EP0814168B1 - Procédé de tannage du cuir - Google Patents

Procédé de tannage du cuir Download PDF

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Publication number
EP0814168B1
EP0814168B1 EP97109282A EP97109282A EP0814168B1 EP 0814168 B1 EP0814168 B1 EP 0814168B1 EP 97109282 A EP97109282 A EP 97109282A EP 97109282 A EP97109282 A EP 97109282A EP 0814168 B1 EP0814168 B1 EP 0814168B1
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EP
European Patent Office
Prior art keywords
tanning
chromium
iii
leather
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP97109282A
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German (de)
English (en)
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EP0814168A1 (fr
Inventor
Harro Träubel
Fritz Novotny
Helmut Dr. Reiff
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Bayer AG
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Bayer AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/28—Multi-step processes
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents
    • C14C3/18—Chemical tanning by organic agents using polycondensation products or precursors thereof

Definitions

  • the invention relates to a method for pretanning and tanning leather using blocked polyisocyanates containing ether groups and mineral tannins.
  • the tanning transforms animal skins into leather by cross-linking the collagen.
  • One of the most important characteristics of leather is that of untanned hides increased shrinkage temperature, i.e. the improved hot water resistance, and the white appearance (non-transparent, non-pigment-like) after the Dry.
  • the type of tanning that is still dominant today is chrome tanning that using chromium (III) compounds under the influence of OH ions cross-linking covalent bonds with the carboxyl groups of Collagen are formed.
  • the one with polyfunctional vegetable tannins available hydrogen bonds to the amide groups of collagen are, however, much weaker, which can also be seen in a moderately increased shrinking temperature affects.
  • Aliphatic aldehydes, e.g. Glutaraldehyde, which lead to crosslinking via the primary amino groups of the collagen, has been recommended as tanning agents (US Pat. No. 2,941,859).
  • the emerging aldimines can, however, react reversibly back to aldehyde and amine in the presence of water.
  • aliphatic diisocyanates such as hexamethylene diisocyanate (DE-PS 72 981) has not been able to assert itself for toxicological reasons.
  • the invention relates to a method for tanning using
  • reaction products to be used according to the invention can be derived from the from A, B and optionally C available intermediates with NCO contents from 3 to 50, preferably 5 to 45, in particular 20 to 45% by weight (based on Intermediate) by subsequent blocking of the free isocyanate groups receive.
  • the products according to the invention then contain - calculated as sodium salt and solids-related - 9.7 to 78, preferably 14 to 74, in particular 46.5 to 74% by weight carbamoyl sulfonate groups.
  • Suitable organic polyisocyanates A) are aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic polyisocyanates as described, for example, by W. Siefken in Liebigs Annalen der Chemie 562, pages 75 to 136.
  • Preferred polyisocyanates A) are compounds of the formula Q (NCO) n with an average molecular weight below 800, where n is a number of at least 2, preferably from 2 to 4, Q is an aliphatic C 4 -C 12 -hydrocarbon radical, a cycloaliphatic C 6 - C 15 hydrocarbon radical, an araliphatic C 7 -C 15 hydrocarbon radical or a heterocyclic C 2 -C 12 radical with 1 to 3 heteroatoms from the series oxygen, sulfur, nitrogen, for example (i) diisocyanates such as ethylene diisocyanate, 1.4 -Tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-2-isocyana
  • Particularly preferred polyisocyanates A are those with a molecular weight of 140 to 400 with NCO groups bonded to aliphatics or cycloaliphatics, such as, for example, 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,5-diisocyanato-2,2-dimethylpentane, 2 , 2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,3- and 1,4-diisocyanatohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane, 1-isocyanato-1-methyl-4-isocyanatomethyl-cyclohexane and 4,4'-diisocyanatodicyclohexyl-methane, and any mixtures of such diisocyanates.
  • araliphatic polyisocyanates such as the xylylene di
  • diisocyanates are preferably used.
  • the higher-functionality polyisocyanates are preferably im essentially from trimeric 1,6-diisocyanatohexane or 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane and optionally dimeric 1,6-diisocyanatohexane or 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane and the corresponding higher homologues of isocyanurate groups and optionally polyisocyanate mixtures containing uretdione groups with a NCO content of 19 to 24 wt .-%, as is known by catalytic Trimerization and with the formation of isocyanurate of 1,6-diisocyanatohexane or 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane can be obtained and which preferably have an (average) NCO functionality of 3.2 to 4.2.
