EP1488013A1

EP1488013A1 - Use of polyelectrolytes in the production of leather

Info

Publication number: EP1488013A1
Application number: EP03709772A
Authority: EP
Inventors: Stephan Hüffer; Gunther Pabst; Tilman Lüdecke TAEGER; Stefan Schroeder; Philippe Lamalle
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2002-03-15
Filing date: 2003-03-12
Publication date: 2004-12-22
Also published as: WO2003078664A1; JP2005527658A; BR0308353A; AR038964A1; CN1291041C; KR20040099330A; AU2003214115A1; CN1643166A; US20050210596A1

Abstract

The invention relates to a method for producing semi-finished goods and intermediate stages in the production of leather using one or more organic polyelectrolytes. The inventive method comprises at least one of the following steps: (a) adding one of more polyelectrolytes and 0 0.7 wt. % lime, in relation to the salt weight, directly before or in the lime pit, (b) adding one or more polyelectrolytes prior to or during decalcification, (c) adding one or more polyelectrolytes prior to or during descaling, (d) adding one or more polyelectrolytes and a total of between 0 - 3 wt. % alkali or alkaline earth salt, in relation to the pelt weight, directly prior to or during the pickling process.

Description

Use of polyelectrolytes in leather production

description

The present invention relates to the use of one or more organic polyelectrolytes for the production of leather or fur skins. In particular, the present invention relates to a process for the production of semi-finished products and intermediates in the production of leather using one or more organic polyelectrolytes, comprising at least one of the following steps:

(a) addition of one or more polyelectrolytes and 0 to 0.7% by weight of lime, based on the salt weight, immediately before or in the liming,

(b) adding one or more polyelectrolytes before or during decalcification,

(c) adding one or more polyelectrolytes before or during the pickling,

(d) addition of one or more polyelectrolytes and a total of 0 to 3% by weight of alkali metal or alkaline earth metal salt, based on the pelt weight, immediately before or in the pimple.

During leather production, the skin goes through the pH range from strongly alkaline to acidic at least once. Collagen, which is an essential component of animal skins, is converted into the various charge states anionically, neutrally or zwitterionically and cationically. So-called swellings, also known as acid swellings, are observed in particular at an acidic pH. The swellings generally cause irreversible damage to the skin to be tanned, in particular to extreme loose grain and greatly reduced tear resistance, see a. F. Stather, tanning areas and tanning technology, Akademie Verlag Berlin, 3rd ed. P. 84, 1957.

In order to avoid the swelling, tanneries usually add significant amounts of table salt to the pickle fleets or the formulations in the so-called pickle, generally 4 to 7% by weight, based on the weight of the skin. This results in a considerable salt load in the wastewater.

Attempts have also already been made to use so-called non-swelling acids based on naphthalenesulfonic acids or naphtholsulfonic acids and the corresponding alkali salts (see, for example, E. Heidemann, Fundamentals of Leather Manufacturing, Roether-Verlag Darmstadt, pages 197-9, 1993). It is to be take care that the use of non-swelling acids can reduce the salt load, but at the same time significantly increase the COD value of the wastewater. Even against the background of the poor biodegradability of the above-mentioned non-swelling acids, the environmental friendliness of the tanning process cannot be sustainably improved.

Swelling also occurs in the alkaline pH range, especially in the liming. Around 3% by weight of lime in the form of CaO or hydrated lime (hydrated lime) is usually added to the liming. Furthermore, 1.5 to 2% by weight of NaSH or Na ₂ S is added to the liming agent as a depilatory agent. It is observed that the lime only dissolves to a certain percentage, the rest remains undissolved as sediment, but is important for the process. The high amount of lime is held responsible for significant environmental problems. The calcium salt load in the wastewater has to be reduced by complex measures. Attempts to replace calcium with sodium in the form of sodium hydroxide or sodium carbonate are reported by P. Thanikaivelan et al. in JALCA 2001, 96, 222. However, the results were unsatisfactory. For example, leathers made using sodium carbonate or sodium bicarbonate were not soft enough for commercial purposes' (page 225). Even with sodium hydroxide were un- usually ^'made satisfactorily leather being processed.

J.H. Bowes et al. report in J. Biochem. 1950, 46, 1-8 and 524-9 on the swelling of collagen in alkaline solution. Particularly in alkaline solutions with a pH below 11.5, strong swellings of the collagen are observed.

It is known from DE 29 42 964 that the amount of lime in the liming can be reduced by up to 50% (page 4, line 14) if polyacrylic acid with a K value of 10 to 150 is added, determined according to Fikentscher. Smoother pelts and leather with less lime shade are obtained (Examples 5 and 6).

From DE 29 42 858 it is known that by adding polyacrylic acid with K values over 150, determined according to Fikentscher, the formation of chafe marks can be reduced. Such high molecular weight polyacrylic acid is difficult to handle, however, because solutions with 1% by weight of high molecular weight polyacrylic acid already have such high viscosities that the solutions cannot be applied.

