EP0533011B1 - Procédé pour la production du cuir tanné au chrome - Google Patents

Procédé pour la production du cuir tanné au chrome Download PDF

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Publication number
EP0533011B1
EP0533011B1 EP92115270A EP92115270A EP0533011B1 EP 0533011 B1 EP0533011 B1 EP 0533011B1 EP 92115270 A EP92115270 A EP 92115270A EP 92115270 A EP92115270 A EP 92115270A EP 0533011 B1 EP0533011 B1 EP 0533011B1
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EP
European Patent Office
Prior art keywords
minutes
chromium
chrome
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
EP92115270A
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German (de)
English (en)
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EP0533011A1 (fr
Inventor
Bernhard Dr. Wehling
Franz Dr. Schade
Joachim Dr. Kochta
Herbert Burkhardt
Peter Schindlmayr
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Bayer AG
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Bayer AG
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Publication date
Application filed by Bayer AG filed Critical 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
    • C14C3/04—Mineral tanning
    • C14C3/06—Mineral tanning using chromium compounds
    • 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
    • C14C1/00—Chemical treatment prior to tanning
    • C14C1/08—Deliming; Bating; Pickling; Degreasing

Definitions

  • the peeling material is tanned after picking with standard chrome (III) salts. After mechanical dewatering and any splitting, the resulting wet blue is folded to the desired thickness.
  • the chrome leather produced with the help of the substances described above differs in leather character in terms of feel (see, for example, Das Leder 37 (1986) 12, 221-224), fullness, softness and dyeability from conventionally chrome-tanned and folded leather. Experience has shown that such serious deviations in the property profile are not tolerated by the leather manufacturer and / or processor.
  • a pretreatment can also be carried out with special non-tanning condensation products, which gives a substrate that can be machine-dewatered and folded or split or folded without problems.
  • the skin material pretreated in this way can be stored indefinitely after appropriate preservation under normal conditions.
  • the resulting leather after chrome tanning does not differ in its application properties from conventionally chrome-tanned and folded leather.
  • the invention thus relates to a process for the production of chrome leather, characterized in that the descaled, pickled and pickled skin material in the usual manner in an aqueous liquor with a non-tanning condensation product of (i) aromatic C6-C24-sulfonic acids which are 0.8 to 3 Contain sulfonic acid groups per molecule, and (ii) formaldehyde pretreated and folded after mechanical dewatering or split (in the case of uncleaved pelt material) and folded and then chrome-tanned with commercially available chromium (III) salts and post-treated as usual.
  • the usual aftertreatment generally includes neutralization, retanning, coloring and oiling.
  • the pretreatment agents used according to the invention are condensation products of aromatic sulfonic acids which do not contain any phenolic hydroxyl groups, e.g. those of naphthalene or diaryl ethers, e.g. the ditolyl ether, preferably the ⁇ -naphthalenesulfonic acid, with formaldehyde.
  • Aromatic sulfonic acids preferred for the condensation contain 1 to 2 sulfonic acid groups per molecule.
  • 1.1 to 1.8, preferably 1.4 to 1.5 mol of 100% sulfuric acid can be used per mole of naphthalene.
  • the sulfonation is generally carried out at from 120 to 160, preferably 140 to 150 ° C. it is usually completed within 1 to 3 hours.
  • 0.4 to 0.8, preferably 0.55 to 0.65, mol of formaldehyde are added (mostly in the form of its aqueous solution).
  • the condensation can take place at temperatures from 95 to 120 ° C, preferably from 110 to 120 ° C; it is usually completed within 2 to 5 hours.
  • the mixture is neutralized to a pH of 5 to 8, preferably 6 to 6.5, with alkali metal hydroxide solution or to a pH of 2 to 5, preferably 3 to 3.5, using ammonia.
  • these products are adjusted to an acid number (mgKOH / g) of 20 to 60 with 1 to 8, preferably 3 to 4% by weight, based on the condensation product, of C4-C8-dicarboxylic acid (eg glutaric acid).
  • the condensation products used according to the invention do not have a single-gene effect (Bibliothek des Leders, Vol. 3, p. 65, Umschau-Verlag, Frankfurt / Main, 1st ed. 1985) in the sense of a covalent collagen crosslinking, as is the case, for example, with polyfunctional aldehydes and isocyanates or in Collagen cross-linking by hydrogen bonding with phenol-containing exchange / vegetable tannins or in the sense of collagen cross-linking by complex formation of mineral tannins.
  • a single-gene effect (Bibliothek des Leders, Vol. 3, p. 65, Umschau-Verlag, Frankfurt / Main, 1st ed. 1985) in the sense of a covalent collagen crosslinking, as is the case, for example, with polyfunctional aldehydes and isocyanates or in Collagen cross-linking by hydrogen bonding with phenol-containing exchange / vegetable tannins or in the sense of collagen cross-linking by complex formation of mineral tannins.
  • shrinkage temperatures of less than 65 ° C. are achieved. At the same time, however, they cause extremely strong drainage of the skin material on the wilting machine and enable trouble-free mechanical folding without any signs of burns.
  • the fold thickness of the skin material pretreated in this way corresponds to the thickness of the chrome-tanned finished leather and makes additional folding unnecessary.
  • Another advantage is that the timing of this wet white process largely corresponds to the production rhythm of conventional chrome leather production.
  • the pestle material obtained by customary soaking and liming is descaled in the usual way, pickled and with pH values of organic and / or inorganic acids 2 to 6, preferably 2.5 to 4.5 adjusted (pounded).
  • the pretreatment is then carried out with 3 to 15, preferably 4 to 8% by weight (based on the pelt weight) of the above-mentioned condensation products, calculated as a solid.
  • the hides pretreated in this way can be folded without any problems or, in the case of uncleaved nakedness, split and folded.
  • the skins are then chrome-tanned with commercially available chromium (III) salts and finished in the usual way.
