derivatives and / or petroleum fractions and their secondary products (see H. Herfeld, "Library of Leather", Vol. 4, (1985), pp. 59 ff.).

In particular, high-quality leather such as car upholstery leather has to meet certain criteria. On the one hand the softness is essential, on the other hand the authenticity to light and heat influences and finally the so-called fogging behavior. DIN 75201 defines fogging as condensation of evaporated volatile components from the vehicle interior on the glass panes, especially on the windshield. The same standard also describes a gravimetric and a reflectometric method for characterizing the fogging behavior of leather.

EP 0 498 634 A2 recommends special polymers for the production of so-called low-fogging leather, the aqueous dispersions being essentially free of organic solvents and containing an amphiphilic copolymer which consists of a predominant proportion of at least one hydrophobic monomer and a small proportion of at least one hydrophilic monomer. Treatment of the leather with these dispersions leads to a gravimetric test according to DES. 75201 to good results. Reflectometric studies have not been disclosed. These amphiphilic copolymers are preferably prepared in an aqueous emulsion polymerization. However, due to the different hydrophilicity of the monomers to be used, this naturally leads to problems in the copolymerization behavior, which in extreme cases can lead to the monomers each forming homopolymers in an undesirable manner. Another consequence of the inherently unfavorable solution conditions is a time-consuming post-processing to destroy residual monomers. In order to achieve good emulsion stability, it is also necessary to add a sufficient amount of an emulsifier (lauryl sulfate was used in the examples given), which can lead to wastewater problems in leather processing.

EP 0466 392 B1 describes a process for the preparation of polymers which contain both pendant hydrophobic groups and pendant alkoxylated groups and which are obtained by derivatizing polymers after the actual polymerization process using customary processes. For example, polymers are preferably produced from simple monomers such as acrylamide and / or acrylic acid by conventional polymerization and then derivatized with a mixture of primary or hydrophobic amines and primary or secondary alkoxylated amines. Such derivatized polymers are used as thickeners and soil release agents.

EP 0 927 271 B1 describes a further process for the preparation of polymers which are obtained by polymerizing acrylic acid and / or methacrylic acid and / or their acid chlorides and / or their anhydrides with further copolymerizable water-soluble monomers and with copolymerizable water-insoluble monomers and subsequently Implementation of the polymers with amines are shown. According to DEM 75201 B (gravimetry), 1.2 mg and 1.5 mg are listed for leather that has been treated with the listed sample products; the leather treated with the comparative products (Magnopal SOF, low-fogging polymer greasing agent, and Chromopol LFC, low-fogging greasing agent based on fish oils, both Stockhausen GmbH & Co. KG) achieved values of 3.9 mg and, respectively, 3.5 mg. The reflectometric values according to DEM 75201 A of the sample products are 51% and 55%, those of the comparison products are 34% and 40%.

A process is described in US Pat. No. 5,348,807 in which selected amphiphilic copolymers are used as solvent-free, low-fogging fatliquors. In addition to these polymers, EP 0 753 585 A2 describes a low-fogging surface treatment for furniture leather and a process in which a specially treated virgin oil acts as the basis for greasing agents. Native oils used are soybean, lard, safflower and sunflower oil. After distillation, these oils with a fatty acid content (<C ₁₆ ) of less than 3% are reacted with bisulfite or bisulfate, emulsified and used.

For ecological reasons, there is also a growing demand for high-fat lipids. The fat must be completely absorbed by the collagen. In wet blue semi-finished products, the mostly anionic fatliquor is fixed by the C_nom (E __) cations. In wet white semi-finished products that are manufactured without cationic metal salts, these binding sites are therefore missing. As a result, using commercially available fatliquors made according to the state of the art, the bath consumption is poor, i.e. the remaining fleet has a high COD value. According to the prior art, chemical modification of the greasing agent improves the bath consumption, which is usually done by depositing the greasing components on the leather surface. As a result, the connections are not fixed in the leather, which leads to leathers with high fogging values according to DEM 75201.

All of the described prior art methods have in common that they either describe polymers or fatliquors on a native basis and that these products are special classes of substances. In addition, all of these processes ignore the environmental aspect with regard to very good fleet wastage.

DE 101 43 949 AI describes a fatliquor mixture which contains a combination of a chemically modified native fatliquoring component or, alternatively, a polymeric component with a special emulsifier combination and which is characterized by excellent leather properties and excellent liquor consumption. This composition is also characterized by a relatively high viscosity, which is of great advantage for practical use in the tannery and is therefore a desirable property of leather greasing agents.