From DE 19 30 225 it is known that a copoly er of 155 parts of acrylic acid and 31.5 parts of dimethyl sulfate-quaternized dimethylaminoethyl methacrylate as an additive to a conventional one Pimples with 5% by weight of table salt (example b), based on the weight of the nakedness, can be used for the pimples.

From FR 14 15 763 a method for pickling sheep's bare skin is known, in which polyacrylic acid is added to a classic pickle with 5% by weight of table salt, based on the skin.

The present invention is therefore based on the object of providing a method for producing leather which avoids the above-mentioned disadvantages of the prior art. In particular, the object of the present invention was to provide a method by means of which wastes which can be recycled more easily can be obtained during the splitting.

It has now surprisingly been found that the object can be achieved by using organic polyelectrolytes in the manufacture of semi-finished products and intermediate stages in the manufacture of leather. The present invention therefore relates to a process for producing semifinished products and intermediates in the production of leather using one or more organic polyelectrolytes, comprising at least one of the following steps:

(b) adding one or more polyelectrolytes before or during decalcification,

(c) adding one or more polyelectrolytes before or during the pickling,

Semi-finished products and intermediate stages in leather production or the production of fur skins are understood to mean those semi-finished products and intermediate stages which pass through the skins' after the various stages in the production of leather before the actual tanning, known to the person skilled in the art, for example, as nakednesses and pimples.

Organic polyelectrolytes are generally understood to mean organic polymers with a large number of ionically dissociable groups, which can be an integral part of the polymer chains or can be attached to the side. In general, each of the statistical repeat units carries at least one group that is ionically dissociable in aqueous solution. In the context of the present invention, so-called ionomers are also counted among the organic polyelectrolytes, which are those organic polymers in which many, but not every repeating unit carries an ionically dissociable group. Polymers with only one or two ionizable groups at the respective chain ends, or in the case of branched polymers a number of dissociable groups corresponding to the number of chain ends, are not polyelectrolytes for the purposes of the present invention.

Polybases, polyacids, polyampholytes or their polysalts or mixtures thereof can be used in the process according to the invention. Polyacids are organic polyelectrolytes which dissociate in an aqueous medium with the elimination of protons, for example polyvinylsulfonic acid, polyvinylsulfuric acid, polyvinylphosphonic acid, polymethacrylic acid or polyacrylic acid or copolymers. Polybases are organic polyelectrolytes which contain groups or residues which can be protonated by reaction with Bronsted acids, for example polyethyleneimines, polyvinylamines or polyvinylpyridines. Polyampholytes are usually understood to mean those polymers which contain both repeat units which dissociate in an aqueous medium with the elimination of protons, and also repeat units which can be protonated by reaction with Bronsted acids. Poly salts are usually understood to mean single or in particular multiple deprotonated polyacids.

Synthetic polyelectrolytes are preferably used in the process according to the invention.

The organic polyelectrolytes used in the process according to the invention are known as such and preferably contain at least 3 identical or different repeat units of the general formulas I to IV

For the purposes of the present invention, polyelectrolytes are also to be understood as meaning those polymers having repeating units I to IV which are not linear, but are branched, crosslinked, hyperbranched or dendrimeric and in which the repeating units A ¹ , A ² and / or A ¹ * are not exclusively are terminal.

Other organic polyelectrolytes which can be used in the process according to the invention have at least 3 repeat units of the formulas V a or V b:

The variables are defined as follows:

n is an integer from 3 to 50,000, preferably 20 to 10,000 and particularly preferably up to 5000.

A ^ A ¹ * ionic or ionizable groups of the formulas VI to XIII

in which the variables are defined as follows:

R ¹ are the same or different and selected from each

Hydrogen, OH, CN,

Cχ-C o-alkyl, selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl, n-pentyl, iso-pentyl, sec.- Pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-a yl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-hexadecyl and n-egg cosyl; preferably -C ₆ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl , Neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, particularly preferably C 1 -C ₄ -alkyl such as methyl, ethyl, n-propyl, iso-propyl , n-butyl, iso-butyl, sec-butyl and tert-butyl;

C -C o-hydroxyalkyl, for example 2-hydroxy-n-propyl, preferably ύ-C ₂ -C o-hydroxyalkyl, for example 2-hydroxyethyl, 2-hydroxy-n-propyl, 3-hydroxypropyl, 4-hydroxy- n-butyl, 6-hydroxy-n-hexyl, ω-hydroxydecyl, ω-hydroxy-n-dodecyl, ω-hydroxy-n-hexadecyl or ω-hydroxy-eicosyl;

C ₆ -C ₁₄ aryl, for example phenyl, α-naphthyl, β-naphthyl, 9-anthracenyl, in particular phenyl, Ci-C _δ alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert. -Butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy;

Carboxylic acid esters, for example C00CH ₃ , C00C ₂ Hs, COO-nC ₃ H ₇ ,

COO-iso-C ₃ H ₇ , COO-nC ₄ H ₉ , COO-iso-C ₄ H ₉ , COO-tert. -CH ₉ , COO- CH ₂ CH (C ₂ H ₅ ) (CH ₉ ), COO-CH ₂ CH ₂ OH, COO-CH ₂ -CH ₂ -CH ₂ -OH, COO- (CH ₂ ) ₄ -OH , COO- (CH) ₆ -OH, COO (CH ₂ -CH ₂ -0) _r -H, COO (CHCH ₃ -CH ₂ -0) _r -H; in which

r is an integer from 1 to 100, preferably 2 to 50;