  • the finished leather obtained by the process according to the invention has no differences in the property profile compared to conventionally produced chrome leather.
  • the leathers can be dyed brilliantly and are therefore particularly suitable for the production of high-quality aniline leather for processing into furniture, shoe upper and clothing leather.
  • the shavings obtained by the process according to the invention are chromium-free and offer various options for disposal.
  • condensation products used according to the invention can be used in spray-dried form or as an aqueous solution.
  • dilution ratios mentioned in the following examples relate to parts by weight, the larger number in each case meaning the parts of water.
  • the concentrations of the acids to be diluted correspond to the usual practice: formic acid 85%, sulfuric acid 96%.
  • naphthalene 1 mol of naphthalene is sulfonated with 1.43 mol of 100% sulfuric acid at 145 ° C for 3 hours.
  • the sulfonation mixture is allowed to cool somewhat and is condensed for 3 hours at 115-117 ° C. with 0.64 mol of formaldehyde, which is used in the form of its 30% strength aqueous solution.
  • the reaction mixture is then allowed to cool to 80 ° C. and aqueous ammonia is then added to a pH of 3.5.
  • the product is preferably spray-dried, but can also be used as a 40-60% strength aqueous solution.
  • washed 800 kg of beef pelts (split by 2 mm) in the tanning drum are first washed with 100% (based on pelt weight; like all the following% data) water at 35 ° C. for 15 minutes.
  • the fleet is drained and then is without liquor, decalcified with 1.3% ammonium chloride and 0.4% citric acid for 45 minutes, 80% water at 35 ° C added and pickled with 0.2% of a commercially available pickling agent (with 1500 tryptic units) for 120 minutes (pH value of the liquor 7.7).
  • the cross-section of the nakedness no longer gives a red color with phenolphthalein.
  • the wet whites are unloaded, wilted and, if necessary, folded to 1.0 mm thickness after 24 hours of intermediate storage. About 30 kg of chromium- free shavings are obtained per 100 kg of bare material used.
  • chromium-syntan complex commercially available chromium-containing synthetic retanning agent with 12% chromium (III) oxide
  • the remaining liquor has a chromium (III) oxide content of 1.8 g / l, a final pH of 3.3 and a final temperature of 35 ° C.
  • the mixture is then neutralized to pH 6.5 in the usual way, greased and finished by intermediate drying.
  • the descaled, pickled and pickled pelts (slit thickness 2 mm) in Example 1a) are mixed in the pickling liquor with 2.3% (based on pelt weight, like all the following% data) of a commercially available synthetic fat, and after 15 minutes 9% a commercially available, slightly organically masked chromium (III) sulfate solution with 15% chromium (III) oxide and 40% basicity (according to Schorlemmer) was added. After a running time of 90 minutes, 0.35% magnesium oxide is added and the process is continued for 10 hours. The final pH is 3.8 and the final temperature is 38 ° C. The chromium oxide (III) content of the remaining liquor is 5.9 g / l.
  • the resulting wet blues (with approx. 3.8% chromium (III) oxide, based on anhydrous wet blue) are wilted and folded to a thickness of 1.0 mm.
  • the folded wet blues have the same chromium (III) oxide content as that in example 1a) after the chrome-tanned wet whites have been folded.
  • About 28 kg of chrome shavings with about 3.8% chromium (III) oxide, based on anhydrous chrome shavings, are obtained per 100 kg of bare material used.
  • the mixture is then neutralized to pH 6.5 in the usual way, greased and finished by intermediate drying.
  • the wet white leather produced in example 1a is wilted and folded.
  • 100 kg of folded wet whites in 250% water (based on fold weight; like all the following% data) are mixed with 1.5% of a commercially available, synthetic fat and drummed for 15 minutes.
  • 0.4% formic acid diluted 1:10 with water
  • 0.4% formic acid diluted 1:10 with water
  • a commercially available chrome tanning agent with 26% chromium (III) oxide and 33% basicity (according to Schorlemmer) are added.
  • 3% fat is added (see above).
  • the mixture is then neutralized to pH 6.5 in the usual way, greased and finished by intermediate drying.
  • Example 1a After 24 hours, the wet whites are folded to a thickness of 1 mm and processed as in Example 1a). However, care must be taken to ensure that the pH in the chrome tanning is increased to approximately 3.5 by adding 1.1% (instead of 0.9%) of sodium bicarbonate.
  • Example 4 100 kg of beef peat pretreated as in Example 4 are mixed with 0.5% formic acid (1:10 with water) and 0.6% sulfuric acid (1:10 diluted with water) pickled (pimple pH 3.2). The pretreatment is carried out with 17% of an aqueous solution (50%) of the condensation product to be used according to the invention. The wet whites are then wilted, split and folded as in Example 4 and processed as in Example 2.
  • condensation product 6% of the condensation product to be used according to the invention and 0.1% are now added to the pickling liquor Sodium bisulfite (for H2S elimination) added. After one hour, 1% of a commercially available natural fat (oil product) is added and the product is tumbled on for 12 hours.
  • the final pH is 3.2 and the final temperature is 31 ° C.
  • the wet whites are unloaded, wilted and, if necessary, folded to 1.8 mm thickness after 24 hours of intermediate storage. Approx. 36 kg of chrome-free shavings are obtained per 100 kg of bare material used.
  • the mixture is then neutralized to pH 4.7 with 1.5% of a commercially available neutralizing tanning agent and 0.5% sodium bicarbonate, and the liquor is drained off after 45 minutes.
  • the neutralized Chrome leather is retanned in the usual way (with a combination of exchange, resin or polymer and vegetable tannins), dyed and greased.
  • condensation product to be used according to the invention 4% of the condensation product to be used according to the invention is added to the pickling liquor. After 30 minutes, 0.5% of a commercially available synthetic exchange tanning agent based on bis (4-hydroxyphenyl) sulfone is added. After a further 60 minutes, 1.5% of a commercially available synthetic fat is added and the process is continued for 12 hours.
  • the final pH is 3.5 and the final temperature is 33 ° C.
  • Example 1 After draining off the remaining fleet, the wet whites are unloaded, withered and folded, chrome-tanned and finished as in Example 1.

