EP1540021A1

EP1540021A1 - Stuffing agent for leather based on mixtures of modified, native oils with alcoxylated alkanols, use thereof and method for treating leather

Info

Publication number: EP1540021A1
Application number: EP03748006A
Authority: EP
Inventors: Ralph Lunkwitz; Andreas Seitz
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2002-09-12
Filing date: 2003-09-11
Publication date: 2005-06-15
Also published as: KR20050057313A; CN100396796C; CN1681945A; BR0314178A; AR041178A1; AU2003267342A1; US20060150342A1; DE10242401A1; WO2004027096A1

Abstract

The invention relates to a stuffing agent comprising A) a mixture of modified native oils containing a1) at least one oxidized sulphitized native oil and a2) at least one oxidized sulphatized native oil, B) an emulsifier mixture containing b1) at least one C6- C14-alkanol which is alkoxylated with 4 - 12 alkylene oxide units, b2) at least one C12- C24-alkanol which is alkoxylated with 15 - 40 alkylene oxide units and b3) at least one C12- C24-alkanol which is alkoxylated with 50 - 100 alkylene oxide units, in addition to C) optionally one linear, cyclic or branched polymer of dialkylsilandiol SiR2(OH)2, wherein R represents methyl, ethyl, n-propyl or phenyl, and/or D) optionally one compound of general formula (II), wherein R<l> and R<2> are identical or different and are selected independently from each other from the group consisting of H, M, saturated linear aliphatic C1- C18-alkyl and saturated branched aliphatic C3- Cl8 alkyl, wherein at least one of the two radicals R<1> and R<2> H, M with M = alkali metal, 0.5 alkaline earth metal, and M+ is selected from the group of H+, NH4+, alkali metal+ and 0.5 alkaline earth metal+. The invention also relates to the use of the inventive stuffing agents in the production of leather and/or in the treatment of leather with aqueous dispersions of said stuffing agents.

Description

LUBRICANT FOR LEATHER, BASED ON MIXTURES OF MODIFIED, NATURAL OILS WITH ALKOXYLATED AL ANOLES, THEIR USE AND METHOD FOR TREATING LEATHER

The present invention relates to fatliquors based on mixtures of modified, native oils with alkoxylated alkanols, their use in the production and / or treatment of leather and hides, and to processes for the production and / or treatment of leather and hides with these fatliquoring agents.

In leather production, greasing agents serve 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" 1985, Volume 4, p. 13 et seq.). Commercial greasing agents generally consist of greasing substances, such as native fats, native oils, waxes, resins and their derivatives and / or petroleum fractions and their secondary products, and wax-like products such as "wool fat", in raw, cleaned and / or prepared ( Lanolin) form (see H. Herfeld, "Bibliothek des Leders" 1985, Volume 4, pp. 59 ff.) The fatty substances can - if desired - be chemically modified, ie they can have a modified chemical structure.

The chemical modification of the greasing substances generally consists in that the double bonds contained in these substances are at least partially subjected to addition reactions or oxidation reactions. Modifications that are frequently carried out include, for example, the addition of sulfites, which introduces sulfonic acid groups into the fatty substances, or air oxidation, which introduces oxygen functions and, in some cases, oligomerizations also occur. However, (partial) hydrolysis of the fats, transesterifications and similar modification reactions are also possible.

These chemical modifications make it possible to apply the relevant technical applications

Properties of the greasy substances such as hydrophilicity, hydrophobicity, solubility, dispersibility, penetration and anchoring properties, special purposes or to optimally adapt to the requirements of the user. Especially high Quality car upholstery leather has to meet certain criteria. On the one hand, the softness of the leather is essential, on the other hand the fastness to light and warmth and finally the so-called fogging behavior.

The DUST 75201 defines "fogging" as the condensation of evaporated components from the vehicle interior such as the upholstery leather on the glass panes, especially on the windshield. This can lead to a deteriorated view through the windshield, especially when driving at night, and thus to a safety risk. According to D N 75201, the fogging behavior of leather is characterized by a gravimetric and a reflectometric method.

In order to prevent unwanted fogging, it is therefore an aim to reduce the proportion of organic compounds which can emerge from the treated leather after processing ("volatile organic compounds"). However, the use of organic compounds such as solvents is sometimes difficult to avoid. Because to ensure a good distribution of the fat on the leather, the fat is often diluted with solvent for application. Some possibilities are known from the prior art to avoid this problem.