  • Suitable polyisocyanates A are modified by aliphatic or Polyisocyanates prepared with cycloaliphatic diisocyanates with uretdione and / or Isocyanurate, urethane and / or allophanate, biuret or oxadiazine structure, such as they for example in DE-OS 1 670 666, 3 700 209 and 3 900 053 and in the EP 336 205 and 339 396 are described by way of example.
  • Suitable polyisocyanates are e.g. also the ester group-containing polyisocyanates, e.g.
  • the use of monofunctional and more than difunctional isocyanates in both cases is preferably to a maximum of each 10 mol%, based on all polyisocyanates A, limited.
  • the polyether alcohols B are accessible in a manner known per se by alkoxylation of suitable starter molecules. Any mono- or polyhydric alcohols with a molecular weight of 32 to 250 can be used as starter molecules to produce the polyether alcohols. Monofunctional aliphatic C 1 -C 18 , preferably C 1 -C 4 alcohols are preferably used as starter molecules.
  • the use of methanol, butanol, ethylene glycol monomethyl ether or ethylene glycol monobutyl ether as starter is particularly preferred.
  • Alkylene oxides suitable for the alkoxylation reaction are in particular Ethylene oxide and propylene oxide, which are in any order at the Alkoxylation reaction can be used. Any other epoxies such as butylene oxide, dodecene oxide or styrene oxide can also be used become. Pure polyethylene oxide alcohols are particularly preferred.
  • Polyalkylene oxide alcohols containing ester groups can also be used.
  • Suitable polyalkylene oxide alcohols containing ester groups are OH-terminated polyester ethers which, by reacting aliphatic C 2 -C 8 -dicarboxylic acids or their esters or acid chlorides with polyethers from the group consisting of polyethylene oxides, polypropylene oxides, their mixtures or mixed polyethers, with 0 per OH equivalent of the polyether, 8 to 0.99 equivalents of carboxyl groups or their derivatives are used, are available and have an average molecular weight below 10,000, preferably below 3,000.
  • the NCO-reactive components C which may also be used include Common mono- to tetrafunctional used in polyurethane chemistry Building blocks such as alcohols, amines, amino alcohols and mercaptans with molecular weights below 6,000, preferably below 2,000, e.g. Polyester, polyetherester, Aminopolyethers and polycarbonates, provided they do not fall under definition B.
  • Preferred components C are "greasing” or “re-greasing” long-chain, optionally branched so-called fatty alcohols or fatty amines 12 to 30 carbon atoms and OH groups containing esters of natural fatty acids such as stearic acid, oleic acid, palmitic acid, linoleic acid, linolenic acid etc.
  • Very particularly preferred components C are natural OH groups Fats and oils such as castor oil.
  • reaction products from the components to be used according to the invention A to D can contain up to 20% by weight of component C.
  • Preferred blocking agents D are the sodium salts of sulphurous or disulphurous acid, ie sodium bisulphite (NaHSO 3 ) or sodium disulphite (Na 2 S 2 O 5 ).
  • alkali and ammonium salts can also be used advantageously these acids, namely potassium bisulfite, potassium disulfite, lithium bisulfite, lithium disulfite, Ammonium bisulfite, ammonium disulfite and simple tetraalkylammonium salts these acids, such as, for example, tetramethylammonium bisulfite, Tetraethylammonium bisulfite, etc.
  • the salts are preferred as aqueous solutions with solids contents of 5 to 40% by weight are used.
  • reaction products to be used according to the invention can be, for example manufacture as follows:
  • the polyisocyanate is reacted with the polyether alcohol B, until all OH groups are urethanized.
  • the NCO end so obtained Prepolymer is then in a second step with alkali or Ammonium bisulfite or disulfite blocked until all NCO groups are implemented are.
  • the entire process is particularly preferably carried out solvent-free as a one-pot process.
  • the reaction (1st step) is carried out in the temperature range up to 130 ° C., preferably in the range between 50 ° C. and 120 ° C., particularly preferably between 80 ° C. and 110 ° C.
  • the reaction can be followed by titration of the NCO content or by measuring the IR spectra and evaluating the carbonyl band at approx. 2 100 cm -1 and is complete when the isocyanate content is not more than 0.1% by weight above the value which is to be achieved with complete sales. As a rule, response times of less than 4 hours are sufficient.
  • NCO prepolymers thus obtained with NCO contents of 5 to 45% by weight are now in a second step at 0 to 60 ° C, preferably at 10 to 40 ° C implemented aqueous solutions of alkali or ammonium sulfites and water, until all NCO groups have reacted. This generally includes response times from 1 to 12, preferably 3 to 8 hours.
  • the end products are optically clear aqueous solutions, in a few isolated cases stable, finely divided Emulsions with average particle diameters below 8000 nanometers.
  • the NCO prepolymers initially with 20 to 50 wt .-% aqueous solutions of the alkali or ammonium bisulfites or disulfites implement and add the remaining water after 5 to 45 minutes, so that then a solids content of the aqueous preparations of 10 to 50% by weight, preferably 25 to 40 wt .-% results.