One object underlying the present invention was to provide a fatliquor which avoids the disadvantages of the known fatliquors and in particular the favorable product properties of synthetic-polymeric and native fatliquor additives. components, which is expressed, among other things, by the softness of the leather with simultaneous firm grain and good fullness, especially in the case of chrome-free tanned leather. The product should also be able to meet the fogging limit values required by the market.

Accordingly, the present invention relates to a fatliquor for the manufacture and / or treatment of leather containing

(A) at least one native lipoid; (B) at least one polymer based on the monomers acrylic acid and / or methacrylic acid; (C) an emulsifier composition comprising a C ₆ to C ₁₇ alkanol alkoxylated with up to 12 alkylene oxide units or a mixture of two or more such alkanols and a C ₁₂ to C ₂₄ fatty alcohol mixture alkoxylated with at least 15 alkylene oxide units ,

In general, there are no particular restrictions with regard to the native lipoid, as long as the desired product properties can be adjusted with it. Fats, fatty oils, waxes and phospholipids can in principle be used as native lipoids.

In the context of the present invention, preference is given to using, inter alia, phospholipoids - which are known to be phosphoric acid diesters - in which the phosphoric acid can be esterified on the one hand with glycerol or sphingosine and on the other hand with choline, colamine, serine or inositol.

In the context of the present invention, preference is likewise given to using, as native lipoids, inter alia native fats or fatty oils which can be of vegetable or animal origin. Glycerides of natural fatty acids with a sufficient proportion of unsaturated acids may be mentioned in particular.

The mentioned native fats or fatty oils and the phospholipoids can each be present alone or as a mixture. It is thus possible to use a phospholipoid or a mixture of two or more phospholipoids or a fat or fatty oil or a mixture of two or more fats or fatty oils. A mixture of at least one phospholipoid and at least one fat or fatty oil can also be used. Before- In the context of the present invention, a mixture of at least one native oil and at least one native phospholipoid is used.

In general, the at least one native oil and the at least one native phospholipoid can be used as such. It is also possible, for example, to use at least one native oil or at least one native phospholipoid or both at least one native oil and at least one native phospholipoid in a chemically modified manner.

According to a preferred embodiment, lipoid mixtures are used in which each of the native oils and each of the native phospholipoids are chemically modified.

Accordingly, the present invention also describes a fatliquor as described above, which is characterized in that it contains a mixture as at least one chemically modified, native lipoid

(Aa) at least one chemically modified, native oil and

(Ab) at least one chemically modified, native phospholipoid

contains.

With regard to this mixture according to the invention of chemically modified, native oil and chemically modified, native phospholipoid, there are no particular restrictions with regard to the proportion of the mixture or of the fatliquor in the individual compounds.

In general, the mixture according to (A) has a proportion of the at least one chemically modified, native oil in the range from 20 to 50% by weight, preferably in the range from 25 to 45% by weight and particularly preferably in the range from 30 to 40% by weight, based in each case on the total weight of the mixture (A).

With regard to the at least one chemically modified, native phospholipoid, the mixture according to (A) generally has a proportion in the range from 50 to 80% by weight, preferably in the range from 55 to 75% by weight and particularly preferably in the range from 60 to 70% by weight. Accordingly, the present invention also relates to a fatliquor, as described above, which is characterized in that it contains component (Aa) in a range from 20 to 50% by weight and component (Ab) in a range from 50 to 80 wt .-%, each based on the total weight of component (A) contains.

As far as the at least one chemically modified native oil according to (Aa) used as described above is concerned, there are essentially no restrictions on the type of oil and the chemical modification, as long as the desired product properties can be achieved. Preference is given to native oils which have an iodine number of from approximately 10 to approximately 200. Native oils with a low iodine number in the range mentioned are, for example, stearin or tung oil, native oils with a high iodine number in the range mentioned are, for example, the fish oils or the Chaulmoogra oil.

Native oils with an iodine number in the range from 10 to 200, preferably in the range from 30 to 120 and particularly preferably in the range from 40 to 85 are preferably used in the fatliquor according to the invention.

Examples of further particularly preferred native oils are, for example, fish oil, bone oil, nitro oil, claw oil, lard oil, soybean oil, rape oil, nut oil, olive oil, triolein or castor oil.