For example, EP-A 0 498 634 recommends special polymers for the production of leathers with so-called "low fogging" properties. The aqueous dispersions used in leather treatment are essentially free of organic solvents and contain an amphiphilic copolymer. This copolymer consists of a predominant proportion of at least one hydrophobic monomer and a minor proportion of at least one hydrophilic monomer. Leather treatment with these dispersions leads to good results in a gravimetric test according to DLN 75201. Reflectometric studies have not been described.

These amphiphilic copolymers are preferably prepared by emulsion polymerization in aqueous solution. Due to the different hydrophilicity of the monomers to be used, problems naturally arise in the copolymerization behavior. In extreme cases, this can lead to the monomers undesirably forming homopolymers on their own. Another consequence of the inherently unfavorable solution ratios is an expensive work-up to destroy unreacted monomers. In order to achieve good emulsion stability, it is also necessary to use a sufficient amount of an emulsifier (in the examples given Lauryl sulfate was used), which can lead to wastewater problems in leather processing.

EP-B 0 466 392 describes a process for the preparation of polymers which contain both pendant hydrophobic groups and pendant hydrophilic alkoxylated groups. Such polymers are obtained by carrying out derivatization reactions after the actual polymerization process — known to the person skilled in the art. Thus, 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 or primary or secondary alkoxylated amines. The polymers described are used as thickeners and soil release agents. Their use in leather treatment is not described.

In the processes according to WO 98/10103, polymeric fatliquoring agents are produced 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 subsequent reaction of the polymers thus obtained with amines , According to DIN 75201 B (gravimetric test), fogging values of 1.2 mg and 1.5 mg were found for leather that has been treated with these polymeric lubricants. The leather treated with the comparative products Magnopal ^® SOF (low-fogging polymer greasing agent from Stockhausen GmbH & Co. KG) and Chromopol ^® LFC (low-fogging greasing agent based on fish oils from Stockhausen GmbH & Co. KG) achieve fogging values of 3.9 mg and 3.5 mg. The reflectometric values according to DN 75201 A of the polymeric fatliquoring agents are 51% and 55%, that of the comparative products 34% and 40%.

A process is also described in US Pat. No. 5,348,807 in which selected amphiphilic copolymers, consisting of a predominant proportion of hydrophobic and a smaller proportion of hydrophilic assemblies, are used as solvent-free, low-fogging fatliquors. To produce these polymers, acidic or basic substituted esters of unsaturated carboxylic acids, such as, for example, sulfatoethyl (meth) acrylate or dimethylaminoethyl (meth) acrylate, are used as hydrophilic monomers. For example, longer-chain alkenes or (meth) acrylic acid esters of C - to C ₂ -alkanols or vinyl esters of C - to C ₁₂ -carboxylic acids serve as hydrophobic monomers. The substances give good fogging values; however, there is no information about bath consumption. In this process too, the amphiphilic copolymers are preferably prepared by aqueous emulsion polymerization. However, due to the different hydrophilicity of the monomers to be used, this again leads to the problems already mentioned in the discussion of EP-A 0498 634.

EP-B 0 753 585 describes a low-fogging surface treatment for furniture leather in which specially treated native oils, which have less than 3% of fatty acid components with less than 16 carbon atoms, act as the basis for fatliquoring agents. Native oils used are soybean, lard, safflower and sunflower oil. The said native oils are first distilled to remove the undesirable low molecular weight constituents and then reacted with hydrogen sulfite or hydrogen sulfate in order to improve the emulsifiability. Then the (partially) functionalized oils are emulsified and applied.

In order to avoid the use of organic solvents to distribute the fatliquoring agents, a special emulsifier composition comprising three components A, B and C is used according to the applicant's unpublished DE-A 101 43 949.0. Component A is a C ₆ -C 1 -alkanol alkoxylated with 4 to 12 alkylene oxide units, or a mixture of several such alkanols, component B is a C ₂ -C ₂₄ fatty alcohol mixture alkoxylated with 15 to 40 alkylene oxide units and the component C is a C ₁₂ to C ^ fatty alcohol mixture alkoxylated with 50 to 100 alkylene oxide units. The alkylene oxide units are expediently alkylene oxide units having 2 to 4, preferably 2 to 3, carbon atoms. The building blocks of the polyether chains can all be the same or different and - if they are different - they can be arranged randomly or in blocks. The proportions by weight of the components in the emulsifier composition are 20 to 60, preferably 25 to 50, in particular 28 to 40% by weight for component A, 20 to 70, preferably 25 to 60, in particular 30 to 45% by weight for component B. -% and for component C 10 to 50, preferably 15 to 40, in particular 22 to 32 wt .-% of the total weight of the composition.