  • reaction products to be used according to the invention one uses generally amounts of 1 to 20, preferably 3 to 15% by weight of reaction product, based on sheer weight.
  • Suitable mineral tannins are salts of aluminum, chromium, iron, titanium and zircon.
  • 100 ° C are reached and - in Dependence of the quantity used and process control (pH, temperature etc.) - clearly exceeded.
  • a particularly preferred working method is the use of tanning chromium compounds that are stable at high pH values.
  • pH-resistant chromium compounds are described, for example, in EP-A 304 677; there one uses an aqueous solution of basic chromium (III) sulfate and, per mole of chromium oxide of the basic chromium (III) sulfate, 0.2 to 0.8 mol of aliphatic C 4 -C 6 dicarboxylic acid and subsequent adjustment of the theoretical Basicity to 0 to 50% prepared reaction product, the addition of the reaction product to the pickling liquor as an aqueous solution with a chromium oxide content of at least 5% by weight or in powdered form in an amount of 0.9 to 1.5% by weight chromium oxide (based on pelt weight), the liquor volume is less than 100% by weight (based on pelt weight), the final pH is above 4.0 and the final temperature is above 40 ° C.
  • a chromium (III) compound tans
  • Example 1 of EP-A 304 677 describes a product which has 0.2 mol of glutaric acid with a basicity of 30 per mol of Cr 2 O 3 .
  • This product can be added free of salt and pimples in a short liquor of up to pH 9, preferably 5-8, to the material to be tanned without spontaneous precipitation.
  • the tanning proceeds without having to be basified.
  • Shrinking temperatures of approximately 100 ° C. are achieved with quantities of 1.25% by weight of Cr 2 O 3 (based on shaved weight).
  • a particular advantage of such a combined procedure is the high exhaustion of chromium III salt from the residual liquor of the tanning: With a liquor length of, for example, 50 wt leather tanned through (with a Cr 2 O 3 content in the leather of approx. 3% by weight) and in the remaining liquor of this tanning a Cr 2 O 3 content of 0.4 g per liter at a final pH (the pH -Value drops due to the added tanning agent) of 4.1 found.
  • tanning is described in example A 66, in which after pre-tanning with carbamoylsulfonate formic acid and then a commercial self-dulling chrome tanning agent was added. That kind of Tanning already provides leather with a high shrinking temperature and residual liquors sufficiently good chromium depletion. But if you use a formate or dicarboxylate stabilized Chromium tanning agent according to EP-A 304 677 results in one further reduction in the chromium 3 + ion content of the remaining liquor.
  • retanning can be carried out using synthetic organic polymers (incl. resin tanning agents) or with vegetable tanning agents.
  • the average molecular weights mentioned in this application are number average certain molecular weights.
  • the percentages in the following examples relate to the Weight and on nakedness / leather.
  • the liquor is drained, the leathers are rinsed for 10 minutes at room temperature, then they are wilted and folded to a thickness of 1 mm.
  • the folded leather is placed in a barrel and washed for 10 minutes with 200% (based on the fold weight) of water (from room temperature). The fleet is released.
  • the subsequent mineral tanning is carried out by 50% water at 35 ° C (the pH value has set itself to 6.8) and 5% of a product that after Example 1 of EP-A 304677 was initiated. After 150 minutes Movement sets a pH value of 4.1.
  • the fleet is drained, the leathers have a Ts of 100 ° C. After a Wash the fleet with 300% water at 40 ° C (10 minutes). In The neutralization that now begins becomes 200% water (40 ° C), 3% TANIGAN PAK-N 1 hour (pH 4.7), then 4% CUTAPOL TIS-MF (diluted 1: 4) 30 Leave on for minutes. Then drain and 10 minutes at 200% Washed water (35 ° C).
  • the retanning is done with 150% water (40 ° C) started: 3% TANIGAN BN and 2% TANIGAN LF 20 minutes, then one Solution made of 3% BAYGENAL Braun CGG and 2% BAYKANOL TF-2N (1:20 in 60 ° C warm water) added. After 60 minutes, 100% water (70 ° C) added, after a further 10 minutes 2% formic acid (diluted 1: 5) added and let it run for 30 minutes (pH 3.4). After draining the fleet is in 200% water (50 ° C) with a mixture of 8% CORIPOL MK, 6% CUTAPOL TIS-MF and 1% TETRAPOL SAF (1: 4 diluted with 60 ° C water) Greased for 90 minutes.
  • Example A 1 of EP-A 690 135 12 pieces of 100 g of bare bark in 40% liquor with 0.35% magnesium oxide were allowed to run for 1 hour in a test kettle from Dose (pH 7.4), then 7 , 5% (active substance) of a product according to Example 1 of EP-A 690 135 added, after 3 hours a further 0.35% magnesium oxide (pH 6.6) and then let it run overnight.
  • the resulting leather had a Ts of 77 ° C. 5 of these leathers were treated in 100% liquor with 0.05% formic acid and 0.08% sulfuric acid to a pH of 3, a further 3 with 0.08% sulfuric acid to a pH of 4, and one each with 0.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Claims (5)

