EP0428481A1 - Method of treating leather and furs - Google Patents

Method of treating leather and furs Download PDF

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Publication number
EP0428481A1
EP0428481A1 EP90810849A EP90810849A EP0428481A1 EP 0428481 A1 EP0428481 A1 EP 0428481A1 EP 90810849 A EP90810849 A EP 90810849A EP 90810849 A EP90810849 A EP 90810849A EP 0428481 A1 EP0428481 A1 EP 0428481A1
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Prior art keywords
component
parts
acid
formaldehyde
agent
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EP90810849A
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German (de)
French (fr)
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EP0428481B1 (en
Inventor
Alain Dr. Lauton
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BASF Schweiz AG
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Ciba Geigy AG
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    • 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
    • C14C3/10—Vegetable tanning
    • C14C3/12—Vegetable tanning using purified or modified vegetable tanning 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
    • C14C3/08—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

Definitions

  • the present invention relates to an agent for treating leather and furs, a method for treating these materials and the use of the agent for the production of wet-white leather and furs.
  • condensation products of types (I), (III) and (IV) are known, for example, from Ullmann's Encyclopedia of Industrial Chemistry, Vol. 16, (4), 140 (1979) and can be prepared by the processes described in the references given there.
  • the production can also be carried out under a protective gas such as nitrogen, helium and carbon dioxide.
  • Preferred anionic aromatic syntans are those of groups (I) and (IV), where as (hydroxy) arylsulfonic acid, sulfonated (hydroxy) -naphthalene and sulfonated xylene (as technical mixture), and as diaryl ether sulfonic acid, sulfonated Ditolyl ethers are preferred.
  • component (B) such polymers and copolymers of (meth) acrylic acid, maleic acid, itaconic acid and / or their hydroxy compounds are mentioned which have a molecular weight of 1,000 to 30,000, particularly 2,000 to 15,000. These polymer compounds can be prepared in a manner known per se (cf., for example, E. Müller, Houben-Weyl, Methods of Organic Chemistry, Volume 14 / I, 1961, 1010-1080 and Volume 14 / II, 1963, 631-633 and 705 -713; Kirk-Othmer (3rd) volume 20, 216-219 and FR-A-2 463 810).
  • the weight ratio of the anionic aromatic syntan to component (B) is advantageously 1: 0.03 to 2.2, preferably 1: 0.05 to 2.0.
  • the agent according to the invention can additionally contain a saturated mono- or dicarboxylic acid with a total of 1 to 8 carbon atoms, such as the ants, vinegar, propion, n-butter, isobutter, n-valerian, trimethyl vinegar, capron, Contain n-heptyl, caprylic, oxalic, malonic, amber, glutaric, adipic, pimelic and cork acids.
  • the weight ratio of the compo The component (A) to this acid [component (C)] is 1: 0 to 0.08, preferably 1: 0 to 0.05.
  • the agent according to the invention can also contain, as optional component (D), a sequestering agent such as the tetrasodium salt of ethylenediaminetetraacetic acid and the neutral or acidic sodium pyrophosphate, in a weight ratio of component (A) to component (D) of 1: 0 to 0.08, preferably 1: 0 up to 0.05.
  • a sequestering agent such as the tetrasodium salt of ethylenediaminetetraacetic acid and the neutral or acidic sodium pyrophosphate
  • the optional component (D) acts as a complexing agent and is preferably used in the composition in the case of an iron-free treatment agent, provided the iron content of the oleum used in the production of component (A) is relatively high.
  • the agent according to the invention can be used for pre-tanning leather or for tanning furs.
  • a method for producing wet-white leather and furs thus represents a further subject of the invention.
  • the process for producing wet-white leather and furs is characterized in that after pickling these materials are treated in the presence of a water-soluble chromium, aluminum, iron or zirconium salt or a mixture thereof with an agent according to the invention.
  • the salts that can be used are ready-to-use tanning salts and are described in the relevant specialist literature.
  • Examples of such salts are basic chromium (III) chloride or sulfate, a chrome alum, optionally basic aluminum chloride or sulfate, an alum, iron (III) chloride or sulfate, zirconium oxychloride and zirconium sulfate. Mixtures of the chromium and aluminum salts mentioned can also be used well.
  • the aluminum salts and especially the aluminum sulfate Al2 (SO4) 3 ⁇ 16 H2O.
  • the weight ratio, agent according to the invention (as dry matter) to aluminum salt (as Al2O3) is 1: 0.08 to 1.5, preferably 1: 0.1 to 1.0.
  • Agents according to the invention which do not contain any of the salts mentioned can also be used as after tanning agents with good filling and softening properties can be used.
  • the conventional method is used to treat pickled pelts or furs (skins) with an aqueous solution which contains the agent according to the invention, and then to wet-white material thus obtained in the usual way with vegetable or synthetic tanning agents or chrome tanning agents is tanned.
  • 100 to 200, preferably 100 to 150 parts by weight of water and 3 to 30 parts by weight of the aqueous composition according to the invention are used per 100 parts by weight of pale or fur.
  • Wet-white materials with a shrinking temperature of 60 to 75 ° C., good lightfastness and a light intrinsic color are obtained.
  • agents according to the invention are particularly well suited for the production of wet white leather and furs, their use for this purpose represents a further subject of the invention.
  • the preparation of the agent according to the invention is generally carried out in such a way that an aqueous solution of component (A) is optionally mixed with components (C) and (D) and then with component (B).
  • the aqueous compositions according to the invention preferably contain 64 to 76% by weight of component (A), 18 to 36% by weight of component (B), 0 to 7% by weight of component (C), 0 to 4% by weight of the component (D) and ad 100% by weight of water.
  • the agents thus obtained are liquid and have good storage stability. However, they can be dried if necessary.
  • 100 parts of the sulfonation mixture obtained by heating 520 parts of naphthalene and 560 parts of concentrated sulfuric acid at 140 to 160 ° C. for several hours to water solubility, are obtained with 56 parts of a dihydroxydiphenyl sulfone, obtained by heating 540 parts of phenol for 3 hours and 180 parts of 60% oleum to 170 to 180 ° C and distilling off the excess phenol, and 50 parts of water and 29 parts of formaldehyde (37%) heated at 105 to 110 ° C for 1 hour.
  • the product obtained is then made weakly acidic with ammonia.
  • a water-soluble clear solution is obtained which has a dry content of 51%.
  • 100 parts of the sulfonation mixture obtained by heating 160 parts of xylene mixture and 240 parts of concentrated sulfuric acid at 130 to 135 ° C. for several hours to water solubility, are mixed with 40 parts of a dihydroxydiphenyl sulfone, 32 parts of water and 35 parts of formaldehyde [37%] for 3 hours heated to 100 to 105 ° C.
  • the product obtained is then made weakly acidic with ammonia.
  • a water-soluble clear solution is obtained which has a dry content of 60%.
  • 100 parts of a pickled wool sheepskin are treated in a fleet of 1000 parts of water, from 20-35 ° C and 5 ° Bé, and 5 to 10 parts of an electrolyte-stable fatliquor for 1 hour and then with 20 parts of the according to the manufacture
  • Example 2 prepared agent and 2 parts of a 65% basic aluminum sulfate solution (22% Al2O3) treated overnight in the liquor. Then the pH is adjusted to 3.5-3.8 with soda. After 2 hours, it is rinsed, dried and finished as usual.
  • the wool sheepskin treated in this way has a shrinking temperature of approx. 65 ° C, is soft and has a natural white color.
  • 100 parts of a pickled veal pellet [pH of the liquor 3.5] are treated with 100 parts of water, 6 parts of 85% formic acid and 7 parts of the agent prepared according to preparation example 5 for 6 hours at 30 ° C. in a rolling barrel.
  • a wet-white leather is obtained which can be stored, wilted and rolled. Its shrinking temperature is around 69 ° C.