In particular for the greasing of Cr-free tanned leathers and skins, according to the applicant's unpublished DE 102 07 277.9, greasing agents are used which contain at least one modified native oil and at least one stabilizer LnR. Here R stands for an n-valent, optionally substituted with carbonyl, alkylcarbonyloxy, alkylcarbamoyl and / or alkoxycarbonyl groups and / or containing O, N (H) and / or S units, saturated or unsaturated, linear aliphatic C ₃ to C ₃₀ or branched aliphatic C ₄ to C ₃₀ or (hetero) cycloaliphatic C to C30 or (hetero) aromatic C ₄ to C3o hydrocarbon radical, n for an integer from 1 to 10, and L for a hydroxyphenyl radical which is substituted by R ^a , R ^b and R ^c . R ^a is H or methyl, R ^b is methyl, ethyl or tert-butyl, R ^c is methyl, tert-butyl, cyclohexyl or methylcyclohexyl. In addition, the stabilizer LJ has a total of at least 20 C atoms, in particular a total of at least 28 C atoms, and in the case of n = 2, -R- also stands for -S-, -O-, -N (H) - , -CH ₂ -, - (CH ₂ ) ₂ -, -CH (CH ₃ ) -, - (CH ₂ ) ₃ -, -CH (C ₂ H ₅ ) - or -C (CH ₃ ) ₂ -.

All of the prior art methods described above have in common that either polymers or fatliquors based on chemically modified native oils are used, and that these products are special, relatively narrow classes of substances. Good liquor exhaustion and consequently a high-exhaustion fat agent is present when the fat agent is absorbed as completely as possible by the collagen of the leather and / or skins. This is desirable from the point of view of environmental protection because of the associated less polluted wastewater and from the economic point of view because of the then less expensive wastewater treatment.

In "wet blue" semifinished products, i.e. Cr-tanned semifinished products, the mostly anionic fatliquor is fixed by the chromium (III) cations. "Wet white" semifinished products, i. H. Cr-free tanned semi-finished products are produced without cationic metal salts, which is why these binding sites are missing. When using commercially available greasing agents which are manufactured according to the state of the art, the bath consumption is often insufficient, 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 poorly fixed in the leather and therefore leather with high fogging values according to DIN 75201 is obtained.

The object of the present invention is to provide a lubricant which largely avoids the disadvantages of the prior art. The leathers treated with these greasing agents should be sufficiently draining and, if necessary, have sufficient fastness to light and heat and should be low in VOC. The fatliquoring agents according to the invention should also color and emboss the leather well.

According to the invention, the object is achieved comprehensively by means of a lubricant A) containing a mixture of modified native oils

al) at least one oxidized sulfited virgin oil and a2) at least one oxidized sulfated virgin oil,

B) containing an emulsifier mixture

bl) at least one C ₆ - bis alkoxylated with 4 to 12 alkylene oxide units

-C alkanol, b2) at least one C ₁₂ - bis alkoxylated with 15 to 40 alkylene oxide units

C ^ -alkanol and b3) at least one C ₁₂ - bis alkoxylated with 50 to 100 alkylene oxide units

C ₂ alkanol, and

C) optionally a linear, cyclic or branched polymer of a dialkylsilanediol SiR ₂ (OH) ₂ , where R is methyl, ethyl, n-propyl or phenyl, and / or

D) optionally a compound of the general formula (II)

where R ¹ and R ^{2 are} identical or different and are selected independently of one another from the group consisting of H, M, saturated linear aliphatic - to cig-alkyl and saturated branched aliphatic C ₃ - to cig-

Alkyl, at least one of the two radicals R ¹ and R ² ≠ H, M with M = alkali metal, 0.5 alkaline earth metal, and M ^{+ is} selected from the group H ⁺ , NH ⁺ , alkali metal ⁺ and 0.5 alkaline earth metal ⁺ . The greasing agents according to the invention are particularly suitable for greasing leather and skins, since the leather and skins treated in this way show low fogging and low VOC values, in particular the leather and skins treated in this way are easy to color and emboss and have a pleasant feel. The presence of the fatliquoring agents according to the invention in the leather treatment liquors (undiluted or in the form of aqueous dispersions, see below) leads to good bath consumption and thus to low COD values with good anchoring of the fatliquoring agent inside the leather.

Components A to D are now explained in more detail below.