Carboxamides CO-NR ³ R ⁴ or CO-NR ³ RCH ₃ ⁺ or CO-NR ³ R ⁴ C ₂ H ₅ ⁺ ,

Groups of the formula CO-X ¹ - (CH ₂ ) _m -NR ³ R ⁴ or CO-X ¹ - (CH ₂ ) _m -NR ³ RCH ₃ ⁺ or

CO-Xl- (CH ₂ ) χ _π -NR ³ RC ₂ H ₅ ⁺ ,

in which

m is an integer from 0 to 4, preferably 2 or 3,

X ^{1 is} oxygen or NH,

and the optionally occurring positive charge or positive charges are saturated by counterions such as Cl ^~ or CH S0 ₄ ^~ .

R ² is selected from hydrogen,

-C ₂ -o-alkyl, selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-hexadecyl and n-eicosyl; preferably -C ₆ alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl , neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, particularly preferably C 1 -C 4 -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n- Butyl, iso-butyl, sec-butyl and tert. Butyl; δ

- C ₃ -C ₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;

C ₇ -C ₃ aralkyl, preferably C ₇ to C 1 phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1 -Methyl-1-phenylethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl;

C ₆ -Cχ ₄ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9th -Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;

- C -C o-Hydroxyalkyl, for example 2-hydroxy-n-propyl, preferably ω-C-C o-hydroxyalkyl, for example 2-hydroxyethyl, 2-hydroxy-n-propyl, 3-hydroxypropyl, 4-hydroxy- n-butyl, 6-hydroxy-n-hexyl, ω-hydroxydecyl, ω-hydroxy-n-dodecyl, ω-hydroxy-n-hexadecyl or ω-hydroxy-eicosyl, very particularly preferably 2-hydroxyethyl.

R ³ and R ⁴ are the same or different and selected from hydrogen and -CC ₄ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert.- butyl.

A ² ionic or ionizable groups, preferably selected from

-N (R ² ) -, -C0-N (R ² ) -, -N ⁺ (R ² ) ₂ -, -CO-N ⁺ (R ² ) ₂ -, wherein R ² is defined as above.

Anions such as, for example, halide, preferably chloride or bromide, and also sulfate, hydrogen sulfate, phosphate, silicate, hydrogen phosphate and / or dihydrogen phosphate are used to saturate positive charges in the polyelectrolyte according to the invention.

In at least one repeating unit per molecule, R ² is not equal to hydrogen, ie at least one nitrogen atom is exhaustively alkylated, arylated or aralkylated.

M is selected from Hydrogen,

Alkali metal ions, for example Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ or Cs ⁺ or mixtures thereof, preferably Na ⁺ or K ⁺ ,

Ammonium ions of the general formula N (R ⁵ ) ⁺ , where the radicals R ^{5 are} identical or different and selected from

-C-C o-alkyl, selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec.- Pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl , n-dodecyl, n-hexadecyl and n-eicosyl; preferably Cχ-C ₆ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl , neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, particularly preferably Cχ-C ₄ -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert. Butyl;

C ₃ -Cχ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;

C ₇ -Cχ aralkyl, preferably C - to Cχ ₂ -phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1- Methyl-1-phenylethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl;

C ₆ -Cχ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthrhryl, 3-phenanthryl, 4-phenanthryl and 9- Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;

C -C o-hydroxyalkyl, for example 2-hydroxy-n-propyl, preferably ω-C -C o ~ hydroxyalkyl, for example 2-hydroxyethyl, 2-hydroxy-n-propyl, 3-hydroxypropyl, 4-hydroxy-n -butyl, 6-hydroxy-n-hexyl, ω-hydroxydecyl, ω-hydroxy-n-dode-cyl, ω-hydroxy-n-hexadecyl or ω-hydroxy-eicosyl, very particularly preferably 2-hydroxyethyl,

- and especially hydrogen. Mixtures of the aforementioned ions can also be selected.

In a preferred embodiment, repeating units III of the polyelectrolytes used according to the invention are designed such that A ^{1 is} COOH and A ¹ * C00 (CH ₂ -CH ₂ -0) _r -H.

At least 15 mol% of the repeating units A ¹ in formula I or III are preferably selected from COOH or COOM groups, and M is as defined above.

In each case two of the radicals A ¹ and A ¹ * can be connected to one another to form a divalent ring system with 1 to 20 ring members, for example in the manner of the following formula XIV (three ring members):

In formula XIV, X stands for a divalent group such as CH ₂ , 0 or NH, N-Cχ-Co-alkyl or also N ^~ , the negative charge being saturated by the above-mentioned cations and the alkyl radicals being as defined above.

