EP0245205B1 - Composition aqueuse constituée par un phénol sulfoné, une amine et un sel tannant, sa préparation et son utilisation comme agent de tannage - Google Patents

Composition aqueuse constituée par un phénol sulfoné, une amine et un sel tannant, sa préparation et son utilisation comme agent de tannage Download PDF

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Publication number
EP0245205B1
EP0245205B1 EP87810273A EP87810273A EP0245205B1 EP 0245205 B1 EP0245205 B1 EP 0245205B1 EP 87810273 A EP87810273 A EP 87810273A EP 87810273 A EP87810273 A EP 87810273A EP 0245205 B1 EP0245205 B1 EP 0245205B1
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EP
European Patent Office
Prior art keywords
parts
component
process according
composition
phenol
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Expired - Lifetime
Application number
EP87810273A
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German (de)
English (en)
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EP0245205A3 (en
EP0245205A2 (fr
Inventor
Alain Dr. Lauton
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis AG
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Ciba Geigy AG
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Publication of EP0245205A2 publication Critical patent/EP0245205A2/fr
Publication of EP0245205A3 publication Critical patent/EP0245205A3/de
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Publication of EP0245205B1 publication Critical patent/EP0245205B1/fr
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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

Definitions

  • component (A) of the composition of the invention SO3 or especially oleum.
  • reaction products of phenol and oleum are particularly suitable for component (A), the molar ratio (phenol) :( SO3) especially (1) :( 1.4-1.8).
  • Component (A) is known per se.
  • British Patent 683,084 the production of reaction products from phenol and oleum, which, however, with e.g. Formaldehyde and urea or thiourea are further implemented and also used as tanning agents.
  • FR-A-2,263,304 describes tanning agents which are obtained by sulfonation of a phenolic compound and a non-phenolic aromatic compound and subsequent condensation. These tanning agents are used together with a chrome or zirconium salt.
  • Component (A) used according to the invention is a mixture of polyhydroxy-polyphenylsulfonic sulfonic acids, which presumably contains a 3,3'-dihydroxydiphenylsulfonic disulfonic acid as the main component.
  • component (B) Preferably come for component (B) as primary, secondary or tertiary C1-C4-alkylamine, C2-C3-alkanolamine or C2-C6-alkylenediamine, especially mono-, di- or triethanolamine, dimethylethanolamine, ethylenediamine and N-hydroxyethyl-ethylenediamine , as poly-C2-C3-alkylene-polyamine with 3 to 5 nitrogen atoms N, N-dimethylpropylene diamine, pentamethylene diamine, hexamethylene diamine, triethylene tetramine, and tetraethylene pentamine and especially as a heterocyclic amine, for example morpholine obtainable from diethanolamine and sulfuric acid.
  • diethanolamine is the focus of interest.
  • the ready-to-use tanning salts suitable for component (c) are described in the relevant specialist literature. These are usually chromium, aluminum, iron or zirconium salts. 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 are also well suited for use as component (C).
  • the optional component (D) is used in the composition according to the invention, preference is given to the tetrasodium salt of ethylenediaminetetraacetic acid or the neutral or acidic sodium pyrophosphate (Na4P2O7 or Na2H2P2O7).
  • the optional component (D) acts as a complexing agent and is preferably used in the composition in the case of an iron-free tanning agent, provided the iron content of the oleum used in the production of component (A) is relatively high.
  • the weights of component (C) in the weight ratio of component (A) to component (C) are advantageously based on the metal atom of the corresponding tanning salts.
  • chrome tanning salts as component (C)
  • a maximum of 0.375 parts of chromium per part of component (A) can be used. Higher amounts of chromium would no longer be soluble in the composition and would lead to inhomogeneous compositions.
  • preferred compositions contain components (A) and (C) in a weight ratio (A) :( C) of (1) :( 0.03 to 0.5), based on the metal atom of component (C), at most 0.375 parts of chrome are present.
  • compositions which have the highest possible levels of tanning salts are desirable, since the tanning salts as component (c) are cheaper in comparison with the reaction products of phenol and oleum as component (A), the tanning effect of the composition on both component (A) and also on the component (C) is due.
  • compositions are particularly preferred which contain the components (A) and (C) in a weight ratio (A) :( C) of (1) :( 0.3 to 0.375).