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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)
  • Cosmetics (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

There are described a composition for treating leathers and pelts, comprising (A) an anionic aromatic syntan and (B) a polymer and/or copolymer of an unsaturated C3-C5-mono- or dicarboxylic acid and/or hydroxy compounds thereof, a method for preparing wet-white leathers and pelts, and also the use of the composition for said preparation.

Description

Die vorliegende Erfindung betrifft ein Mittel zur Behandlung von Leder und Pelzen, ein Verfahren zur Behandlung dieser Materialien sowie die Verwendung der Mittel zur Her­stellung von Wet-white Leder und Pelzen.The present invention relates to an agent for treating leather and furs, a method for treating these materials and the use of the agent for the production of wet-white leather and furs.

Bei der Herstellung von Leder fallen nach dem Chromgerben grosse Mengen Lederabfälle an, die aus dem Schneiden der nassen Wet-blue Leder herrühren. Diese Wet-blue Abfälle sind reich an Chromsalzen, deren Beseitigung ein grosses Problem darstellen. Die Her­stellung von Wet-white Leder nimmt deshalb ständig an Bedeutung zu. Bei der Herstel­lung dieser Leder werden Aluminiumsalze eingesetzt, welche vor der Chromgerbung mit­tels einer sauren Behandlung zum grössten Teil noch entfernt werden müssen.In the manufacture of leather, large amounts of leather waste result from the chrome tanning, which result from cutting the wet blue leather. These wet-blue wastes are rich in chromium salts, the elimination of which is a major problem. The production of wet-white leather is therefore becoming increasingly important. In the manufacture of this leather, aluminum salts are used, which for the most part have to be removed before the chrome tanning with an acid treatment.

Es wurden nun Mittel gefunden, mit welchen diese saure Behandlung vermieden werden kann.Means have now been found with which this acidic treatment can be avoided.

Das erfindungsgemässe Mittel ist dadurch gekennzeichnet, dass es

  • (A) ein anionisches aromatisches Syntan und
  • (B) ein Polymerisat und/oder Copolymerisat einer ungesättigten C₃-C₅-Mono- oder Di­carbonsäure und/oder deren Hydroxyverbindungen enthält.
The agent according to the invention is characterized in that it
  • (A) an anionic aromatic syntan and
  • (B) contains a polymer and / or copolymer of an unsaturated C₃-C₅ mono- or dicarboxylic acid and / or its hydroxy compounds.

Als anionische aromatische Syntane sind zu erwähnen, die Kondensationsprodukte aus sulfonierten Vorprodukten mit Formaldehyd oder Formaldehyd und Harnstoff sowie die nicht kondensierten sulfonierten Vorprodukte, wie z.B.

  • (I) Formaldehyd-Kondensationsprodukte von 4,4′-Dihydroxydiphenylsulfonen mit (Hydroxy)arylsulfonsäuren,
  • (II) Umsetzungsprodukt aus Phenol und einem Sulfonierungsmittel, wobei das Mol­verhältnis (Phenol):(SO₃) (1):(1,1-2,2) beträgt
  • (III) Kondensationsprodukte aus 4,4′-Dihydroxydiphenylsulfon und sulfoniertem 4,4′-Dihydroxydiphenylsulfon mit Formaldehyd oder Formaldehyd und Harnstoff, und
  • (IV) Formaldehyd-Kondensationsprodukte aus Diarylethersulfonsäure und 4,4′-Di­hydroxydiphenylsulfon.
As anionic aromatic syntans, mention should be made of the condensation products from sulfonated precursors with formaldehyde or formaldehyde and urea, and the uncondensed sulfonated precursors, such as, for example
  • (I) formaldehyde condensation products of 4,4'-dihydroxydiphenyl sulfones with (hydroxy) aryl sulfonic acids,
  • (II) reaction product of phenol and a sulfonating agent, the molar ratio (phenol) :( SO₃) (1) :( being 1.1-2.2)
  • (III) condensation products of 4,4'-dihydroxydiphenyl sulfone and sulfonated 4,4'-dihydroxydiphenyl sulfone with formaldehyde or formaldehyde and urea, and
  • (IV) Formaldehyde condensation products from diaryl ether sulfonic acid and 4,4'-dihydroxydiphenyl sulfone.