The polyelectrolytes used according to the invention preferably contain carboxyl groups, the carboxyl groups being present as free acid or completely or to a certain percentage as a salt, i.e. in a neutralized form. It is preferred that the carboxyl groups are neutralized to a certain percentage. For example, 20 to 99 mol%, particularly preferably 50 to 95 mol%, of neutralized carboxyl groups are particularly suitable.

Very high molecular weight compounds which are produced from at least 60 mol% of the monomers acrylic acid, methacrylic acid and maleic acid or mixtures thereof or the relevant salts are very particularly preferably used as polyelectrolytes. In particular, these include polyacrylates or polyacrylic acid-maleic anhydride copolymers with a molar proportion of maleic anhydride of 1 to 40%, especially 1 to 15%.

In order to arrive at the polyelectrolytes known per se used according to the invention, polymers or copolymers are synthesized by known processes, which are composed of one or more known olefinically unsaturated monomers. Before- Drawn monomers which give the polyelectrolytes used according to the invention in the polymerization are olefinically unsaturated mono- or polyvalent carboxylic acids. Acrylic acid, methacrylic acid, crotonic acid, fumaric acid and maleic acid are particularly preferred; acrylic acid, methacrylic acid and maleic acid are very particularly preferred. Acrylic acid, methacrylic acid and maleic acid can also be used well as an anhydride in the polymerization. All monomers can be used in the polymerization as free acids, as a salt in neutralized form according to the above definition and also as a mixture of free acid and salt. The polyelectrolytes are synthesized by methods known per se. The polymerization is preferably carried out by free radicals, as described, for example, in DE-A 31 38 574.

Comonomers can also be used in the polymerization. Suitable comonomers are, for example

Vinyl ethers such as, for example, methyl vinyl ether, ethyl vinyl ether, vinyl n-propyl ether, vinyl isopropyl ether, n-butyl vinyl ether, vinyl isobutyl ether, vinyl tert-butyl ether,

(Meth) acrylic acid derivatives such as methyl acrylate, methyl ^{'methacrylate,} ethyl acrylate, ethyl methacrylate, acrylamide, methacrylamide, tert. -Butyl acrylamide, tert. -Butyl acrylate, tert-butyl methacrylate, acrylonitrile,

Olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene 1-decene, 1, 3-butadiene, isobutene, isoprene, vinyl chloride, vinylidene chloride;

Vinyl aromatics such as styrene, α-methylstyrene,

Maleimide, N-methyl maleimide.

Mixtures of the comonomers listed above are also suitable.

In order to obtain the polyelectrolytes with the repeating units Va and / or Vb known per se and used in the process according to the invention, benzenesulfonic acid or naphthylsulfonic acid is usually condensed with one or more aldehydes of the general formula R ⁱ -CHO at temperatures of, for example, 80 to 120 ° C. and Pressures from 1 to 20 atmospheres, for example. The use of polyelectrolytes which contain monomers with hydrolyzable units is also considered to be according to the invention if the hydrolyzable units are fully or partially hydrolyzed.

The polyelectrolytes used according to the invention have a number average molecular weight from 500 to 150,000 g, preferably from 1000 to 70,000 g and particularly preferably up to 10,000 g. The width of the molecular weight distribution M _w / M _n is in the range from 1.2 to 50, preferably 1.5 to 15 and particularly preferably 2 to 15.

The polyelectrolytes used according to the invention preferably carry an average of at least 3 repeating units I to IV per molecule, it being possible for these groups or repeating units to be the same or different. The polyelectrolytes used according to the invention preferably carry on average at least 4 groups of the formulas I to IV, particularly preferably at least 5.

The polyelectrolytes described above can be used at various stages in processes for the production of semifinished products and intermediate stages in the production of leather or in the production of fur skins.

The polyelectrolytes described above are preferably used in the liming, before or in the decalcification, before or in the pickle or before or in the pimple.

A particular aspect of the present invention is the use of the organic polyelectrolytes described above in the liming, and another aspect of the present invention is a method of treating skins by using the polyelectrolytes described above in the liming.

In the following, data in% by weight relate to the salt weight, unless stated otherwise.

To use the organic polyelectrolytes described above in the liming, the procedure is expediently that the amount of lime is significantly reduced and instead an inorganic basic alkali metal compound, for example a hydroxide or a carbonate of an alkali metal, preferably of sodium or potassium and very particularly preferably of sodium, and add one or more of the polyelectrolytes described above. Other suitable inorganic basic alkali metal compounds are alkali metal silicates. A preferred variant of the method according to the invention consists in reducing the amount of lime used in the liming to 0.1 to 0.7% by weight, particularly preferably 0.01 to 0.5% by weight. In another particularly preferred variant, lime is completely dispensed with.

According to the invention, 0.001 to 100% by weight of one or more polyelectrolytes is added, preferably 0.005% to 50% by weight. 0.03 to 10% by weight are particularly preferred, 0.1 to 5% by weight being very particularly preferred.