Component A

Fats of plant or animal origin, in particular glycerides of natural fatty acids, with a sufficient proportion of unsaturated acids are expediently used as native oils. Well-suited native oils are those with an iodine number of approx. 10 to approx. 200. In the lower section of this range you can find e.g. Stearin and tung oil, in the upper section in particular the fish oils and the Chaulmoogra oil. Preference is given to native oils with iodine numbers from approximately 30 to approximately 120, in particular from 40 to 85.

Examples of particularly preferred modified native oils are modified fish oil, claw oil, lard oil, soybean oil, rapeseed oil, nut oil, olive oil and castor oil.

Modified native oils which have a relatively high degree of oxidation and a relatively low degree of sulfitation or sulfation are particularly advantageous.

The oxidation products, sulfitation products or sulfation products of the mono- or polyunsaturated fats are formed by the reaction of the olefinic double bonds present in the fats with the oxidation, sulfitation or sulfation reagents. All double bonds present in the fats or only a part of them can react.

For example, air at temperatures of 60 to 80 ° C is used as the oxidation reagent. However, the oxidation can also be carried out in other ways known to the person skilled in the art. A relatively high degree of oxidation in the sense of this invention is when Δd, the difference in the specific weights of the oil or fat before and after the oxidation, is in the range from 0.01 to 0.1 g / ml, preferably from 0.03 to 0 .05 g / ml. The sulfitation is generally carried out by reaction in aqueous Na ₂ S ₂ θ5 solution. However, it can also be carried out in other ways known to the person skilled in the art. A relatively low degree of sulfitation in the sense of this invention is when the native oil with 2 to 8% by weight, preferably 3 to 5% by weight, of its weight with a sulfite, calculated as sodium bisulfite (Na ₂ S ₂ O ₅ ) has been implemented.

The oxidized, sulfited native oil is obtained by oxidizing native oil such that the difference Δd in the specific weights of the unoxidized and oxidized native oil is in the range from 0.01 to 0.1 g / ml, preferably in the range from 0. 03 to 0.05 g / ml, and then the oxidized native oil with 2 to 8 wt .-% of its weight, preferably with 3 to 5 wt .-% of its weight, with a sulfite - calculated as sodium bisulfite (Na ₂ S ₂ Os) - is implemented.

The sulfation is generally carried out by reaction in ≥ 60% by weight aqueous H ₂ SO solution, preferably in ≥ 98% by weight aqueous H ₂ S 0 solution. No particular requirements are imposed on the purity of the solution, so that technical H ₂ SO solution can also be used. The sulfation is therefore particularly preferably carried out in a concentrated technical HSO solution. The use of oleum is also possible. However, the reaction can also be carried out in other ways known to the person skilled in the art, for example by reaction with SO ₃ or ClSO ₃ H. A relatively low degree of sulphation in the sense of this invention is present when the native oil is 3 to 9% by weight. , preferably with 4 to 8 wt .-%, its weight with H ₂ SO - calculated as 98 wt .-% - aqueous H ₂ SO solution - has been implemented.

The oxidized, sulfated native oil is obtained by oxidizing native oil such that the difference Δd in the specific weights of the unoxidized and oxidized native oil is in the range from 0.01 to 0.1 g / ml, preferably in the range from 0. 03 to 0.05 g / ml, and the thus oxidized native oil then with 3 to 9% by weight, preferably with 4 to 8% by weight, of its weight with H ₂ SO - calculated as 98% by weight % aqueous H ₂ SO solution - is implemented.

Component B

Component B is an emulsifier mixture of the individual components bl, b2 and b3. The alkylene oxide units of the alkanols thus alkoxylated are expediently those having 2 to 4, preferably 2 to 3, carbon atoms. I.e. that is, the alkoxylated long-chain and long-chain alkanols known from the prior art are obtained by reacting the corresponding alkali nols or alkanol mixtures, as they are present in fatty alcohols, with the desired molar amounts of the alkylene oxides, such as ethylene, propylene or butylene oxide. Depending on how the alkylene oxides are metered into the batches, the units of the polyether chains obtained therefrom can all be the same or different and - if they are different - can be arranged statistically or in blocks. The reaction can be catalyzed by small amounts of water and / or alkali.

The emulsifier mixture contains in particular 20 to 60, preferably 25 to 50, particularly preferably 28 to 40% by weight of a component bl or a mixture of components bl, 20 to 70, preferably 25 to 60, particularly preferably 30 to 45% by weight. % of a component b2 or a mixture of components b2 and 10 to 50, preferably 15 to 40, particularly preferably 22 to 32% by weight, of a component b3 or a mixture of components b3, in each case based on the total weight of the emulsifier mixture.