Die Kondensationsprodukte der Typen (I), (III) und (IV) sind z.B. aus Ullmanns Enzyklo­pädie der technischen Chemie Bd. 16, (4), 140 (1979) bekannt und können nach den in den dort angegebenen Referenzen beschriebenen Verfahren hergestellt werden. Die Herstel­lung kann auch unter einem Schutzgas, wie Stickstoff, Helium und Kohlendioxid ausge­führt werden.The condensation products of types (I), (III) and (IV) are known, for example, from Ullmann's Encyclopedia of Industrial Chemistry, Vol. 16, (4), 140 (1979) and can be prepared by the processes described in the references given there. The production can also be carried out under a protective gas such as nitrogen, helium and carbon dioxide.

Das Umsetzungsprodukt des Typs (II) und dessen Herstellung sind aus EP-A-0245205 bekanntThe reaction product of type (II) and its preparation are known from EP-A-0245205

Bevorzugte anionische aromatische Syntane, als Komponente (A), sind jene der Gruppen (I) und (IV), wobei als (Hydroxy)arylsulfonsäure, sulfoniertes (Hydroxy)-naphthalin und sulfoniertes Xylol (als technisches Gemisch), und als Diarylethersulfonsäure, sulfonierter Ditolylether bevorzugt sind.Preferred anionic aromatic syntans, as component (A), are those of groups (I) and (IV), where as (hydroxy) arylsulfonic acid, sulfonated (hydroxy) -naphthalene and sulfonated xylene (as technical mixture), and as diaryl ether sulfonic acid, sulfonated Ditolyl ethers are preferred.

Als Komponente (B) sind solche Polymerisate und Copolymerisate der (Meth)acrylsäure, Maleinsäure, Itakonsäure und/oder deren Hydroxyverbindungen zu erwähnen, welche ein Molekulargewicht von 1000 bis 30000, besonders 2000 bis 15000 aufweisen. Diese Polymerverbindungen können nach an sich bekannter Weise hergestellt werden (vgl. z.B. E. Müller, Houben-Weyl, Methoden der organischen Chemie, Band 14/I, 1961, 1010-1080 und Band 14/II, 1963,631-633 und 705-713; Kirk-Othmer (3.) Band 20, 216-219 und FR-A-2 463 810).As component (B), such polymers and copolymers of (meth) acrylic acid, maleic acid, itaconic acid and / or their hydroxy compounds are mentioned which have a molecular weight of 1,000 to 30,000, particularly 2,000 to 15,000. These polymer compounds can be prepared in a manner known per se (cf., for example, E. Müller, Houben-Weyl, Methods of Organic Chemistry, Volume 14 / I, 1961, 1010-1080 and Volume 14 / II, 1963, 631-633 and 705 -713; Kirk-Othmer (3rd) volume 20, 216-219 and FR-A-2 463 810).

Das Gewichtsverhältnis vom anionischen aromatischen Syntan zu Komponente (B) be­trägt zweckmässigerweise 1:0,03 bis 2,2, vorzugsweise 1:0,05 bis 2,0.The weight ratio of the anionic aromatic syntan to component (B) is advantageously 1: 0.03 to 2.2, preferably 1: 0.05 to 2.0.

Das erfindungsgemässe Mittel kann zusätzlich eine gesättigte Mono- oder Dicarbonsäure mit insgesamt 1 bis 8 C-Atomen, wie die Ameisen-, Essig-, Propion-, n-Butter-, Isobutter-, n-Valerian-, Trimethylessig-, Capron-, n-Heptyl-, Capryl-, Oxal-, Malon-, Bernstein-, Glutar-, Adipin-, Pimelin- und Korksäure enthalten. Das Gewichtsverhältnis der Kompo­ nente (A) zu dieser Säure [Komponente (C)] beträgt 1:0 bis 0,08, vorzugsweise 1:0 bis 0,05.The agent according to the invention can additionally contain a saturated mono- or dicarboxylic acid with a total of 1 to 8 carbon atoms, such as the ants, vinegar, propion, n-butter, isobutter, n-valerian, trimethyl vinegar, capron, Contain n-heptyl, caprylic, oxalic, malonic, amber, glutaric, adipic, pimelic and cork acids. The weight ratio of the compo The component (A) to this acid [component (C)] is 1: 0 to 0.08, preferably 1: 0 to 0.05.

Das erfindungsgemässe Mittel kann noch als fakultative Komponente (D) ein Sequestrier­mittel wie das Tetranatriumsalz der Ethylendiamintetraessigsäure und das neutrale oder saure Natriumpyrophosphat, in einem Gewichtsverhältnis Komponente (A) zu Kompo­nente (D) von 1:0 bis 0,08, vorzugsweise 1:0 bis 0,05, enthalten. Die fakultative Kompo­nente (D) wirkt als Komplexierungsmittel und wird in der Zusammensetzung vorzugs­weise bei einem eisenfreien Behandlungsmittel mitverwendet, sofern der Eisengehalt des bei der Herstellung der Komponente (A) eingesetzten Oleums relativ hoch ist.The agent according to the invention can also contain, as optional component (D), a sequestering agent such as the tetrasodium salt of ethylenediaminetetraacetic acid and the neutral or acidic sodium pyrophosphate, in a weight ratio of component (A) to component (D) of 1: 0 to 0.08, preferably 1: 0 up to 0.05. The optional component (D) acts as a complexing agent and is preferably used in the composition in the case of an iron-free treatment agent, provided the iron content of the oleum used in the production of component (A) is relatively high.