As already described above, these native oils are suitably chemically modified in the context of the present invention. In general, this chemical modification consists in the fact that the C-C double bonds contained in the native oils have at least partially been subjected to addition and / or oxidation reactions. The native oils are preferably modified by adding sulfites to the double bonds, thereby introducing sulfonic acid groups. Also preferably, oxygen functions can be introduced by air oxidation or oligomerizations can occur. Hydrolysis or partial hydrolysis of the native oils, transesterifications or similar reactions are also preferably possible as a chemical modification.

Modified native oils which have a relatively high degree of oxidation and a relatively low degree of sulfation are particularly advantageous in the context of the fatliquor according to the invention, the chemically modified oils being formed by reaction of the olefinic double bonds present in the oils with the oxidation and / or the sulfi - Formation reagents. In particular, all of the oils present in the which olefinic double bonds or only a part thereof react with the oxidation and / or the sulfitation reagents.

Air is preferably used as the oxidation reagent, the reaction with the olefinic double bonds present in the native oils being carried out at temperatures, for example preferably in the range from 60 to 80.degree. The oxidation can also be carried out in accordance with other types known to the person skilled in the art. The term “relatively high degree of oxidation” as used in the context of the present application denotes a degree of oxidation of the native oils, on the basis of which the difference in the specific weights of the oil before and after the oxidation, Δd, generally in the range from 0.01 to 0.1 g / ml, preferably in the range from 0.01 to 0.07 g / ml and particularly preferably in the range from 0.02 to 0.05 g / ml.

The sulfitation mentioned above is generally carried out by reacting the native oil with aqueous bisulfite liquor. It can also be carried out according to other methods known to those skilled in the art. The term “relatively low degree of sulfitation”, as used in the context of the present application, denotes a degree of sulfitation of the native oils which results from a reaction of the native oil with generally 2 to 8% by weight and preferably 3 to 5% by weight. Sulfite, calculated as sodium bisulfite (Na ₂ S ₂ Os) and based on the weight of the native oil, results.

A very particularly preferred chemically modified, native oil is an oxidized and sulfated oil as described above, selected from the group consisting of fish oil, claw oil, lard oil, soybean oil, rapeseed oil, nut oil, olive oil and castor oil, is used in the fatliquor according to the invention, further preferably used as chemically modified, virgin oil oxidized and sulfated rapeseed oil.

Accordingly, the present invention also relates to a fatliquor, as described above, which is characterized in that a chemically modified, native oil according to (Aa) is sulfated rapeseed oil.

According to a very particularly preferred embodiment of the fatliquor according to the invention, oxidized, sulfated rapeseed oil is used as the only chemically modified, native oil according to (Aa). Examples of particularly preferred phospholipoids are lecithin and cephalin, it being possible, as described above, to use, for example, chemically unmodified lecithin or chemically unmodified cephalin.

Accordingly, the present invention also describes a fatliquor as described above, which is characterized in that a native phospholipoid is chemically unmodified lecithin.

Modified phospholipoids which are partially acetylated, in which an esterified fatty acid has been partially replaced by esterified acetic acid in accordance with methods known to the person skilled in the art are further preferred. This partial transesterification allows the viscosity and the hydrophilicity of the modified phospholipoid to be adjusted. Acetylated lecithin is used as a particularly preferred modified phospholipoid in the context of the present invention.

The degree of acetylation of the modified phospholipoid is generally in the range from up to 60%, preferably in the range up to 50%, particularly preferably in the range from 30 to 50% and particularly preferably in the range from 35 to 45%.

Accordingly, the present invention also relates to a fatliquor, as described above, which is characterized in that a chemically modified, native phospholipoid is acetylated lecithin.

As far as the at least one polymer based on the monomers acrylic acid and / or methacrylic acid is concerned, there are no particular restrictions in this regard as long as the desired product property can be achieved therewith.

The polymer used according to the invention and based on the monomers acrylic acid and / or methacrylic acid generally has a molecular weight Mw in the range from 2,500 to 150,000 g / mol, preferably in the range from 5,000 to 130,000 g / mol, more preferably in the range from 10,000 to 110,000 g / mol, further particularly preferably in the range from 25,000 to 100,000 g / mol and particularly preferably in the range from 50,000 to 90,000 g / mol.