Component bl is preferably at least one C ₈ -C ₁₂ -alkanol alkoxylated with 4 to 12 alkylene oxide units, particularly preferably at least one CIO-alkanol alkoxylated with 4 to 12 alkylene oxide units. Component b2 is preferably at least one C ₁₄ to C ₂ alkanol alkoxylated with 15 to 40 alkylene oxide units, particularly preferably a C ₁₆ to g alkanol alkoxylated with 15 to 40 alkylene oxide units. Component b3 is preferably at least one C 1 -C ₂₀ -alkanol alkoxylated with 50 to 100 alkylene oxide units, particularly preferably a C ₆ -C-alkanol alkoxylated with 50 to 100 alkylene oxide units.

In addition, component bl is preferably alkoxylated with 5 to 10 alkylene oxide units and / or component b2 with 20 to 30 alkylene oxide units and / or component b3 with 50 to 100 alkylene oxide units. Component bl is particularly preferably alkoxylated with 5 to 10 alkylene oxide units and component b2 with 20 to 30 alkylene oxide units and component b3 with 50 to 100 alkylene oxide units.

Component C

Component C is the reaction product which is obtained by polymerizing a dialkylsilanediol SiR ₂ (OH) ₂ , where R is methyl, ethyl, n-propyl or phenyl. The polymer thus obtained can be linear, cyclic or branched. It preferably has a viscosity of 30 to 1000 mPa-s, preferably 80 to 500 mPa * s, measured in pure substance at 20 ° C. Component C can be either a homo- or a copolymer , The fat according to the invention Detergent can contain both no and one or more components C. The fatliquoring agent according to the invention preferably contains at least one component C.

The polymers of the general formula (I) and their preparation are known to the person skilled in the art and are described, for example, in EP-A 0 213 480, in Jürgen Falbe, Manfred Regitz, Römpp Chemie Lexikon 1992, 9th edition, Georg Thieme Verlag Stuttgart - New York , Volume 5, pp. 4167 ff., In particular under "Silicones" and "Siloxane", and in Ullmanns Encyclopedia of Industrial Chemistry 1982, 4th edition, Verlag Chemie Weinheim, Volume 21, pp. 511 - 543, in particular under "Silicon -Oils ". The silicone oils described in EP-A 0 213 480 are made part of the present technical teaching by reference.

Component D

In the connection of the general formula (II)

in which R and R are identical or different and are independently selected from the group consisting of H, M, saturated linear aliphatic - to s-alkyl and saturated branched aliphatic C - to cis-alkyl, at least one of the two radicals R ¹ and R ² ≠ H, M with M = alkali metal, 0.5 alkaline earth metal, and

M ^{+ is} selected from the group H ⁺ , NH ⁺ , alkali metal ⁺ and 0.5 alkaline earth metal ⁺ , it is a sulfited succinic acid mono- or diester. The diesters can be both mixed esters and diesters with the same alcohol. These are preferably diesters with the same alcohol.

The fatliquoring agent according to the invention can contain neither one nor one or more of the compounds of the general formula (II). The fatliquoring agent according to the invention preferably contains at least one compound of the general formula (II). R ¹ and R ² are preferably independently of one another from the group methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, n-octyl, n-dodecyl, n-tridecyl, n-tetradecyl and n-hexadecyl and / or M ⁺ = H ⁺ or Na ⁺ .

The compound of general formula (II) can be prepared by a process comprising the following steps:

i) Reaction of at least one substance selected from the group maleic anhydride, maleic acid, fumaric acid with at least one saturated aliphatic Ci to C ₁₈ alkanol in a molar ratio (0.1 to 1) to (2 to 5) to one

Compound of the general formula (purple) or (Illb)

(ffla) (Ulb) where R ¹ and R ^{2 are} identical or different and are selected independently of one another from the group consisting of H, saturated linear aliphatic Ci to C ₁₈ alkyl and saturated branched aliphatic C ₃ - to C ₁₈ - Alkyl, at least one of the two radicals R ¹ and R ² ≠ H, and

ii) reaction of the compounds of the general formula (purple) or (IIIb) obtained by step i) with a derivative of the sulfurous acid, in particular with Na ₂ S ₂ O ₅ , to give a compound of the general formula (II) with M ⁺ = Get Na ⁺ .