Das erfindungsgemässe Mittel kann zum Vorgerben von Leder oder zum Gerben von Pel­zen (Fellen) verwendet werden. Somit stellt ein Verfahren zur Herstellen von Wet-­white-Leder und -Pelzen einen weiteren Erfindungsgegenstand dar.The agent according to the invention can be used for pre-tanning leather or for tanning furs. A method for producing wet-white leather and furs thus represents a further subject of the invention.

Das Verfahren zur Herstellung von Wet-white-Leder und -Pelzen ist dadurch gekenn­zeichnet, dass man diese Materialien nach dem Pickeln in Gegenwart eines wasser­löslichen Chrom-, Aluminium-, Eisen- oder Zirkoniumsalzes oder eines Gemisches davon mit einem erfindungsgemässen Mittel behandelt.The process for producing wet-white leather and furs is characterized in that after pickling these materials are treated in the presence of a water-soluble chromium, aluminum, iron or zirconium salt or a mixture thereof with an agent according to the invention.

Die einsetzbaren Salze sind gebrauchsfertige Gerbesalze und sind in der einschlägigen Fachliteratur beschrieben. Als Beispiele solcher Salze sei basisches Chrom(III)-chlorid oder -sulfat, ein Chromalaun, gegebenenfalls basisches Aluminiumchlorid oder -sulfat, ein Alaun, Eisen(III)-chlorid oder -sulfat, Zirkonoxychlorid und Zirkoniumsulfat genannt. Auch Gemische der genannten Chrom- und Aluminiumsalze können gut eingesetzt wer­den. Bevorzugt sind indessen [CrCl₂(OH₂)₄]Cl·2 H₂O, [Cr(OH₂)₆]Cl₃, Cr(OH)SO₄, Cr₂(OH)₄SO₄, KCr(SO₄)₂·12 H₂O, AlCl₃·6 H₂O, Al₂(SO₄)₃·16 H₂O, Al₂(OH)₄SO₄, Al(OH)₂Cl, Al(OH)Cl₂, KAl(SO₄)₂·12 H₂O, Fe(SO₄)₃·9 H₂O,Zr(OH)₂SO₄, ZrOCl₂·8 H₂O und Zr(SO₄)₂·4 H₂O.The salts that can be used are ready-to-use tanning salts and are described in the relevant specialist literature. Examples of such salts are basic chromium (III) chloride or sulfate, a chrome alum, optionally basic aluminum chloride or sulfate, an alum, iron (III) chloride or sulfate, zirconium oxychloride and zirconium sulfate. Mixtures of the chromium and aluminum salts mentioned can also be used well. Preferred are, however, [CrCl₂ (OH₂) ₄] Cl · 2 H₂O, [Cr (OH₂) ₆] Cl₃, Cr (OH) SO₄, Cr₂ (OH) ₄SO₄, KCr (SO₄) ₂ · 12 H₂O, AlCl₃ · 6 H₂O, Al₂ (SO₄) ₃ · 16 H₂O, Al₂ (OH) ₄SO₄, Al (OH) ₂Cl, Al (OH) Cl₂, KAl (SO₄) ₂ · 12 H₂O, Fe (SO₄) ₃ · 9 H₂O, Zr (OH) ₂SO₄ , ZrOCl₂ · 8 H₂O and Zr (SO₄) ₂ · 4 H₂O.

Im Vordergrund des Interesses stehen die Aluminiumsalze und besonders das Aluminium­sulfat Al₂(SO₄)₃·16 H₂O. Das Gewichtsverhältnis, erfindungsgemässes Mittel (als Trockensubstanz) zu Aluminiumsalz (als Al₂O₃), beträgt 1:0,08 bis 1,5, vorzugsweise 1:0,1 bis 1,0.In the foreground of interest are the aluminum salts and especially the aluminum sulfate Al₂ (SO₄) ₃ · 16 H₂O. The weight ratio, agent according to the invention (as dry matter) to aluminum salt (as Al₂O₃) is 1: 0.08 to 1.5, preferably 1: 0.1 to 1.0.

Erfindungsgemässe Mittel, die kein der genannten Salze enthalten, können auch als Nach­ gerbestoffe mit gut füllenden und weichmachenden Eigenschaften verwendet werden.Agents according to the invention which do not contain any of the salts mentioned can also be used as after tanning agents with good filling and softening properties can be used.

Hierbei geht man nach konventionellen Methoden so vor, dass man gepickelte Blösse oder Pelze (Felle) mit einer wässrigen Lösung behandelt, welche das erfindungsgemässe Mittel enthält, und anschliessend das so erhaltene Wet-white-Material auf übliche Weise mit vegetabilen oder synthetischen Gerbstoffen oder Chromgerbstoffen gegerbt wird. In der Regel werden auf 100 Gewichtsteile Blösse bzw. Fell 100 bis 200, vorzugsweise 100 bis 150 Gewichtsteile Wasser und 3 bis 30 Gewichtsteile des wässrigen erfindungsgemässen Mittels eingesetzt. Man erhält Wet-white-Materialien mit einer Schrumpfungstemperatur von 60 bis 75°C, einer guten Lichtechtheit und eine helle Eigenfarbe.The conventional method is used to treat pickled pelts or furs (skins) with an aqueous solution which contains the agent according to the invention, and then to wet-white material thus obtained in the usual way with vegetable or synthetic tanning agents or chrome tanning agents is tanned. As a rule, 100 to 200, preferably 100 to 150 parts by weight of water and 3 to 30 parts by weight of the aqueous composition according to the invention are used per 100 parts by weight of pale or fur. Wet-white materials with a shrinking temperature of 60 to 75 ° C., good lightfastness and a light intrinsic color are obtained.