Landscapes

  • 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 (6)

  1. Procédé de production de cuir tanné au chrome, caractérisé en ce qu'on fait subir un prétraitement à un matériau de peau déchaulée, encuvée et pickelée dans un bain aqueux avec un produit de condensation à effet non tannant à base de (i) acides sulfoniques aromatiques en C₆-C₂₄, qui contiennent 0,8 à 3 groupes acides sulfoniques par molécule, et (ii) formaldéhyde et, après essorage mécanique, on déraie et (dans le cas de matériau de peau planée non refendu) on refend et on déraie et ensuite on tanne au chrome avec des sels de chrome(III) habituels du commerce et, comme d'habitude, on poursuit le traitement.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise comme composés aromatiques sulfonés des produits de sulfonation de naphtalène et d'éthers diaryliques.
  3. Procédé selon la revendication 1, caractérisé en ce que, après chaulage, on utilise du matériau de peau planée refendu.
  4. Procédé selon la revendication 1, caractérisé en ce qu'on traite le matériau de peau planée refendu avec 3-15% en poids du produit de condensation rapporté au matériau de peau planée, calculé sous forme de solide.
  5. Procédé selon la revendication 1, caractérisé en ce qu'on utilise le produit de condensation en combinaison avec une substance tannante.
  6. Procédé selon la revendication 5, caractérisé en ce qu'on utilise comme substances tannantes des composés d'aluminium et/ou de titane, des aldéhydes, des oxazolidines ou des composés contenant des groupes phénoliques, le cas échéant en combinaison entre eux.
EP92115270A 1991-09-19 1992-09-07 Procédé pour la production du cuir tanné au chrome Expired - Lifetime EP0533011B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4131202 1991-09-19
DE4131202A DE4131202A1 (de) 1991-09-19 1991-09-19 Verfahren zur herstellung von chromleder