The polyelectrolyte (s) can be added individually or together with the inorganic basic alkali metal compound (s). One or more polyelectrolytes and the inorganic basic alkali metal compound (s) can also be added in one portion or in several portions and in each case before or during ashing. It is preferred to add it immediately at the start of ashing. It is also in accordance with the invention, for example, to add a portion of polyelectrolyte immediately before the liming or during or at the end of the switch and a further portion - together with the inorganic basic alkali metal compound (s) - during ashing. If one wishes to add the polyelectrolyte or polyelectrolytes in ^" several portions, the quantitative ratio of polyelectrolyte in the individual portions is not critical. It has proven to be expedient to choose portions of approximately the same size. Another conceivable variant is in the first portion Add 1.1 to 10 times as much polyelectrolyte as in the second; another conceivable variant is to add 1.1 to 10 times as much polyelectrolyte in the second portion as in the first. Analogously, the amount of the inorganic basic or to be added can Alkali metal compounds can be divided into several portions.

In a further variant of the process according to the invention, the polyelectrolyte is changed in situ; for example, polyacrylates or polymethacrylates can be used as the polymeric acids and converted into the polyalkali metal salt of the polyelectrolyte in question by the basic alkali metal compound used.

According to the invention, the polyelectrolyte (s) can be added in bulk or in solution, preferably in aqueous solution. In a preferred variant of the process according to the invention, in addition to the organic electrolytes described above, one or more amine compounds are added in the liming, in particular one or more hydroxylamine compounds or hydrazine compound fertilize. Hydroxylamine compounds obey the general formula XV a or b

R7

R ⁵ R ⁷ R5 /

\ / \

0—N 0 - -N ⁺ - R ⁸ [anion]

\ \

R6 R6

XV a XV b

in which the variables are defined as follows:

R ⁵ to R ⁸ are the same or different and selected from

Hydrogen,

Cχ-C ₂₀ alkyl,

C ₆ -Ci ₄ aryl,

wherein alkyl and aryl radicals are defined as above.

At least one of the radicals R ⁵ to R ⁸ in formula XV a or XV b is preferably hydrogen.

As an anion, for example, halide, preferably chloride or bromide, sulfate, hydrogen sulfate, phosphate, hydrogen phosphate and / or dihydrogen phosphate may also be mentioned.

The use of hydroxylamine compounds of the general formula XV a is preferred. The use of hydroxylamine as the free base is very particularly preferred.

Hydrazine compounds obey the general formula XVI

R ⁵ R7 \ / XVI

N- N / \

_R 8 R6

in which the radicals R ⁵ to R ^{8 are} as defined above and which may be protonated. If one or more hydroxylamine compounds of the general formula XV a are used, the amount of basic alkali metal compound can be reduced.

It is particularly favorable to use one or more hydroxylamine compounds of the general formula XV a or XV b or one or more hydrazine compounds of the formula XIV together with alkali metal hydroxide and alkali metal carbonate in the liming in addition to the polyelectrolyte.

The amount of hydroxylamine compounds of the general formula XV a or XV b or one or more hydrazine compounds of the formula XIV, which is preferably used in the liming, is 0.5 to 10% by weight.

Of course, tanning agents which are customary in tanning, such as biocides, enzymes, depilatory agents, surfactants and emulsifiers, can also be added to the solution of the polyelectrolyte.

Another aspect of the present invention is the addition of one or more of the polyelectrolytes described above before or during the decalcification. According to the invention, 0.001 to 100% by weight of one or more polyelectrolytes is added, preferably 0.005% to 50% by weight. 0.03 to 10% by weight are particularly preferred, 0.1 to 5% by weight being very particularly preferred.

Another aspect of the present invention is the addition of one or more of the polyelectrolytes described above before or during the pickling. According to the invention, 0.001 to 100% by weight of one or more polyelectrolytes is added, preferably 0.005% to 50% by weight. 0.03 to 10% by weight are particularly preferred, 0.1 to 5% by weight being very particularly preferred.

Another particular aspect of the present invention is the use of the polyelectrolytes described above in front of or in the pimple, preferably immediately before the pimple, and a further aspect of the present invention is a method for treating skins by using the polyelectrolytes described above in or before the pimple.

In the following, the data in% by weight relate to the weight of the skin, unless stated otherwise.

To use the polyelectrolytes described above in front of or in the pimple, one can expediently proceed by reducing the amount of salt used (usually 5 to 10% by weight) of alkali metal halide, usually common salt, and instead using an used amount of one or more polyelectrolytes.

According to the invention, 0.001 to 100% by weight of one or more polyelectrolytes is used, preferably 0.005% to 50% by weight. 0.03 to 10% by weight are particularly preferred, 0.1 to 5% by weight being very particularly preferred.

According to the invention, 0 to 3, preferably 0 to 1 and particularly preferably 0 to 0.5% by weight of one or more inorganic alkali metal or alkaline earth metal salts, for example alkali metal halides such as sodium fluoride, are added before or in the pimple, preferably immediately before the pimple. Sodium chloride, sodium bromide, potassium chloride or potassium bromide or mixtures thereof. Other inorganic alkali metal salts such as Glauber's salt (sodium sulfate) or inorganic alkaline earth metal salts such as magnesium chloride or magnesium sulfate can also be added. In a very particularly preferred variant, at least 0.01 to 0.2% by weight of inorganic alkali metal or alkaline earth metal salts, in particular sodium chloride, are used; in another very particularly preferred variant, the use of alkali or alkaline earth metal salts is dispensed with entirely. It is very particularly preferred to use a maximum of 0.05% by weight of alkali metal halide, in particular sodium chloride.