The polymer is further preferably used in the process according to the invention as an aqueous solution or dispersion of at least one salt of the polymer. Accordingly, at least one carboxyl group of the polymer used according to the invention is present as a salt, the preferred cations of this salt being monovalent ions such as, for example, the alkali metal ions such as lithium, sodium, potassium, rubidium or cesium or an ammonium ion, NH ₄ ⁺ or, for example, as ammonium ion a suitable mono-, di-, tri- or tetraalkylammonium ion can also be used.

The polymer salt used according to the invention can have, for example, one or more different of the cations mentioned above. In the event that two or more different polymers are used, the different polymers can independently of one another have a single or two or more different cations mentioned above.

According to a particularly preferred embodiment of the composition according to the invention, the at least one polymer is used as the sodium salt.

If, according to a preferred embodiment, an acrylic acid homopolymer is used, it is generally in the range from 20 to 80%, preferably in the range from 30 to 70% and particularly preferably in the range from 40 to 60% of the carboxyl groups of the polymer as salt, particularly preferably as the sodium salt.

If, according to a further preferred embodiment, a methacrylic acid homopolymer is used, it is generally in the range from 5 to 60%, preferably in the range from 10 to 50% and particularly preferably in the range from 20 to 40% of the carboxyl groups of the polymer as salt, particularly preferably as the sodium salt.

In the context of the present invention, preference is given to using homopolymers made from acrylic acid monomers and homopolymers made from methacrylic acid monomers, with more preference being given to using homopolymers made from acrylic acid monomers.

Accordingly, the present invention also describes a fatliquor as described above, which is characterized in that a polymer according to (B) is a polyacrylic acid. Accordingly, the present invention also relates to a fatliquor, as described above, which is characterized in that the at least one polymer according to (B) is a polyacrylic acid with a molecular weight in the range from 2,500 to 150,000 g / mol.

Mixtures of two or more polyacrylic acids can also be used in the context of the present invention, the molecular weights of the different polyacrylic acids being in the abovementioned ranges. Accordingly, for example, polyacrylic acid mixtures are conceivable in which a polyacrylic acid has a molecular weight M _w in the range from 2,500 to 70,000 g / mol or 5,000 to 50,000 g / mol or 10,000 to 25,000 g / mol and another polyacrylic acid has a molecular weight Mw in the range from 70,000 to 150,000 g / mol or 90,000 to 130,000 g / mol or 100,000 to 110,000 g / mol. Mixtures of three or more polyacrylic acids with different molecular weights are also conceivable.

Mixtures of at least one acrylic acid homopolymer and at least one methacrylic acid homopolymer can also be used in the composition according to the invention, the individual different homopolymers each being able to have different molecular weights independently of one another.

Instead of or in addition to the homopolymers described above, copolymers of acrylic acid and methacrylic acid can also be used according to the invention. Instead of acrylic acid or methacrylic acid, other ethylenically unsaturated monomers such as itacenic acid, fumaric acid, maleic acid or their anhydrides can be used as comonomer. It is also possible to use suitable acidic or basic substituted acrylates or methacrylates. Terpolymers of acrylic acid, methacrylic acid and one of the other monomers mentioned above can also be used, for example.

As already described above, the polymers are preferably used according to the invention as an aqueous solution or dispersion. Depending on the polymer or polymer mixture, it is possible here for at least one polymer to be dissolved in the aqueous mixture and for at least one further polymer to be dispersed.

The aqueous solution or dispersion generally contains the polymer in a proportion in the range from 5 to 40% by weight, preferably in the range from 10 to 40% by weight, further preferably in the range from 20 to 40% by weight. and particularly preferably in the range from 25 to 35% by weight, based in each case on the total weight of the aqueous solution or the aqueous dispersion.

In addition to water, the aqueous solution or dispersion can contain at least one solubilizer or at least one further solvent or both at least one solubilizer or at least one further solvent. Examples of solvents which may be mentioned are glycols, diethylene glycol, dipropylene glycol, butyl diglycol, hexylene glycol or oligoethylene glycols having 3 to 7 ethylene units being further preferred.

As far as the emulsifier composition according to (C) is concerned, there are essentially no restrictions with regard to the individual alkanols and the fatty alcohols.

The alkylene oxide units are generally alkylene oxide units with at least 2 C atoms, preferably with 2 to 4 C atoms and particularly preferably with 2 to 3 C atoms. Ethylene oxide units are particularly preferred. The alkylene oxide units of the respective polyether chains can be the same or different. In the latter case, the alkylene oxide units can be arranged randomly or in blocks or partially in blocks.