Da die erfindungsgemässen Mittel sich besonders gut zur Herstellung von Wet-white-­Leder und -Pelzen eignen, stellt deren Verwendung zu diesem Zweck einen weiteren Er­findungsgegenstand dar.Since the agents according to the invention are particularly well suited for the production of wet white leather and furs, their use for this purpose represents a further subject of the invention.

Bei der Herstellung des erfindungsgemässen Mittels wird im allgemeinen so verfahren, dass man eine wässrige Lösung der Komponente (A) gegebenenfalls mit den Komponen­ten (C) und (D) und anschliessend mit der Komponente (B) vermischt.The preparation of the agent according to the invention is generally carried out in such a way that an aqueous solution of component (A) is optionally mixed with components (C) and (D) and then with component (B).

Bevorzugt enthalten die erfindungsgemässen wässrigen Mittel 64 bis 76 Gew.% der Kom­ponente (A), 18 bis 36 Gew.% der Komponente (B), 0 bis 7 Gew.% der Komponente (C), 0 bis 4 Gew.% der Komponente (D) und ad 100 Gew.% Wasser.The aqueous compositions according to the invention preferably contain 64 to 76% by weight of component (A), 18 to 36% by weight of component (B), 0 to 7% by weight of component (C), 0 to 4% by weight of the component (D) and ad 100% by weight of water.

Die so erhaltenen Mittel sind flüssig und sind gut lagerstabil. Sie können aber gegebenen­falls getrocknet werden.The agents thus obtained are liquid and have good storage stability. However, they can be dried if necessary.

Die in den nachfolgenden Vorschriften und Beispielen angegebenen Prozente und Teile beziehen sich auf das Gewicht.The percentages and parts given in the following regulations and examples refer to the weight.

HerstellungsvorschriftenManufacturing regulations Vorschrift ARegulation A

100 Teile des Sulfonierungsgemisches, erhalten durch mehrstündiges Erhitzen von 520 Teilen Naphthalin und 560 Teilen konzentrierter Schwefelsäure auf 140 bis 160°C bis zur Wasserlöslichkeit, werden mit 56 Teilen eines Dihydroxydiphenylsulfons, erhalten durch 3-stündiges Erhitzen von 540 Teilen Phenol und 180 Teilen 60 %igem Oleum auf 170 bis 180°C und Abdestillieren des überschüssigen Phenols, und 50 Teilen Wasser und 29 Teilen Formaldehyd (37 %ig) 1 Stunde lang auf 105 bis 110°C erhitzt. Das erhaltene Produkt wird anschliessend mit Ammoniak schwach sauer gestellt. Man erhält eine was­serlösliche klare Lösung die ein Trockengehalt von 51 % besitzt.100 parts of the sulfonation mixture, obtained by heating 520 parts of naphthalene and 560 parts of concentrated sulfuric acid at 140 to 160 ° C. for several hours to water solubility, are obtained with 56 parts of a dihydroxydiphenyl sulfone, obtained by heating 540 parts of phenol for 3 hours and 180 parts of 60% oleum to 170 to 180 ° C and distilling off the excess phenol, and 50 parts of water and 29 parts of formaldehyde (37%) heated at 105 to 110 ° C for 1 hour. The product obtained is then made weakly acidic with ammonia. A water-soluble clear solution is obtained which has a dry content of 51%.

Vorschrift BRegulation B

Man verfährt wie in Vorschrift A angegeben, setzt jedoch 31 Teile eines Dihydroxydi­phenylsulfons ein. Man erhält eine klare wasserlösliche Lösung die ein Trockengehalt von 47 % besitzt.The procedure is as described in instruction A, but 31 parts of a dihydroxydiphenyl sulfone are used. A clear water-soluble solution is obtained which has a dry content of 47%.

Vorschrift CRegulation C

100 Teile des Sulfonierungsgemisches, erhalten durch mehrstündiges Erhitzen von 160 Teilen Xylolgemisch und 240 Teilen konzentrierter Schwefelsäure auf 130 bis 135°C bis zur Wasserlöslichkeit, werden mit 40 Teilen eines Dihydroxydiphenylsulfons, 32 Tei­len Wasser und 35 Teilen Formaldehyd [37 %ig] 3 Stunden lang auf 100 bis 105°C er­hitzt. Das erhaltene Produkt wird anschliessend mit Ammoniak schwach sauer gestellt. Man erhält eine wasserlösliche klare Lösung die ein Trockengehalt von 60 % besitzt.100 parts of the sulfonation mixture, obtained by heating 160 parts of xylene mixture and 240 parts of concentrated sulfuric acid at 130 to 135 ° C. for several hours to water solubility, are mixed with 40 parts of a dihydroxydiphenyl sulfone, 32 parts of water and 35 parts of formaldehyde [37%] for 3 hours heated to 100 to 105 ° C. The product obtained is then made weakly acidic with ammonia. A water-soluble clear solution is obtained which has a dry content of 60%.

HerstellungsbeispieleManufacturing examples Beispiel 1:Example 1:

Zu einer Lösung aus 200 Teilen des gemäss Vorschrift A hergestellten phenolischen Gerbstoffes werden 10 Teile Glutarsäure, 5 Teile Tetranatriumsalz der Ethylendiamintetraessigsäure und 100 Teile einer 30 %igen wässrigen Polymethacrylsäure mit einem Molekulargewicht von 9000 zugegeben. Man erhält 315 Teile einer dickflüssi­gen, hellbraunen, gut fliessbaren Lösung, die nach 3-monatiger Lagerung homogen ist, d.h. keinerlei Trübungen oder Ausflockungen aufweist.10 parts of glutaric acid, 5 parts of tetrasodium salt of ethylenediaminetetraacetic acid and 100 parts of a 30% strength aqueous polymethacrylic acid with a molecular weight of 9000 are added to a solution of 200 parts of the phenolic tanning agent prepared according to regulation A. 315 parts of a viscous, light brown, free-flowing solution are obtained which is homogeneous after 3 months of storage, i.e. shows no cloudiness or flocculation.