  1. Procédé pour le tannage avec l'utilisation
    I. de produits de réaction contenant des groupes sulfonate de carbamoyle à partir
    A. de polyisocyanate organique,
    B. par groupe isocyanate de A. de 0,01 à 0,4 équivalents de polyétheralcool avec des unités poly(oxyde d'alkylène) insérées (les équivalents se rapportent aux groupes hydroxyle du polyétheralcool), les unités poly(oxyde d'alkylène) étant constituées de 40 à 100% en mol d'unités poly(oxyde d'éthylène) d'une longueur de séquence de 5 à 70,
    C. éventuellement d'autres constituants NCO-réactifs, et
    D. de bisulfites ou de disulfites d'ammonium ou d'alcalis,
       et ensuite
    II. de matières minérales de tannage de la série du chrome (III), du fer (II), du fer (III), de l'aluminium (III), du titane (IV) et du zirconium (IV) sans picklage à une valeur de pH supérieure à 4.
  2. Procédé selon la revendication 1, d'après lequel on utilise comme matière minérale de tannage un complexe de dicarboxylate en C4-C6 du chrome.
  3. Procédé selon la revendication 1, un sulfate d'ammoniumtitanyle et/ou un sulfate de titanyle complexé par un citrate étant utilisés comme matière minérale de tannage.
  4. Procédé selon la revendication 1, un sel basique d'aluminium actif pour le tannage étant appliqué.
  5. Procédé selon la revendication 1, un composé de zirconium actif pour le tannage étant utilisé.
EP97109282A 1996-06-21 1997-06-09 Procédé de tannage du cuir Expired - Lifetime EP0814168B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19624821 1996-06-21
DE19624821A DE19624821A1 (de) 1996-06-21 1996-06-21 Verfahren zur Gerbung von Leder