The alkoxylated alkanols or fatty alcohols used according to the invention are generally obtained from the reaction of the corresponding alkanols or from mixtures of two or more thereof or fatty alcohols or from mixtures of two or more thereof with the desired molar amounts of the alkylene oxides, such as ethylene oxide, propylene oxide or Obtain butylene oxide. Depending on how the alkylene oxides are metered into the batches, statistical or block-like or both statistical and block-like polyether chains can be produced in a targeted manner. Such reactions can be catalyzed, for example, by small amounts of water and / or additions of alkali.

The emulsifier compositions according to the invention are generally prepared by mixing the components with stirring and optionally with gentle heating, whereupon the finished emulsifier mixture is used to produce the greasing agent according to the invention.

The emulsifier composition can, if appropriate, be converted into a solution by adding water, for example preferably having a solids content in the range from about 40 to about 80% by weight based on the total weight of the emulsifier composition. Other concentrations of the emulsifier compositions are possible. This solution can then be used to produce the fatliquor according to the invention.

It is also conceivable to add the individual components of the emulsifier composition separately from one another in the preparation of the fatliquor without first producing a mixture of the individual emulsifier components.

According to a preferred embodiment of the fatliquoring agent according to the invention an alkoxylated with at least 15 alkylene oxide units C ₁₂ - C ^ fatty alcohol mixture used to, on the one hand an alkoxylated with 15 to 30 alkylene oxide units C ₁₂ - to C _M fatty alcohol mixture and the other one with 40 contains up to 100 alkylene oxide units alkoxylated C ₁₂ to C ₂₄ fatty alcohol mixture.

Accordingly, the present invention also relates to a fatliquor, as described above, which is characterized in that it is used as component (C)

(Ca) a C ₆ -C ₁₇ -alkanol alkoxylated with 4 to 12 alkylene oxide units or a mixture of two or more such alkanols and

(Cb) an alkoxylated with 15 to 30 alkylene oxide units C ₁₂ - to C ^ fatty alcohol mixture and (Cc) an alkoxylated with 40 to 100 alkylene oxide units C ₁₂ - to C ₂₄ -

Fatty alcohol mixture

contains.

The present invention also describes the emulsifier composition itself containing

(Ca) a C ₆ to C ₁₇ alkanol alkoxylated with 4 to 12 alkylene oxide units or a

Mixture of two or more such alkanols and (Cb) a C ₁₂ to C ^ fatty alcohol mixture alkoxylated with 15 to 30 alkylene oxide units and (Cc) a C ₁₂ to C ₂₄ alkoxylated with 40 to 100 alkylene oxide units

Fatty alcohol mixture. According to a further preferred embodiment of the fatliquor according to the invention, the emulsifier components according to (Ca) have an average of 8 to 17 C atoms, particularly preferably 10 to 17 C atoms and particularly preferably an average of 13 to 15 C atoms, and the emulsifier components according to (Cb ) and (Cc) independently of one another on average 14 to 20 carbon atoms, particularly preferably on average 16 to 18 carbon atoms.

Emulsifier compositions are further preferred in which component (Ca) averages 5 to 10 alkylene oxide units, component (Cb) averages 20 to 30 alkylene oxide units and component (Cc) averages 50 to 100 alkylene oxide units. point.

The emulsifier composition (C) generally contains the component (Ca) in a proportion in the range from 40 to 80% by weight, preferably in the range from 45 to 75% by weight and particularly preferably in the range from 50 to 70% by weight. %, each based on the total weight of the emulsifier composition.

The component (Cb) in the emulsifier composition (C) is generally in a proportion in the range from 10 to 50% by weight, preferably in the range from 10 to 40% by weight and particularly preferably in the range from 15 to 30% by weight. -%, each based on the total weight of the emulsifier composition.

Component (Cc) in the emulsifier composition (C) is generally in a proportion in the range from 10 to 50% by weight, preferably in the range from 10 to 40% by weight and particularly preferably in the range from 15 to 30% by weight. -%, each based on the total weight of the emulsifier composition.

Accordingly, the present invention also relates to a fatliquor, as described above, which is characterized in that the emulsifier composition according to (C) contains the component (Ca) in a proportion in the range from 40 to 80% by weight, the component (Cb) in in a proportion of 10 to 50% by weight and component (Cc) in a proportion of 10 to 50% by weight, in each case based on the weight of component (C).