Beispiel 2:Example 2:

Zu einer Lösung aus 200 Teilen des gemäss Vorschrift B hergestellten phenolischen Gerbstoffes werden 9 Teile 85 %iger Ameisensäure und 200 Teile 30 %iger wässriger Polymethacrylsäure mit einem Molekulargewicht von 5000 zugegeben. Man er­hält 409 Teile einer dickflüssigen, braunen, gut fliessbaren Lösung, die nach 3-monatiger Lagerung homogen ist.9 parts of 85% formic acid and 200 parts of 30% aqueous polymethacrylic acid with a molecular weight of 5,000 are added to a solution of 200 parts of the phenolic tanning agent prepared according to regulation B. This gives 409 parts of a viscous, brown, easily flowable solution which is homogeneous after 3 months of storage.

Beispiel 3:Example 3:

Zu einer Lösung aus 200 Teilen des gemäss Vorschrift B hergestellten phenolischen Gerbstoffes werden 100 Teile einer aus einem Monomeranteil von 70 % Methacrylsäure und 30 % Acrylsäure hergestellten 35 %igen Polymethacrylsäure vom Molekulargewicht 10000 gegeben. Man erhält 300 Teile einer dickflüssigen, braunen Lösung, die nach 3-monatiger Lagerung homogen ist.100 parts of a 35% polymethacrylic acid prepared from a monomer fraction of 70% methacrylic acid and 30% acrylic acid are added to a solution of 200 parts of the phenolic tanning agent prepared according to regulation B. Given molecular weight 10,000. 300 parts of a viscous, brown solution are obtained which is homogeneous after 3 months of storage.

Beispiel 4:Example 4:

Zu einer Lösung aus 200 Teilen des gemäss Vorschrift C hergestellten phenolischen Gerbstoffes werden 10 Teile einer 85 %igen Ameisensäure und 60 Teile einer 50 %igen wässrigen Polyacrylsäure vom Molekulargewicht 5000 gegeben. Man er­hält 270 Teile einer dickflüssigen, braunen, gut fliessbaren Lösung, die nach 3-monatiger Lagerung homogen ist.10 parts of an 85% strength formic acid and 60 parts of a 50% strength aqueous polyacrylic acid with a molecular weight of 5000 are added to a solution of 200 parts of the phenolic tanning agent prepared according to regulation C. 270 parts of a viscous, brown, easily flowable solution are obtained which is homogeneous after 3 months of storage.

Beispiel 5Example 5

Zu 200 Teilen eines Dihydroxydiphenylsulfons, erhalten durch 3-stündiges Erhitzen von 540 Teilen Phenol und 180 Teilen 60%igem Oleum auf 170 bis 180°C und Abdestillieren des überschüssigen Phenols, werden 200 Teile einer 30%igen wässrigen Lösung des Na­triumsalzes einer Polymethacrylsäure vom Molekulargewicht 9200 gegeben. Nach der Trocknung des erhaltenen Produkts erhält man 260 Teile eines braunen Pulvers.200 parts of a dihydroxydiphenyl sulfone, obtained by heating 540 parts of phenol and 180 parts of 60% oleum at 170 to 180 ° C. for 3 hours and distilling off the excess phenol, are added to 200 parts of a 30% aqueous solution of the sodium salt of a polymethacrylic acid of molecular weight 9200 given. After drying the product obtained, 260 parts of a brown powder are obtained.

AnwendungsbeispieleExamples of use Beispiel 1:Example 1:

100 Teile einer gepickelten Kalbsblösse [pH der Flotte 3,5] werden mit 100 Teilen Wasser und 6 Teilen des gemäss Herstellungsbeispiel 2 hergestellten Mittels während 3 bis 4 Stunden bei 20°C in rollendem Fass behandelt. Anschliessend werden noch 2 Teile einer 65 %igen basischen Aluminiumsulfatlösung (22 % Al₂O₃) zugegeben und weitere 6 Stunden behandelt. Man erhält ein Wet-white-Leder, das gelagert, ab­gewelkt und gewalzt werden kann. Seine Schrumpfungstemperatur liegt bei ca. 70°C. In gleicher Weise hergestellte Wet-white-Leder können wahlweise mit vegetabilen und syn­thetischen Gerbstoffen oder mit Chromgerbstoffen nachgegerbt werden.100 parts of a pickled veal pellet [pH of the liquor 3.5] are treated with 100 parts of water and 6 parts of the agent prepared according to Production Example 2 for 3 to 4 hours at 20 ° C. in a rolling barrel. Then 2 parts of a 65% basic aluminum sulfate solution (22% Al₂O₃) are added and treated for a further 6 hours. A wet-white leather is obtained which can be stored, wilted and rolled. Its shrinking temperature is around 70 ° C. Wet-white leather produced in the same way can be retanned using vegetable and synthetic tanning agents or chrome tanning agents.

Beispiel 2:Example 2:

Man vertährt wie in Beispiel 1 beschrieben, verwendet jedoch 6 Teile des ge­mäss Herstellungsbeispiel 4 angefertigten Mittels anstatt 6 Teilen des Mittels gemäss Herstellungsbeispiel 2. Man erhält ein Wet-white-Leder mit guter Lichtechtheit und einer Schrumpfungstemperatur von ca. 70°C.The procedure is as described in Example 1, but 6 parts of the composition prepared according to Preparation Example 4 are used instead of 6 parts of the composition according to Preparation Example 2. Wet white leather with good lightfastness and a shrinking temperature of approx. 70 ° C. is obtained.