Maleic anhydride is preferably used in step i). Alkanols which are preferably used are methanol, ethanol, propanol, isopropanol, 1-butanol, 2-methylpropanol, tert-butanol, 1-pentanol, 3-methylbutanol, 2,2-dimethylpropanol, 1-hexanol, 2-ethylhexanol, 1-octanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol and 1-hexadecanol.

The pressure during the process is in particular from 1 bar (= normal pressure) to 5 bar. The process is preferably carried out at 80 to 100 ° C., the upper limit for the reaction temperature being determined by the boiling point of the alcohol used becomes. The person skilled in the art is familiar with further details on carrying out the process and preparing the other compounds of the general formula (II).

The fatliquoring agent according to the invention can be used in the manufacture and / or treatment of leather and hides. The invention therefore also relates to the use of the described lubricants according to the invention in leather production. Their use serves to soften the leather, to increase its fullness and strength and to protect against moisture, dirt and chemical influences from the outside.

The fatliquor according to the invention can be undiluted or, depending on the wishes of the user, in the form of aqueous dispersions (aqueous preparations), advantageously with solids contents of 40 to 80% by weight, preferably with solids contents of 50 to 80% by weight, particularly preferably with solids contents of 60 to 75% by weight can be provided. The invention thus also relates to a method for greasing leather and skins by treatment with the aforementioned aqueous preparations.

The preferred, particularly preferred and very particularly preferred composition of the fatliquoring agent according to the invention is shown in Table 1 below. The weight specifications relate to the total weight of the fatliquor. Other suitable additives known to the person skilled in the art may also be present.

Table 1: Composition of the fatliquor according to the invention

The components of the preferred fatliquoring agents according to the invention, namely the modified native oils according to the invention (component A) and the emulsifier mixture according to the invention (component B), and optionally the polymer of the general formula (I) (component C) and the compound of the general formula (II) ( Component D), the fat liquors together, in the form of a preparation, or in any Order separately - with stirring and, if necessary, gentle heating.

The following embodiments illustrate the invention.

embodiments

The composition of the fatliquoring agents FM1 to FM4 used according to the invention is shown in Table 2. The proportion of the individual components is given in% by weight, based on the total fatliquor.

Component al is a 93% by weight aqueous solution of oxidized sulfited rapeseed oil, the rapeseed oil being air-oxidized up to Δd = 0.01 to 0.1 g / ml and then with 4% by weight Na ₂ S ₂ Os - based on the weight of the rapeseed oil - was implemented. Component a2 is a 96% by weight aqueous solution of oxidized sulfated rapeseed oil, the rapeseed oil being air-oxidized up to Δd = 0.01 to 0.1 g / ml and then with 6% by weight 98% by weight. -% aqueous H ₂ S0 - based on the weight of the rapeseed oil - was implemented.

The non-ionic surfactant is Lutensol® AT 25 from BASF AG Ludwigshafen, a ₆ - to s-fatty alcohol mixture which has been ethoxylated with 25 moles of ethylene oxide. The nonionic surfactant Siligen® WL from BASF AG in Ludwigshafen is a mixture of linear C ₁₆ - to C ₈ fatty alcohols, which has been ethoxylated with 80 mol ethylene oxide. The non-ionic surfactant Lutensol® ON 70 from BASF AG in Ludwigshafen is the linear Cι ₀ - fatty alcohol, which was ethoxylated with 7 mol ethylene oxide.

The dialkyl sulfosuccinate Empimin® AMI from BASF AG in Ludwigshafen is the reaction product of maleic anhydride with 2-ethylhexanol in a 1: 2 molar ratio and subsequent sulfite addition to the double bond of the maleic acid (di) ester thus obtained. Silicon Oil® AK 350 from Wacker Chemie in Burghausen is a polydimethylsiloxane with a viscosity of 350 mPa * s - measured at 20 ° C. Densodrin® BA from BASF AG in Ludwigshafen is a 25% by weight aqueous solution of the copolymer, which is obtained by polymerizing a mixture of α-olefins having 20 to 24 carbon atoms with maleic anhydride in a molar ratio of 1 to 1 and then neutralizing with aqueous NaOH solution and has a number-average molar mass M _n of 10,000 g / mol. Table 2: Composition of the fatliquor FM1 to FM4

Example 1 Treatment of Cr-tanned leather with fatliquoring agents EMI to FM4 according to the invention

100 parts by weight of chrome cowhide with a thickness of 1.0 mm are moved in 200 parts by weight of water at 35 ° C for 10 minutes in a barrel. The liquor is then drained off and the chrome cowhide thus washed is agitated in a solution of 2.5 parts by weight of sodium formate in 150 parts by weight of water at 35 ° C. for 30 minutes. Then 0.8 part by weight of sodium hydrogen carbonate, dissolved in 12 parts by weight of water, is added, as a result of which a pH of 6.5 is set. In this liquor, the leather is kept moving at 30 ° C for 60 minutes. Then 2 parts by weight of FM1 fatliquor, which was diluted with water in a ratio of 1 to 3, are added to the liquor and the movement of the leather is continued at 60 ° C. for 60 minutes. Then the fleet is drained.