The present invention therefore also describes the emulsifier composition itself containing (Ca) 50 to 70% by weight of a C ₁₃ to C 12 alkanol alkoxylated with 5 to 10 alkylene oxide units or a mixture of two or more such alkanols and

(Cb) 15 to 30% by weight of a C ₁₆ to C ₁₈ fatty alcohol mixture alkoxylated with 20 to 30 alkylene oxide units and (Cc) 15 to 30% by weight of a C ₁₆ alkoxylated with 50 to 100 alkylene oxide units up to C ₁₈ -fatty alcohol mixture,

where the percentages by weight are based in each case on the weight of component (C) and the sum of the percentages by weight from (Ca), (Cb) and (Cc) 100.

In very general terms, the present invention also describes the use of the emulsifier composition as described above, and of component (Ca) or (Cb) or (Cc) or components (Ca) and (Cb) or components (Ca) and (Cb) or Components (Ca) and (Cc) or components (Ca) and (Cb) and (Cc) for the production of a fatliquor for the production and / or treatment of leather.

The present invention also generally describes the use of component (Ca) or (Cb) or (Cc) or components (Ca) and (Cb) or components (Ca) and (Cb) or components (Ca) and ( Cc) or the components (Ca) and (Cb) and (Cc) for the production and / or for the treatment of leather.

In general, the fatliquoring agents according to the invention contain components (A), (B) and (C) in proportions in the range from 50 to 90% by weight with respect to component (A), in the range from 5 to 25% by weight with regard to Component (B) and in the range of 1 to 10% by weight with respect to component (C), the weight of component (B) being calculated as the weight of the aqueous solution or dispersion of the at least one polymer.

Accordingly, the present invention also relates to a fatliquor, as described above, which is characterized in that it contains component (A) in a proportion in the range from 50 to 90% by weight, component (B) in a proportion in Contains range of 5 to 25 wt .-% and component (C) in a proportion in the range of 1 to 10 wt .-%, the weight of component (B) as the weight of the aqueous solution or dispersion of the at least one polymer is expected. According to a preferred embodiment, the fatliquoring agents according to the invention contain components (A), (B) and (C) in proportions in the range from 55 to 85% by weight with respect to component (A), in the range from 10 to 25% by weight with regard to component (B) and in the range from 2 to 9% by weight with regard to component (C), the weight of component (B) being calculated as the weight of the aqueous solution or dispersion of the at least one polymer.

According to a particularly preferred embodiment, the fatliquoring agents according to the invention contain components (A), (B) and (C) in proportions in the range from 60 to 80% by weight with respect to component (A), in the range from 10 to 20% by weight. % with respect to component (B) and in the range from 3 to 8% by weight with respect to component (C), the weight of component (B) being calculated as the weight of the aqueous solution or dispersion of the at least one polymer.

In addition to components (A), (B) and (C) described above, the fatliquoring agents according to the invention can also contain other suitable constituents. For example, further fatliquors known from the prior art can be contained in the fatliquor according to the invention. Additional emulsifiers and / or diluents, in particular water, may also be present. For example, glycols are preferably contained in the fatliquor, with diethylene glycol, dipropylene glycol, butyl diglycol, hexylene glycol or oligoethylene glycols having 3 to 7 ethylene units being further preferred. According to a particularly preferred embodiment, the composition according to the invention contains dipropylene glycol.

According to a preferred embodiment, a composition according to the invention contains the at least one further constituent mentioned, for example preferably the at least one glycol, preferably dipropylene glycol, in a proportion in the range from generally 1 to 20% by weight, preferably from 3 to 17% by weight. and particularly preferably from 5 to 15% by weight, in each case based on the total weight of the composition.

The composition according to the invention can be produced according to all suitable methods. In particular, the order in which the constituents contained in the composition according to the invention are combined is essentially as long as the processability is ensured. In particular, mesophase, for example, could occur in the production of the composition according to the invention, which could, for example, have a disadvantageous effect on the stirrability of the composition. It is therefore preferred that, for example, the at least one native lipoid is initially introduced, then the at least one polymer based on the monomers acrylic acid and or or methacrylic acid is added, and the emulsifier composition is then added. This can be followed, for example, by the addition of further solvent, for example to set the desired degree of dilution. In a likewise preferred embodiment, the emulsifier composition is not produced in a separate step and then added as such, but the constituents of the emulsifier composition are used individually and in succession to produce the fatliquoring agent according to the invention. If, for example, a modified, native oil and a native phospholipid are used as the at least one lipoid, it is particularly preferred to initially introduce the oil and then to add the phospholipid, further preferably the oil and the phospholipid at a temperature in the range from 40 to 50 ° C are mixed together.