Beispiel 3:Example 3:

100 Teile eines gepickelten Wollschaffelles werden in einer Flotte aus 1000 Teilen Wasser, von 20-35°C und 5°Bé, und 5 bis 10 Teilen eines elektrolytstabilen Fettungsmittels 1 Stunde lang behandelt und dann mit 20 Teilen des gemäss Herstellungs­ beispiel 2 angefertigten Mittels und 2 Teilen einer 65 %igen basischen Aluminiumsulfat­lösung (22 % Al₂O₃) über Nacht in der Flotte behandelt. Danach wird der pH-Wert mit Soda auf 3,5-3,8 eingestellt. Nach 2 Stunden wird gespült, getrocknet und wie üblich fertiggestellt. Das so behandelte Wollschaffell besitzt eine Schrumpfungstemperatur von ca. 65°C, ist weich und hat eine weisse, natürliche Eigenfarbe.100 parts of a pickled wool sheepskin are treated in a fleet of 1000 parts of water, from 20-35 ° C and 5 ° Bé, and 5 to 10 parts of an electrolyte-stable fatliquor for 1 hour and then with 20 parts of the according to the manufacture Example 2 prepared agent and 2 parts of a 65% basic aluminum sulfate solution (22% Al₂O₃) treated overnight in the liquor. Then the pH is adjusted to 3.5-3.8 with soda. After 2 hours, it is rinsed, dried and finished as usual. The wool sheepskin treated in this way has a shrinking temperature of approx. 65 ° C, is soft and has a natural white color.

Beispiel 4Example 4

100 Teile einer gepickelten Kalbsblösse [pH der Flotte 3,5] werden mit 100 Teilen Was­ser, 6 Teilen 85%iger Ameisensäure und 7 Teilen des gemäss Herstellungsbeispiel 5 her­gestellten Mittels während 6 Stunden bei 30°C in rollenden Fass behandelt. Man erhält ein Wet - White Leder, das gelagert, abgewelkt und gewalzt werden kann. Seine Schrump­fungstemperatur liegt bei ca. 69°C.100 parts of a pickled veal pellet [pH of the liquor 3.5] are treated with 100 parts of water, 6 parts of 85% formic acid and 7 parts of the agent prepared according to preparation example 5 for 6 hours at 30 ° C. in a rolling barrel. A wet-white leather is obtained which can be stored, wilted and rolled. Its shrinking temperature is around 69 ° C.

Claims (15)

1. Verfahren zur Herstellung von Wet-white-Leder und -Pelzen, dadurch gekennzeichnet, dass man diese Materialien nach dem Pickeln in Gegenwart eines wasserlöslichen Chrom-, Aluminium-, Eisen- oder Zirkoniumsalzes oder eines Gemisches davon mit einem Mittel behandelt, das
(A) ein anionisches aromatisches Syntan und
(B) ein Polymerisat und/oder Copolymerisat einer ungesättigten C₃-C₅-Mono- oder Dicarbonsäure und/oder deren Hydroxyverbindungen
enthält.1. A process for the production of wet white leather and furs, characterized in that these materials are treated after the pickling in the presence of a water-soluble chromium, aluminum, iron or zirconium salt or a mixture thereof with an agent which
(A) an anionic aromatic syntan and
(B) a polymer and / or copolymer of an unsaturated C₃-C₅ mono- or dicarboxylic acid and / or their hydroxy compounds
contains. 2. Verfahren gemäss Anspruch 1, worin als Komponente (A) Formaldehyd-Konden­sationsprodukte von 4,4′-Dihydroxydiphenylsulfonen mit (Hydroxy)arylsulfonsäuren oder Formaldehyd-Kondensationsprodukte aus Diarylethersulfonsäuren und 4,4′-Dihydroxy­diphenylsulfon verwendet wird.2. The method according to claim 1, wherein as component (A) formaldehyde condensation products of 4,4'-dihydroxydiphenyl sulfones with (hydroxy) aryl sulfonic acids or formaldehyde condensation products of diaryl ether sulfonic acids and 4,4'-dihydroxydiphenyl sulfone is used. 3. Verfahren gemäss einem der Ansprüche 1 und 2, worin als Komponente (B) ein Polymerisat und/oder Copolymerisat der (Meth)acrylsäure, Maleinsäure, Itakonsäure und/oder deren Hydroxyverbindungen verwendet wird.3. The method according to any one of claims 1 and 2, wherein a polymer and / or copolymer of (meth) acrylic acid, maleic acid, itaconic acid and / or their hydroxy compounds is used as component (B). 4. Verfahren gemäss einem der Ansprüche 1 bis 3, worin die Komponente (B)ein Molekulargewicht von 1000 bis 30000 aufweist.4. The method according to any one of claims 1 to 3, wherein component (B) has a molecular weight of 1000 to 30,000. 5. Verfahren gemäss einem der Ansprüche 1 bis 4, worin zusätzlich eine Mono- oder Dicarbonsäure mit insgesamt 1 bis 8 C-Atomen verwendet wird.5. The method according to any one of claims 1 to 4, wherein additionally a mono- or dicarboxylic acid with a total of 1 to 8 carbon atoms is used. 6. Verfahren gemäss einem der Ansprüche 1 bis 5, worin zusätzlich ein Sequestriermittel verwendet wird.6. The method according to any one of claims 1 to 5, wherein a sequestering agent is additionally used. 7. Verfahren gemäss Anspruch 1, worin die Komponenten (A) und (B) in einem Gewichtsverhältnis (A):(B) von 1:0,03 bis 2,2 verwendet werden.7. The method according to claim 1, wherein the components (A) and (B) in a weight ratio (A) :( B) of 1: 0.03 to 2.2 are used. 8. Verfahren gemäss einem der Ansprüche 1 bis 7, worin als Komponente (A) ein Kondensationsprodukt aus Naphthalinsulfonsäure, 4,4′-Dihydroxydiphenylsulfon und Formaldehyd verwendet wird.8. The method according to any one of claims 1 to 7, wherein a condensation product of naphthalene sulfonic acid, 4,4'-dihydroxydiphenyl sulfone and formaldehyde is used as component (A). 9. Verfahren gemäss einem der Ansprüche 1 bis 7, worin als Komponente (A) ein Kondensationsprodukt aus einem sulfonierten technischen Xylolgemisch, 4,4′-Dihydroxydiphenylsulfon und Formaldehyd verwendet wird.9. The method according to any one of claims 1 to 7, wherein as the component (A) a condensation product of a sulfonated technical xylene mixture, 4,4'-dihydroxydiphenyl sulfone and formaldehyde is used. 10. Verfahren gemäss einem der Ansprüche 1 bis 7, worin als Komponente (A) ein Kondensationsprodukt aus einem sulfonierten Ditolylether, 4,4′-Dihydroxydiphenylsulfon und Formaldehyd verwendet wird.10. The method according to any one of claims 1 to 7, wherein a condensation product of a sulfonated ditolyl ether, 4,4'-dihydroxydiphenyl sulfone and formaldehyde is used as component (A). 11. Verfahren gemäss einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass die Behandlung in Gegenwart eines Aluminiumsalzes erfolgt.11. The method according to any one of claims 1 to 10, characterized in that the treatment is carried out in the presence of an aluminum salt. 12. Verfahren gemäss einem der Ansprüche 1 bis 11, worin das Mittel gemäss Anspruch 1 und das Aluminiumsalz (als Al₂O₃) in einem Gewichtsverhältnis Mittel:Salz von 1:0,08 bis 1,5 verwendet werden.12. The method according to any one of claims 1 to 11, wherein the agent according to claim 1 and the aluminum salt (as Al₂O₃) are used in a weight ratio agent: salt of 1: 0.08 to 1.5.
EP90810849A 1989-11-13 1990-11-06 Method of treating leather and furs Expired - Lifetime EP0428481B1 (en)