The addition of one or more polyelectrolytes and alkali or alkaline earth metal salts, so an addition of alkali or alkaline earth metal salts is desired, can be carried out separately and together and immediately before or during picking. One or more polyelectrolytes and - if desired - alkali metal or alkaline earth metal salts can also be added in one portion or in several portions and in each case before or during picking. It is also in accordance with the invention, for example, to add a portion of polyelectrolyte immediately before picking and a further portion - together with alkali or alkaline earth metal salt - during picking. If one wishes to add the polyelectrolyte or polyelectrolytes in several portions, the quantitative ratio of polyelectrolyte in the individual portions is not critical. It has proven expedient to choose portions of approximately the same size. Another conceivable variant is to add 1.1 to 10 times as much polyelectrolyte in the first portion as in the second; Another conceivable variant is to add 1.1 to 10 times as much polyelectrolyte in the second portion as in the first. Analogously, the amount of the alkali metal or alkaline earth metal salts to be added can be distributed over several portions. According to the invention, the polyelectrolyte (s) can be added in bulk or in solution, preferably in aqueous solution, it being possible to add auxiliaries customary in tanning, for example biocides, acids such as sulfuric acid, formic acid, hydrochloric acid, oxalic acid or acetic acid, acidic salts, buffers, Fatliquoring agents, resin tanning agents, vegetable tanning agents and fillers, for example kaolin or ligin sulfonate.

The dwell time of the skins in the pimple is usually 10 minutes to 24 hours, preferably 15 minutes to 2 hours and particularly preferably 15 to 45 minutes in the process according to the invention. The picking takes place under conditions otherwise usual in tanning, the temperature is 10 to 35 ° C. and the pressure 1 to 10 bar, normal pressure is particularly expedient.

If, according to the invention, one or more polyelectrolytes are added before or in the liming, the amount of added polyelectrolyte can be reduced in the pimple. In extreme cases, one can do without the additional addition of further polyelectrolytes in or immediately before the pimple.

In a special variant of the process according to the invention, 5 to 100% by weight of one or more polyelectrolytes are added in the liming and in the further steps, decalcification, pickling and pimples, there is no need to add further polyelectrolytes because the concentration of polyelectrolytes is high is enough. In a preferred variant of the process according to the invention, in which the addition of lime is completely dispensed with, a separate decalcification step can be dispensed with; in particular in this variant, a further addition of polyelectrolyte can be dispensed with.

The process according to the invention not only enables semi-finished products and intermediate stages in the production of leather to be obtained which have improved properties compared to the prior art. It is also possible to significantly reduce the wastewater pollution according to the invention. Not only is there a reduction in the sludge load, which consists of lime itself and lime-precipitated organic and inorganic by-products from the manufacture of semi-finished products and intermediate stages, but also a reduced COD value, making wastewater treatment significantly easier and therefore advantageous becomes. Another aspect of the present invention are semi-finished products and intermediates which have been produced by the process according to the invention.

Subsequently, the semi-finished products and intermediate stages are further processed according to methods customary in tanning, i.e. one tans, optionally after a pretanning step, with the usual means, for example Cr (III) compounds, aldehydes, syntans or polymer tannins or a mixture thereof. This is followed by the usual tannery steps such as dyeing, greasing and retanning.

Another aspect of the present invention are leathers which are produced by tanning semifinished products and intermediate stages which have been produced by the process according to the invention. They are characterized by particularly advantageous application properties, in particular by increased tear strength, dyeability and fullness.

The invention is illustrated by working examples.

Working examples:

The values in% by weight relate in each case to the salt weight, unless stated otherwise.

General working instructions for softening hides:

The skin of a South German cattle was first pre-soaked at 28 ° C with 200% by weight of water and 0.2% by weight of an Eusapon® W in a barrel at low speed for 120 minutes. The liquor was drained and then the skin was soaked with 100% by weight of water, 0.2% by weight of Eusapon® W and 0.5% by weight of soda for 19 hours, the barrel being rotated for 5 minutes each hour , The fleet was then drained.

General work regulations:

1. Ashes

80% by weight, based on the salt weight, of water and 1.0% by weight of Mollescal® SF from BASF Aktiengesellschaft were added to the softened skin of a southern German cattle. After a running time of 30 minutes, 0.8% by weight of NaHS and 1% by weight of lime were added. After a further 30 minutes running time, 0.75% by weight NaS was added. After a further 30 minutes of running time, 1.0% by weight of lime and again 0.75% by weight of NaS were added. After 20 minutes, 70% by weight of water and 1.0% by weight of lime were added and a further 20 minutes left. The liquor was drained and the bare skin rinsed with water.