Publications (2)

Publication Number Publication Date
EP0533011A1 EP0533011A1 (fr) 1993-03-24
EP0533011B1 true EP0533011B1 (fr) 1994-10-12

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EP92115270A Expired - Lifetime EP0533011B1 (fr) 1991-09-19 1992-09-07 Procédé pour la production du cuir tanné au chrome

Country Status (6)

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US (1) US5340365A (fr)
EP (1) EP0533011B1 (fr)
JP (1) JP3027480B2 (fr)
CA (1) CA2078411A1 (fr)
DE (2) DE4131202A1 (fr)
ES (1) ES2063559T3 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7118603B2 (en) * 2002-07-15 2006-10-10 Council Of Scientific And Industrial Research Process for the preparation of a formaldehyde-free synthetic tanning agent
CN100535126C (zh) * 2003-08-12 2009-09-02 印度科学工业研究所 合成鞣剂的制备方法
US20080156726A1 (en) * 2006-09-06 2008-07-03 Fassbender Alexander G Integrating recycle stream ammonia treatment with biological nutrient removal
JP4926138B2 (ja) * 2008-08-04 2012-05-09 ナム チョン カンパニー リミテッド 自動車シーツ用スプリットレザーおよびその製造方法
CN102978299B (zh) * 2012-11-29 2014-06-18 际华三五一二皮革服装有限公司 一种轻薄软高强度山羊手套革的制作方法
WO2014112404A1 (fr) * 2013-01-17 2014-07-24 協伸株式会社 Stratifié de cuir et son procédé de fabrication
EP2607499A3 (fr) * 2013-02-14 2013-07-10 Basf Se Procédé destiné à la fabrication de cuir
CN104109723B (zh) * 2014-07-18 2016-02-03 四川德华皮革制造有限公司 一种无甲醛无铬鞣制的毛革两用皮的制备方法
CN104818355B (zh) * 2015-04-17 2016-10-26 四川大学 一种含铬皮革复鞣填充剂及其制备方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB332262A (en) * 1929-01-10 1930-07-10 Bernhard Quendt Process for preliminarily treating hides for promoting the tanning thereof and preparations therefor
DE1288233B (de) * 1965-01-02 1969-01-30 Bayer Ag Verfahren zum Schnellgerben von mittelschweren oder schweren Haeuten
CH513933A (de) * 1968-11-02 1971-10-15 Bayer Ag Verfahren zur Herstellung von Formaldehyd-Kondensationsprodukten von Terphenylsulfonsäuren und deren Verwendung
US4060384A (en) * 1976-09-09 1977-11-29 Seton Company Manufacture of leather
GB8808436D0 (en) * 1987-04-24 1988-05-11 Ici Francolor Tanning agent
GB8802747D0 (en) * 1988-02-06 1988-03-09 Tioxide Group Plc Tanning agent & process
DE3935879A1 (de) * 1989-10-27 1991-05-02 Basf Ag Verfahren zum alleingerben von bloessen und zum nachgerben von chromleder

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Römpps Chemie-Lexikon, 8.Auflage, 1983, Seite 2183 *

Also Published As

Publication number Publication date
EP0533011A1 (fr) 1993-03-24
JP3027480B2 (ja) 2000-04-04
JPH05202400A (ja) 1993-08-10
CA2078411A1 (fr) 1993-03-20
DE4131202A1 (de) 1993-03-25
ES2063559T3 (es) 1995-01-01
DE59200623D1 (de) 1994-11-17
US5340365A (en) 1994-08-23

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