The present invention further relates to the use of the fatliquors described above in the manufacture and / or treatment of leather. In particular, the greasing agents according to the invention are used to soften leather, increase its fullness and strength and to protect it against moisture, dirt and external chemical influences.

Accordingly, the present invention also relates to the use of a fatliquor, as described above, in the manufacture or treatment or in the manufacture and treatment of leather and hides.

In the use according to the invention, the fatliquoring agents according to the invention can be used undiluted or, for example, as an aqueous dispersion. According to a preferred embodiment, such aqueous dispersions contain solids in a proportion in the range from 40 to 80% by weight, more preferably in the range from 50 to 80% by weight and in particular in the range from 60 to 75% by weight.

The present invention therefore also relates to a method for fatliquoring leather and skins, the leather or the skins being brought into contact with at least one aqueous dispersion, which is characterized in that the at least one aqueous dispersion contains a fatliquor as described above in one proportion contains from 40 to 80% by weight. In the context of the present invention, it is particularly preferred to produce the fatliquor containing the above-mentioned components as a highly concentrated product. In this way it is possible for the tanner to dilute and use the product according to his own ideas and specifications. For such concentrated fatliquor compositions, lower transportation costs are still incurred due to lower weight. In the case of this highly concentrated product, it is preferred, for example, to predilute the product before use, degrees of dilution in the range from, for example, 1: 4 to 1: 5 being preferred. A degree of dilution of 1: 4 means that 4 parts by weight of solvent, for example preferably water, are used per part by weight of product.

The present invention is explained in more detail in the following examples.

Examples

Example 1: Preparation of a fatliquor according to the invention

500 kg of oxidized, sulfated beet oil (Δd = 0.03, organically bound SO ₃ 4%) were mixed with 900 kg of acetylated soy lecithin at 40 ° C. in a stirred kettle with anchor stirrer.

After 1 h, 300 kg of a sodium salt of a polyacrylic acid (0.5 mol of NaOH based on COOH of polyacrylic acid, pH 4.5 to 5.5, solids content 30%, M = 70,000 g / mol), 60 kg of a C ₁₃ / C ₁₅ fatty alcohol mixture with 7 mol EO), 20 kg of a Cι ₆ / C ₁₈ fatty alcohol mixture (fatty alcohol C ₁₆ / C ₁₈ ethoxylate with 80 mol EO) and 20 kg of a further Cie / Cis fatty alcohol mixture (fatty alcohol C ₁₆ / C ₁₈ - ethoxylate mixed with 25 mol EO) and 200 kg dipropylene glycol.

For complete homogenization, stirring was continued for 1 h.

Example 2: Preparation of a comparative fatliquor

500 g of oxidized, sulfated beet oil (Δd = 0.03, organically bound SO ₃ 4%) were placed in a stirrer flask at 40 ° C. Then 300 g of a sodium salt of a polyacrylic acid (0.5 mol of NaOH based on COOH of polyacrylic acid, pH 4.5 to 5.5, solids content 30%, M _w = 70,000 g / mol), 60 g of a (Fatty alcohol cis / cis ethoxylate with 7 mol EO), 20 g of a C ₁₆ / C ₁₈ fatty alcohol mixture (fatty alcohol C ₁₆ / C ₁₈ ethoxylate with 80 mol EO) and 20 g of another C ₁₆ / C ₁₈ - Fatty alcohol mixture (fatty alcohol C ₁₆ / C ₁₈ ethoxylate with 25 mol EO) and 200 g dipropylene glycol added.

For complete homogenization, stirring was continued for 1 h.

Example 3: Leather production using the fatliquor according to the invention

100 parts by weight of chrome cowhide with a fold thickness of 1.4 to 1.6 mm were placed in 100 parts by weight of water at 35 ° C. and adjusted to a pH of 4.5 by adding sodium formate and sodium hydrogen carbonate. The leather was drummed at 35 ° C. for 90 minutes in a barrel and then washed with 100 parts by weight of water.

After the liquor had been drained, the retanning was carried out by adding 100 parts by weight of water (all at 35 ° C.), then 2 parts by weight of high molecular weight polymer tanning agent (Relugan ^® RE). After 15 min moving in the barrel 1 part by weight of synthetic auxiliary tanning agent (Tamol ^® M) was added and incubated for another 15 minutes. emotional. Now 4 parts by weight of vegetable tanning agent (Mimosa) and 4 parts by weight of resin tanning agent (Relugan ^® D and S) were added.