For retanning, the leather is added in a mixture of 100 parts by weight of water at 35 ° C., 5 parts by weight of a commercially available vegetable tanning agent (Tara) and 5 parts by weight of a commercially available liquid sulfone tanning agent which has been diluted with water at 35 ° C. in a ratio of 1 to 3 35 ° C for 60 minutes. Then 2.5 parts by weight of a commercially available anionic leather dye are added to the liquor and the leather is dyed at 35 ° C. for 60 minutes. Then 100 parts by weight of water at 60 ° C. and after 5 minutes 10 parts by weight of fatliquor FM1, which was diluted 1: 5 with water at 60 ° C., are added to the liquor. The fleet then has a pH of 6.9.

Without further supply of heat, 15 parts by weight of 8.5% by weight of formic acid are added to the liquor in the course of 30 minutes, the pH dropping to 3.6. The leather is agitated in the liquor for a further 30 minutes, then the liquor is drained off, and the leather is rinsed for 10 minutes with 200 parts by weight of water at 35 ° C. and further processed as usual.

The example was repeated analogously using the fatliquor FM2 to FM4.

You get leather with good firm grain, at the same time good fullness and medium softness. The leather surface has a pleasant grip.

Example 2 Treatment of Cr-free tanned leather with fatliquor FM1 to FM4 according to the invention

100 parts by weight of "wet white" cowhide with a fold thickness of 1.0 mm are stirred in 300 parts by weight of water at 35 ° C. for 10 minutes in a barrel. The liquor is then drained off, and the cowhide washed in this way is dissolved in a solution of 2.0 parts by weight Sodium formate in 200 parts by weight of water agitated for 20 minutes at 35 ° C. Then 0.3 part by weight of sodium hydrogen carbonate, dissolved in 4.5 parts by weight of water, is added, whereby a pH of 4.8 is set The leather is briskly moved at 30 ° C. for 60 minutes. Then 2 parts by weight of fatliquor FM1, which was diluted with water in a ratio of 1 to 3, are added to the liquor and the movement of the leather is continued at 60 ° C. for 60 minutes. Then the fleet is drained.

For retanning, the leather is added in a mixture of 100 parts by weight of water at 35 ° C., 6 parts by weight of a commercially available vegetable tanning agent (Tara) and 20 parts by weight of a commercially available liquid sulfone tanning agent which has been diluted with water at 35 ° C. in a ratio of 1 to 3 35 ° C for 120 minutes. Thereafter, 2.0 parts by weight of a commercially available anionic leather dye are added to the liquor and the leather is dyed at 35 ° C. for 60 minutes. Then 100 parts by weight of water at 60 ° C. and after 5 minutes 10 parts by weight of fatliquor FM1, which was diluted with water at 60 ° C. in a ratio of 1 to 5, are added to the liquor. The liquor then has a pH of 5.0.

Without further supply of heat, 15 parts by weight of 8.5% by weight of formic acid are added to the liquor over the course of 30 minutes, the pH dropping to 3.5. The leather is agitated in the liquor for a further 30 minutes, then the liquor is drained off, and the leather is rinsed for 10 minutes with 200 parts by weight of water at 35 ° C. and further processed as usual.

The example was repeated analogously using the fatliquor FM2 to FM4.

Claims

claims

1. comprising a lubricant for the manufacture and / or treatment of leather and hides

A) containing a mixture of modified native oils

B) containing an emulsifier mixture

bl) at least one C ₆ -C 1 alkanol alkoxylated with 4 to 12 alkylene oxide units, b2) at least one alkoxylated with 15 to 40 alkylene oxide units

C ₁₂ to C ₂ alkanol and b3) at least one alkoxylated with 50 to 100 alkylene oxide units

C ₁₂ to C ₂₄ alkanol, and

C) optionally a linear, cyclic or branched polymer of a dialkylsilanediol SiR2 (OH) ₂ , where R is methyl, ethyl, n-propyl or phenyl, and / or

D) optionally a compound of the general formula (II)

1 9 wherein R and R are the same or different and are independently selected from the group consisting of H, M, saturated linear aliphatic Ci to C ₁₈ alkyl and saturated branched aliphatic C ₃ - to C ₁₈ alkyl, at least one of the two radicals R ¹ and R ² ≠ H, M with M = alkali metal, 0.5 alkaline earth metal, and M ^{+ is} selected from the group H ⁺ , NHV ^" , alkali metal ⁺ and 0.5 alkaline earth metal ⁺ .

