EP0470465B1 - Procédé de retannage de cuir qui au préalable a subi un tannage minéral par des acides sulfoniques aromatiques - Google Patents

Procédé de retannage de cuir qui au préalable a subi un tannage minéral par des acides sulfoniques aromatiques Download PDF

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Publication number
EP0470465B1
EP0470465B1 EP91112640A EP91112640A EP0470465B1 EP 0470465 B1 EP0470465 B1 EP 0470465B1 EP 91112640 A EP91112640 A EP 91112640A EP 91112640 A EP91112640 A EP 91112640A EP 0470465 B1 EP0470465 B1 EP 0470465B1
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EP
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Prior art keywords
leather
retanning
agents
salts
sulphonic acids
Prior art date
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Expired - Lifetime
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EP91112640A
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German (de)
English (en)
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EP0470465A1 (fr
Inventor
Franz Dr. Schade
Wilhelm Krümmel
Bernhard Dr. Wehling
Henricus Slaats
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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
    • C14C3/08—Chemical tanning by organic agents
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/62—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds with sulfate, sulfonate, sulfenic or sulfinic groups
    • D06P1/621—Compounds without nitrogen
    • D06P1/622—Sulfonic acids or their salts
    • D06P1/625—Aromatic

Definitions

  • the mono- and disulfonic acids of phenol, cresols, hydroxydiphenylene and naphthols and their alkali and ammonium salts are preferably used.
  • Formaldehyde condensation products of ⁇ -naphthalenesulfonic acid (DE-PS 290 965), diphenyl and ditolyl ether sulfonic acids (US Pat. No. 2,315,951) and terphenyl sulfonic acids are common as retanning agents and as auxiliaries for leveling chemical and / or physical irregularities in the leather surface (US-PS 3 906 037) and their ammonium or alkali salts.
  • So-called exchange tanning agents which are predominantly present as phenol-containing formaldehyde condensation products of aromatic sulfonic acids or their salts, are common practice as retanning and / or leveling agents for chrome leather (GB-PS 1 291 784 and DT-PS 611 671).
  • EP-A-24014 discloses a similar process using sulfonic acids which differ from the present ones in that there is no OH group.
  • the sulfonic acids of the formulas (I) and (II) or their salts which are not like anionic synthetic tanning agents and leveling agents have been condensed with formaldehyde to form larger molecules which are particularly suitable as retanning agents. They offer the advantage that the leather retanned with it or the leather treated before or during the dyeing, with excellent levelness, results in deep and brilliant surface dyeings with anionic dyes. The color depth is similar to that of pure chrome leather that has not been treated with retanning agents and / or leveling agents.
  • Suitable retanning agents of the formulas (I) and (II), which allow a deep and brilliant coloration of the leather with optimal use of the dye range, are preferably partially or completely neutralized with sodium hydroxide or ammonia with phenolsulfonic acids. They can e.g. produce by allowing 2 moles of sulfuric acid monohydrate to act on 1 mole of technical phenol at 110-130 ° C, preferably 120 ° C, for 2 hours for sulfonation and then neutralizing the reaction mixture to the desired final pH and spray-drying in powder transferred or formed as a liquid product with approx. 40% active substance.
  • the sulfonic acids and their salts of the formula (I) or (II) are optimally effective for levelness, brilliance and depth of the coloration of the leather, if they are mixed with anionic dyes in amounts of 2-10%, preferably 3-, before or during the coloration. 6% (based on the so-called fold weight of the leather) act on the leather and let it open. They are particularly good at leveling the color and compensate for the different dyeability of damaged and undamaged areas within individual skins or skins if they are applied to the leather before the dye is added and the dye can then be evenly applied to the equalized leather.
  • Mixtures have also proven to be particularly suitable for simultaneous neutralization and leveling retanning the sulfonic acids and / or their salts used according to the invention, in particular the sodium or ammonium salts with mono- or polybasic, preferably dibasic, carboxylic acids, for example formic, acetic, propionic, succinic, glutaric, adipic, and / or their alkali - (Na, K, Li), ammonium or alkaline earth salts (Mg, Ca, Sr, Ba).
  • sodium or ammonium salts with mono- or polybasic, preferably dibasic, carboxylic acids, for example formic, acetic, propionic, succinic, glutaric, adipic, and / or their alkali - (Na, K, Li), ammonium or alkaline earth salts (Mg, Ca, Sr, Ba).
  • a mixture may be mentioned which contains 70-40 parts by weight of sodium salts of a technical dicarboxylic acid mixture (mixture of succinic, glutaric and adipic acid), as is for example a by-product in the production of adipic acid, 30-60 parts by weight of sodium and / or ammonium salts containing phenolsulfonic acid.
  • a technical dicarboxylic acid mixture mixture of succinic, glutaric and adipic acid
  • a by-product in the production of adipic acid 30-60 parts by weight of sodium and / or ammonium salts containing phenolsulfonic acid.
  • Chromium leather from cowhide or calfskin which is manufactured in the usual way, folded to 1.6-1.8 mm and neutralized to pH 3.8-4.2, is at 100% liquor in a rotating tanning barrel with 6% of a pH 6.5-6.8 adjusted phenolsulfonic acid ammonium salt, which is formed when 2 moles of sulfuric acid monohydrate act on 1 mole of phenol at 120 ° C in the course of 2 hours and then neutralized after cooling and diluting to pH 6.5-6.8 with ammonia and spray dried into powder or formed as a liquid product with approx. 40% active substance.
  • greasing is carried out in the dye bath in the customary manner and then treated with 1.5% formic acid in order to achieve the best possible absorption of the dye and the greasing.
  • this leather corresponds to leather dyed with the same amount of dye without pretreatment, but this results in significantly lower levelness.
  • Chromium cowhide folded to 1.6-1.8 mm thickness and neutralized to pH 3.6-3.8, is treated for 10 minutes with 4% of a phenolsulfonate in a 100% warm liquor.
  • To prepare the sulfonate 2 mols of sulfuric acid monohydrate are allowed to act on 1 mol of phenol at 120 ° C. in the course of 2 hours with vigorous stirring, the mixture is cooled, diluted, neutralized with sodium hydroxide solution and converted into powder form by spray drying.
  • nubuck leather chrome leather, which is folded and neutralized to pH 6.0 (cut color with bromothymol blue yellow to yellow-green), is first washed with 300% water at 40 ° C. After draining the wash liquor is pre-greased for 15 minutes with 2.5% of a sulfited leather greasing agent based on trans in 100% of a 40 ° C warm liquor and then treated in the same liquor for 10 minutes with 1% of an ammonia solution which contains 2.5% by weight NH3 .
  • the above-mentioned potassium phenol sulfonate is prepared by reacting 98 g of sulfuric acid monohydrate with 1 mole of phenol at 120 ° C. for 120 minutes and neutralization with potassium hydroxide.