Subsequently, the ashed nakedness thus obtained was split to a gap thickness of 2.5-2.8 mm and decalcified according to the following procedure:

100% by weight of water and 0.1% by weight of sodium bisulfite and 0.5% by weight of Decaltal® R from BASF Aktiengesellschaft were added to the raw material. After 20 minutes, the liquor was drained off, 50% by weight of water and 0.1% by weight of sodium bisulfite as well as 1.2% by weight of Decaltal® R from BASF Aktiengesellschaft and 0.3% by weight of a mixture consisting of two parts by weight of ammonium sulfate, two parts by weight of formic acid and three parts by weight of adipic acid. The liquor was then drained off and the pelts obtained in this way were cut into strips of about 500 g each.

2. Pimples

Fa Dose% water (20-25 ° C) were ^"SEN The decalcified Rinderblö- prepared by the above method in 15-10-1 Walk barrels. In 100 wt .- inserted. Subsequently, the polyelectrolytes listed in the in Table 1 were in the test barrels are metered in from 1 to 15. Correspondingly, for comparative examples VI to V3, instead of the polyelectrolytes used according to the invention, 7% by weight of common salt (V 1) was used or both (V2) or low molecular weight Picaltal® (V3) was omitted two portions of an acid mixture were added to the test barrels at intervals of 15 minutes, consisting of 50% by weight of formic acid and 50% by weight of a half-concentrated sulfuric acid, each individual portion corresponding to a weight equivalent of 0.6 parts Time until the skin showed complete acid penetration using bromocresol green and, if necessary, corrected the pH of the liquor with concentrated sulfuric acid a to pH 3.0-3.2.

The analysis of the products was carried out by determining the swelling behavior or the change in skin thickness with a thickness meter (mean of a triple determination) and gravimetrically via the amount of water stored (Table 1). Table 1: Pimples of cattle hides

Lignin sulfonate: Borregaard Ind. Ltd., Sampborg, Norway, type DP 581

3. Tanning

For detailed testing of the application-related and physical leather properties, the pimple pelts resulting from Examples 1 to 15 according to the invention and Comparative Examples VI to V3 were first converted into wet-blue semifinished products in 50-1 barrels using the chrome tanning process described below, whereby all percentages by weight relate to the pimple size, unless stated otherwise:

First, the pimple pelts in the respective pimple baths described above were additionally tanned with 1% by weight sodium formate and 7% by weight chromium tanning agent Chromitan® FM for 4 hours at 20 to 40 ° C. Then 0.35% by weight of sodium formate was added and left to stand overnight.

The mixture was then washed with 200% by weight of water and 0.2% by weight of formic acid (15 minutes at 40 ° C.) and the liquor was drained off. It was then washed with 100% by weight of water, 0.5% by weight of sodium bicarbonate, and 2% by weight. % Sodium formate and 1% by weight of a tanning agent based on naphthalenesulfonic acid, commercially available as Tamol® M from BASF Aktiengesellschaft, retanned at a pH of 4.6 to 4.8 and after 1 hour of slow movement at 35 ° C. drained the fleet.

Then, using conventional methods with Luganil®. Colored brown (commercially available from BASF Aktiengesellschaft) at 70 ° C. and with 4% by weight of the lipoderm liqueur® SLW fatliquor and 2% by weight of the Lipoderm Licker® WF fatliquor, both available from BASF Aktiengesellschaft, and 2% by weight .-% formic acid greased. The leather thus obtained was washed with water and dried and stretched out by conventional methods. Then the physical and technical properties were checked.

The physical tensile strength, the tensile strength according to DIN 53328 and the stitch tear strength according to DIN 53331 were determined on the leather samples according to DIN 53329 (Table 2). Furthermore, the grain strength, the fullness and the softness of the leather are rated on a relative scale of 1-5.

Table 2: Application test of the leather according to Examples 1 to 15 and VI to V3

Abundance and softness were rated with marks 1: very good, 2: good, 3: satisfactory, 4: sufficient, 5: poor, 6 unsatisfactory.

Examples 16-25 and comparative examples V4-V5: liming

The softened hides of southern German cattle were fleshed green (about 4 mm thick) and the croupons of the hides were cut into 2.5 kg pieces of skin.

Liming of the comparative examples V4 and V5

For comparative example V4, 100 parts by weight of skin in a rotatable 10-1 barrel with flow-breaking internal internals were successively charged with 60 parts by weight of water, 0.8% by weight of NaSH and 3% by weight of hydrated lime. This was followed by 0.75% by weight sodium sulfide at intervals of 30 minutes. The drum was operated for a further 45 minutes at 15 revolutions / minute. A further 40 parts by weight of water were then metered in. After 10 hours at 23 to 27 ° C. and 5 revolutions / minute, the experiments were ended by draining the liquor and washing the skin twice with 150 parts by weight of water for 15 minutes. Accordingly, for the comparative example V5, the lime content was replaced by 0.9% by weight sodium hydroxide. 1.2. Ashes of Examples 16 to 26 according to the invention

For the tests of Examples 16 to 26 according to the invention, the softened skin pieces were treated in 60% by weight water for 30 minutes at 20-25 ° C. with the polyelectrolyte additives listed in Table 3 (10 revolutions / minute). Then 0.1% by weight of concentrated sodium hydroxide solution and 0.8% by weight of NaHS were metered in at the same time. After 15 minutes, 0.75% by weight sodium sulfide was added three times at intervals of 30 minutes. After a further 15 minutes, the basic agents listed in Table 3 were metered in. After 10 hours at 23 to 27 ° C. and 5 revolutions / minute, the experiments were ended by draining the liquor and washing the skin twice for 15 minutes with 150 parts by weight of water.