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FR2680521A1 (en) * 1991-08-22 1993-02-26 Sandoz Sa PROCESS FOR TANNING, TIGHTENING OR MINERAL REPAIRING OF LEATHER.
EP0574351A1 (en) * 1992-06-09 1993-12-15 Ciba-Geigy Ag Process for the after-treatment of tanned leather and furs
WO2002059382A1 (en) * 2001-01-26 2002-08-01 Clariant International Ltd Production of tanned leather and products suitable therefore
WO2005014865A1 (en) * 2003-08-12 2005-02-17 Council Of Scientific And Industrial Research A process for the preparation of a synthetic tanning agent
US6881356B2 (en) 2001-08-17 2005-04-19 Basf Aktiengesellschaft Method for producing tanning agents containing sulphone
CN103045776A (en) * 2012-12-14 2013-04-17 常熟常圣服饰有限公司 Method for producing fur clothes
CN105238888A (en) * 2015-10-27 2016-01-13 兴业皮革科技股份有限公司 Production technology for preparing wet white leather on basis of Zr-Al-Ti complex

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EP1488013A1 (en) * 2002-03-15 2004-12-22 Basf Aktiengesellschaft Use of polyelectrolytes in the production of leather
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
DE10250112A1 (en) * 2002-10-28 2004-05-06 Bayer Ag Condensation product for giving in Fe-tanned leather

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2680521A1 (en) * 1991-08-22 1993-02-26 Sandoz Sa PROCESS FOR TANNING, TIGHTENING OR MINERAL REPAIRING OF LEATHER.
EP0574351A1 (en) * 1992-06-09 1993-12-15 Ciba-Geigy Ag Process for the after-treatment of tanned leather and furs
WO2002059382A1 (en) * 2001-01-26 2002-08-01 Clariant International Ltd Production of tanned leather and products suitable therefore
US6991659B2 (en) 2001-01-26 2006-01-31 Clariant Finance (Bvi) Limited Production of tanned leather and products suitable therefore
CN100392106C (en) * 2001-01-26 2008-06-04 克莱里安特财务(Bvi)有限公司 Production of tanned leather and products suitable therefore
KR100854236B1 (en) * 2001-01-26 2008-08-25 클라리언트 파이넌스 (비브이아이)리미티드 Production of tanned leather and salts and treatment agents therefor
US6881356B2 (en) 2001-08-17 2005-04-19 Basf Aktiengesellschaft Method for producing tanning agents containing sulphone
WO2005014865A1 (en) * 2003-08-12 2005-02-17 Council Of Scientific And Industrial Research A process for the preparation of a synthetic tanning agent
AU2003250493B2 (en) * 2003-08-12 2009-05-28 Council Of Scientific & Industrial Research A process for the preparation of a synthetic tanning agent
CN103045776A (en) * 2012-12-14 2013-04-17 常熟常圣服饰有限公司 Method for producing fur clothes
CN105238888A (en) * 2015-10-27 2016-01-13 兴业皮革科技股份有限公司 Production technology for preparing wet white leather on basis of Zr-Al-Ti complex

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AR248431A1 (en) 1995-08-18
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DE59008012D1 (en) 1995-01-26
BR9005717A (en) 1991-09-17
EP0428481B1 (en) 1994-12-14
US5256317A (en) 1993-10-26
KR910009936A (en) 1991-06-28

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