After 60 minutes of agitation, the pH was adjusted to 5.5 with sodium bicarbonate. Thereafter, 1.5 parts by weight of an acid-substantive leather dye (Luganil ^® Brown NGB) was added. After 45 minutes in the moving barrel, the pH was adjusted to 3.6 with formic acid for fixation for 30 minutes. Now the liquor was drained again and washed with 100 parts by weight of water at 60 ° C.

The greasing was then carried out by adding 100 parts by weight of water (60 ° C.) and 5 percent by weight of the greasing agent prepared according to Example 1 in a 1: 5 dilution with water. Then was drummed for 60 minutes in the barrel at 60 ° C, a further 100 parts by weight of water are added, drumming for 15 minutes, adjusted by addition of formic acid of pH 3.7 and fixed by adding a cationic fixative (Bastamol ^® B) the fat. After draining the liquor and washing again with 200 parts by weight of water, the leather was dried (hanging drying), conditioned and stabled.

The leather obtained in this way was characterized by excellent softness and firmness of the grain, excellent fullness and a pleasant, velvety feel.

Example 4: Leather production using the comparative fatliquor

Example 4 was carried out analogously to Example 3, with the comparative fatliquor prepared according to Example 2 being used in the oiling step instead of the oiling agent according to the invention.

The leather thus obtained was characterized by only medium softness with poor grain strength and good fullness. The pleasant, velvety feel of the leather described in Example 3 was also missing.

Claims

claims

1. Lubricant for the manufacture and / or treatment of leather, containing

(A) at least one native lipoid;

(B) at least one polymer based on the monomers acrylic acid and / or methacrylic acid;

(C) an emulsifier composition comprising a C ₆ -C ₁₇ -alkanol alkoxylated with up to 12 alkylene oxide units or a mixture of two or more such alkanols and a C ₁₂ -C ₁₂ -fatty alcohol mixture alkoxylated with at least 15 alkylene oxide units.

2. Fatliquor according to claim 1, characterized in that it contains a mixture as at least one native lipoid

(Aa) at least one chemically modified, native oil in a proportion in the range from 20 to 50% by weight and (Ab) at least one native phospholipid in a proportion in the range from 50 to 80% by weight,

each based on the total weight of component (A).

3. fatliquor according to claim 2, characterized in that a chemically modified, native oil according to (Aa) is oxidized, sulfated rapeseed oil.

4. Fatliquor according to claim 2 or 3, characterized in that a chemically modified, native phospholipid is acetylated lecithin.

5. Fatliquor according to one of claims 1 to 4, characterized in that a polymer according to (B) is a polyacrylic acid with a molecular weight in the range from 2,500 to 150,000 g / mol.

6. Fatliquor according to one of claims 1 to 5, characterized in that it is used as component (C) (Ca) an alkoxylated with 4 to 12 alkylene oxide units C ₆ - to C ₁ alkanol or a mixture of two or more such alkanols and (Cb) an alkoxylated with 15 to 30 alkylene oxide units C ₁₂ - to C ^ - fatty alcohol mixture and (Cc) a C ₁₂ - to Cu ~ alkoxylated with 40 to 100 alkylene oxide units

Fatty alcohol mixture

contains.

7. fatliquor according to claim 6, characterized in that the emulsifier composition according to (C) the component (Ca) in a proportion in the range of 20 to 60 wt .-%, the component (Cb) in a proportion of 20 to 70 wt. -% and the component (Cc) in a proportion of 10 to 50 wt .-%, each based on the weight of component (C).

8. Fatliquor according to one of claims 1 to 7, characterized in that it contains component (A) in a proportion in the range from 50 to 90% by weight, component (B) as an aqueous solution or dispersion in a proportion from 5 to 25% by weight and contains component (C) in a proportion in the range from 1 to 10% by weight, the weight of component (B) being calculated as the weight of the aqueous solution or dispersion.

9. Use of a fatliquor according to one of claims 1 to 8 in the manufacture or treatment or in the manufacture and treatment of leather and hides.

10. A process for oiling leather and skins, wherein the leather or the skins are brought into contact with at least one aqueous dispersion, characterized in that the at least one aqueous dispersion contains a fatliquor according to one of claims 1 to 8 in a proportion of Contains 40 to 80 wt .-%.