2. fatliquor according to claim 1, characterized in that the oxidized, sulfited native oil is obtained in that native oil is oxidized so that the

The difference Δd in the specific weights of the unoxidized and oxidized native oil is in the range from 0.01 to 0.1 g / ml, preferably in the range from 0.03 to 0.05 g / ml, and the native oil thus oxidized is subsequently present 2 to 8 wt .-% of its weight, preferably with 3 to 5 wt .-% of its weight, with a sulfite - calculated as sodium bisulfite (Na ₂ S2θ ₅ ) - and that the oxidized, sulfated native oil is obtained that native oil is oxidized such that the difference Δd in the specific weights of the unoxidized and oxidized native oil is in the range from 0.01 to 0.1 g / ml, preferably in the range from 0.03 to 0.05 g / ml, lies, and then the oxidized native oil with 3 to

9, preferably with 4 to 8 wt .-% of its weight with H ₂ SO ₄ - calculated as 98 wt .-% - aqueous H ₂ S0 ₄ solution - is implemented.

3. fatliquor according to one of claims 1 or 2, characterized in that the emulsifier mixture B 20 to 60, preferably 25 to 50, particularly preferably 28 to 40 wt .-%, a component bl or a mixture of components bl, 20 to 70 , preferably 25 to 60, particularly preferably 30 to 45% by weight of a component b2 or a mixture of the components b2 and 10 to 50, preferably 15 to 40, particularly preferably 22 to 32% by weight, a component b3 or a mixture of components b3 contains - each based on the total weight of the emulsifier mixture.

4. fatliquoring agent according to any one of claims 1 to 3, characterized in that the component bl least one alkoxylated with 4 to 12 alkylene oxide units C ₈ - to C ₁₂ - alkanol, preferably at least one alkoxylated with from 4 to 12 alkylene oxide units C ₁₀ Alkanol, and / or that component b2 is at least one Cχ to C ₂₀ alkanol alkoxylated with 15 to 40 alkylene oxide units, preferably a ₆ to cis alkanol alkoxylated with 15 to 40 alkylene oxide units, and / or the component b3 at least one alkoxylated with 50 to 100 alkylene oxide units C ₁₄ - to C ₂ o-alkanol, preferably a 50 to 100 alkylene oxide

Units alkoxylated C ₁₆ to C ₁₈ alkanol.

5. fatliquor according to one of claims 1 to 4, characterized in that the polymer of the general formula (I) has a viscosity of 30 to 1000 mPa ^« s, preferably from 80 to 500 mPa'S, - measured in pure substance at 20 ° C. ,

6. fatliquor according to one of claims 1 to 5, characterized in that in the compound of the general formula (II) R ¹ and R ^{2 are} independently selected from the group methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, n-octyl, n-dodecyl, n-tridecyl, n-tetradecyl and n-hexadecyl and / or M ⁺ = H ⁺ or Na ⁺ .

7. fatliquor according to one of claims 1 to 6, characterized in that the fatliquor 45 to 98 wt .-%, preferably 70 to 96 wt .-%, particularly preferably 78 to 95 wt .-%, a component A or a mixture components A, 2 to 15% by weight, preferably 3 to 10% by weight, particularly preferably 3 to 8% by weight, component B or a mixture of components B, and 0 to 20% by weight, preferably 0.5 to 10% by weight, particularly preferably 1 to 7% by weight, of a component C or a mixture of components C, and 0 to 20% by weight, preferably 0.5 to 10% by weight , particularly preferably 1 to 7 wt .-%, of a component D or a mixture of components D, - each based on the total weight of the fatliquor.

8. Aqueous preparation for the production and / or treatment of leather and hides, characterized in that it contains 40 to 80% by weight of a fatliquor according to claims 1 to 7.

9. Use of a fatliquor according to one of claims 1 to 7 or a preparation according to claim 8 in the manufacture and / or treatment of leather and skins.

10. Process for greasing in the manufacture and / or treatment of leather and skins, characterized in that the leather or skins are treated with aqueous liquors which contain greasing agents according to claims 1 to 7.