2. Further processing (descaling and pimples) of comparative examples V4 and V5 and examples 16 to 25 according to the invention

Decalcification or neutralization was carried out using a mixture consisting of two parts by weight of ammonium sulfate, two parts by weight of formic acid and three parts by weight of adipic acid. For this purpose, the liquor was brought to pH 7.5-8.5 in two metering steps. The penetration of the acid mixture over the skin cross-section was checked with phenolphthalein as an indicator. The time required for this was noted.

The pelts obtained above were then pickled in a conventional pimple bath at 25 ° C. for 30 minutes with 7% by weight of sodium chloride. 1% by weight of Lipoderm Licker® AI was then added and 4% by weight of formic acid were added after a further 20 minutes. After a further half an hour, a pH of 3 was set using concentrated sulfuric acid.

The pimple size (Table 4) was assessed taking into account the criteria of skin thickness increase, weight change (stored water) and the assessment of hair decomposition for completeness. In a further step, to determine the puncture pull-out force according to DIN 53331, the skin pieces prepared above were tanned together in a 50-1 barrel as follows and tanned according to a recipe for producing wet-white furniture leather:

2.5% by weight of a glutardialdehyde formulation, commercially available as Relugan® GT 24 from BASF Aktiengesellschaft, were added to the pimple baths described above. After 90 minutes, 3% by weight of a synthetic tanning agent, commercially available as Basyntan® SW f1. BASF Aktiengesellschaft, given. After 30 minutes, 1% by weight of a tanning agent based on naphthalenesulfonic acid, commercially available as Tamol GM from BASF Aktiengesellschaft, was added and agitated overnight. The mixture was then neutralized with sodium formate and sodium bicarbonate and the liquor was drained off.

The leather thus obtained was washed with water and dried and stretched and folded by conventional methods. Then the physical and technical properties were checked.

The fold thickness of the leather was 2.0-2.2 mm.

Table 3: Use of polyelectrolytes in the liming

Table 4: Analytical data of the wet white furniture leather, made from the bare leather from Table 3

The scar strength was graded as follows: 1 very good, 2 good, 3 satisfactory, 4 sufficient, 5 poor, 6 unsatisfactory.

Claims

Claims:

1. A process for producing semifinished products and intermediates in the production of leather using one or more organic polyelectrolytes, comprising at least one of the following steps:

(b) adding one or more polyelectrolytes before or during decalcification,

(c) adding one or more polyelectrolytes before or during the pickling,

(d) addition of one or more polyelectrolytes and a total of 0 to 3% by weight of alkali metal or alkaline earth metal salt, based on the pelt weight, immediately before or in the spot.

2. The method according to claim 1, characterized in that a polyampholyte is used as the organic polyelectrolyte.

3. The method according to claim 1, characterized in that a polyacid is used as the organic polyelectrolyte.

4. The method according to claim 1, characterized in that a polybase is used as the organic polyelectrolyte.

5. The method according to claim 1, characterized in that a polysalt is used as the organic polyelectrolyte.

6. The method according to any one of the preceding claims, characterized in that one or more hydroxylamine compounds of the general formula XV a or XV b are additionally added in step (a)

R ⁷

R5 R ⁷ R5

\ /

0 - N 0 - N ⁺ R ⁸ [anion]

\ \

R6 R ⁶

XV a ^χ V in which R ⁵ to R ⁸ are the same or different and selected from

Hydrogen,

Cχ-C ₂₀ alkyl,

C ₆ -Cχ ₄ aryl,

and the anion is selected from halide, sulfate, hydrogen sulfate, phosphate, hydrogen phosphate and dihydrogen phosphate or mixtures thereof,

or one or more hydrazine compounds of the formula XVI,

R ⁵ R ⁷

N - N ^

/ \

R ⁸ R ⁶

which can be protonated and in which the radicals R ⁵ to R ^{8 are} as defined above.

7. The method according to claim 6, characterized in that in step (a) hydroxylamine is added.

8. The method according to claim 6, characterized in that one or more hydroxylamine compounds of the general formula XV a or XV b or one or more hydrazine compounds of the formula XVI are used together with alkali metal hydroxide and alkali metal carbonate in step (a).

9. Semi-finished products and intermediates in the manufacture of leather, produced by a process according to claims 1 to 8.

10. Use of semifinished products and intermediates in the manufacture of leather, produced by a process according to claims 1 to 8, for the manufacture of leather.