Landscapes

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

Claims (3)

  1. Procédé de retannage de cuir tanné minéralement, caractérisé en ce qu'on utilise comme produit de retannage des acides sulfoniques ou leurs sels de formules générales
    Figure imgb0007
     dans lesquelles
    R   représente l'hydrogène, -CH₃ ou les restes
    Figure imgb0008
    X   représente l'hydrogène, un ion alcalin, notamment le sodium, le potassium, le lithium ou un ion ammonium
    n   représente 1, 2, 3 ou 4.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise comme produits de retannage des acides phénolmono- ou disulfoniques et/ou leurs sels d'alcalin ou d'ammonium.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'on utilise comme produit de retannage des sels d'ammonium d'acides phénolsulfoniques.
EP91112640A 1990-08-10 1991-07-27 Procédé de retannage de cuir qui au préalable a subi un tannage minéral par des acides sulfoniques aromatiques Expired - Lifetime EP0470465B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4025344A DE4025344A1 (de) 1990-08-10 1990-08-10 Verfahren zum nachgerben mineralisch gegerbter leder mit aromatischen sulfonsaeuren
DE4025344 1990-08-10

Publications (2)

Publication Number Publication Date
EP0470465A1 EP0470465A1 (fr) 1992-02-12
EP0470465B1 true EP0470465B1 (fr) 1994-10-26

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP91112640A Expired - Lifetime EP0470465B1 (fr) 1990-08-10 1991-07-27 Procédé de retannage de cuir qui au préalable a subi un tannage minéral par des acides sulfoniques aromatiques

Country Status (4)

Country Link
US (1) US5352241A (fr)
EP (1) EP0470465B1 (fr)
DE (2) DE4025344A1 (fr)
ES (1) ES2061135T3 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004009096A1 (de) * 2004-02-25 2005-09-15 Bayer Chemicals Ag Lederhilfsmittel
WO2007002194A2 (fr) * 2005-06-21 2007-01-04 Epien Medical, Inc. Procede et materiau pour la reduction d'un biofilm

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB175250A (en) * 1921-02-09 1923-03-14 Ralph Oliver Phillips Improvements in the dyeing and finishing of leather
DE578785C (de) * 1928-08-23 1933-06-20 Chem Fab Pott & Co G M B H Verfahren zur Erhoehung der Lagerbestaendigkeit mineralgarer Leder
US2249757A (en) * 1933-09-26 1941-07-22 Nat Aniline & Chem Co Inc Alkyl hydroxy aromatic sulphonate
CH239956A (de) * 1943-09-30 1945-11-30 Ag Sandoz Verfahren zur Herstellung eines neuen gerbstoffartigen Produktes.
US2409671A (en) * 1943-12-08 1946-10-22 Sonneborn Sons Inc L Substantially oil soluble polyalkyl aromatic sulfonates
US2973240A (en) * 1951-06-21 1961-02-28 Boehme Fettchemie Gmbh Tanning with alkylbenzene sulfonate in combination with chrome tanning
DE2932688A1 (de) * 1979-08-11 1981-02-26 Bayer Ag Verfahren zum nachgerben mineralisch gegerbter leder mit aromatischen sulfonsaeuren
US4830632A (en) * 1986-05-05 1989-05-16 Ciba-Geigy Corporation Aqueous composition from a sulfonated phenol, an amine and a tanning salt, process for the production thereof and use thereof as a tanning agent

Also Published As

Publication number Publication date
US5352241A (en) 1994-10-04
ES2061135T3 (es) 1994-12-01
DE4025344A1 (de) 1992-02-13
EP0470465A1 (fr) 1992-02-12
DE59103328D1 (de) 1994-12-01

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