Publications (2)

Publication Number Publication Date
EP0814168A1 EP0814168A1 (fr) 1997-12-29
EP0814168B1 true EP0814168B1 (fr) 2000-10-18

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EP97109282A Expired - Lifetime EP0814168B1 (fr) 1996-06-21 1997-06-09 Procédé de tannage du cuir

Country Status (5)

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US (1) US5820634A (fr)
EP (1) EP0814168B1 (fr)
JP (1) JPH1060499A (fr)
DE (2) DE19624821A1 (fr)
ES (1) ES2152594T3 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102321771B (zh) * 2011-08-22 2015-03-11 温州大学 一种非铬类金属复合鞣剂及其制备方法

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Publication number Priority date Publication date Assignee Title
DE102004050284A1 (de) * 2004-10-15 2006-04-27 Lanxess Deutschland Gmbh Isocyanat-basierende Gerbstoffe
EP2415879A1 (fr) 2010-08-06 2012-02-08 LANXESS Deutschland GmbH Compositions comprenant au moins un composé contenant des groupes carbamoylsulfonates et leur utilisation comme agents de tannage
CN102168154B (zh) * 2011-03-24 2013-05-08 黄石圣康医药化工有限公司 一种多核低铬革鞣剂的制备方法
EP2508626A1 (fr) * 2011-04-04 2012-10-10 LANXESS Deutschland GmbH Préparations d'agents de tannage solides particulaires
EP2508627A1 (fr) 2011-04-04 2012-10-10 LANXESS Deutschland GmbH Matériau solide particulaire à base de composés comprenant des groupes de carbamoylsulfonate
CN102242228A (zh) * 2011-05-18 2011-11-16 齐河力厚化工有限公司 一种新型的无盐浸酸皮革助剂
EP2540753A1 (fr) 2011-06-29 2013-01-02 LANXESS Deutschland GmbH Composition à base de composés contenant des groupes de carbamoylsulfonate
WO2013001077A1 (fr) 2011-06-29 2013-01-03 Lanxess Deutschland Gmbh Composition à base de composés contenant des groupes sulfonate de carbamoyle
EP2557224A1 (fr) 2011-08-12 2013-02-13 LANXESS Deutschland GmbH Procédé de coloration de substrats contenant des fibres de collagène
EP2557181A1 (fr) 2011-08-12 2013-02-13 LANXESS Deutschland GmbH Procédé d'hydrophobisation de substrats contenant des fibres de collagène
CN103060484B (zh) * 2013-01-24 2015-03-11 焦作隆丰皮草企业有限公司 一种无盐鞣制的制革方法
EP2607499A3 (fr) * 2013-02-14 2013-07-10 Basf Se Procédé destiné à la fabrication de cuir
CN104046707B (zh) * 2014-06-30 2016-05-11 四川大学 铁-锆-铝配合鞣剂及其制备方法
CN104073575B (zh) * 2014-07-16 2016-07-06 四川大学 基于异氰酸酯的毛皮鞣剂及其制备方法
CN105969920B (zh) * 2016-07-25 2018-02-27 兴业皮革科技股份有限公司 一种基于铁锆铝配合物制备黄牛鞋面革的无铬湿态染整工艺
CN114479061A (zh) * 2022-01-21 2022-05-13 四川大学 一种聚醚胺氯三嗪遥爪聚合物鞣剂、制备方法及应用

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DE2739378A1 (de) * 1977-09-01 1979-03-15 Bayer Ag Wasserloesliche kationische oligourethan-harze und deren verwendung zur behandlung von bloesse oder leder
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US5417723A (en) * 1993-03-25 1995-05-23 Bayer Aktiengesellschaft Use of ester urethanes for retanning
DE4422569A1 (de) * 1994-06-28 1996-01-04 Bayer Ag Bisulfit-blockierte Polyisocyanate als Gerbstoffe

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102321771B (zh) * 2011-08-22 2015-03-11 温州大学 一种非铬类金属复合鞣剂及其制备方法

Also Published As

Publication number Publication date
US5820634A (en) 1998-10-13
DE59702486D1 (de) 2000-11-23
JPH1060499A (ja) 1998-03-03
DE19624821A1 (de) 1998-01-02
ES2152594T3 (es) 2001-02-01
EP0814168A1 (fr) 1997-12-29

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