  • the compositions contain components (A) and (D) in a weight ratio (A) :( D) of (1) :( 0 to 0.04).
  • compositions according to the invention have a water content of 40 to 80, preferably 45 to 62 percent by weight.
  • the procedure is generally such that an aqueous solution of component (A) and, if appropriate, component (D) are first mixed with component (B) and then with component (C), which may be present as an aqueous solution .
  • component (A) should first be diluted with water for safety reasons, giving about 50 to 70 percent by weight solutions of component (A).
  • component (B) alone or in admixture with the optional component (D)
  • component (A) and optionally component (D) with component (B) can be carried out in an aqueous medium with moderate external cooling at preferably 60 to 90 ° C.
  • component (C) Only at the end is component (C) added to the mixture of components (A), (B) and optionally (D).
  • Component (D) can be added as a solid with vigorous stirring. This is particularly true when using e.g. Aluminum tanning salts as component (C).
  • component (C) When using chrome tanning salts, it has proven to be particularly advantageous to use component (C) as an aqueous solution, the aqueous solution of component (C) before mixing with components (A), (B) and optionally (D) is usually heated to 60 to 90 ° C. After all the components have been mixed, the composition is generally diluted with water to the preferred water content of 40 to 80 percent by weight.
  • compositions according to the invention obtained in this way are liquid and are particularly suitable for tanning raw materials or for retanning leather of all kinds.
  • the conventional method is used to treat pale or pretanned leather with an aqueous solution which contains the aqueous composition according to the invention, and then the material which has been tanned in the usual way, e.g. by neutralizing, washing out, greasing and drying. If desired, staining can be done.
  • 100 to 200, preferably 140 to 180 parts by weight of water and 5 to 40 parts by weight of the aqueous composition according to the invention are used per 100 parts by weight of leather or leather.
  • 100 parts by weight, preferably descaled, of tanned material is tanned with 140 to 160 parts by weight of water and 10 to 20 parts of the composition according to the invention, or 100 parts by weight in the usual manner with chrome-tanned leather neutralized with, for example, formates or bicarbonates, with 140 to 160 parts by weight Retanned water and 5 to 15 parts of the composition according to the invention.
  • the tanned material is rinsed and, if necessary, subsequently greased with a commercially available fatliquor based on, for example, sulfonated fish oil, sperm oil or claw oil. After drying, a light, brilliant leather is obtained, which has good lightfastness, a firm, compact, smooth grain and a soft handle.
  • the composition according to the invention has the essential advantage of being particularly stable in storage thanks to the presence of component (B). Even after several months of storage, no clouding or flocculation can be found in the composition.
  • composition comprising 166.5 parts of the reaction product from phenol and oleum, 15 parts of diethanolamine, 198 parts of Cr (OH) SO4 (corresponds to 62.3 parts of chromium), 4 parts of tetrasodium salt of ethylenediaminetetraacetic acid and 616.5 parts Contains water. After 3 months of storage, the composition remains homogeneous, i.e. shows no cloudiness or flocculation. A 1% solution of this composition has a pH of 2.9.
  • a filtered solution of 139 parts Cr (OH) SO4 (corresponding to 43.8 parts chromium) and 45.78 parts Al2 (OH) 4SO4 (corresponding to 11.3 parts aluminum) in 484 is now added to the reaction solution, preheated to 70 ° C, Given 72 parts of water.
  • the reaction solution is then kept under stirring at 70 ° C. for 20 minutes and then cooled to 20 ° C. 1000 parts of a composition are obtained which are stable on storage.
  • a 1% solution of this composition has a pH of 3.
  • a storage-stable composition is also obtained if instead of the 4 parts of tetrasodium salt of ethylenediaminetetraacetic acid and the 10 parts of diethanolamine, 3 parts of trisodium phosphate or 7.5 parts of N, N'-dimethyl-propane-diamine are used.
  • Example 2 The procedure is as given in Example 2, but using a filtered solution which has been preheated to 70 ° C. and contains the following parts of tanning salt or water instead of the 45.78 parts of Al2 (OH) 4SO4 and the 484.72 parts of water: example Parts of tannin salt Parts of water 3rd 98.6 AlCl3 ⁇ 6H2O * 431.9 4th 130 Al2 (SO4) 316H2O * 400.5 5 40.3 Al (OH) 2Cl * 490.2 6 47 Al (OH) Cl2 * 483.5 7 195 KAl (SO4) 212H2O * 335.5 8th 76 Fe2 (SO4) 39H2O ** 458.5 * corresponding to 11.03 parts of aluminum ** corresponding to 15 parts of iron
  • compositions with good storage stability are also obtained if, instead of the 65.36 parts of Zr (OH) 2SO4, 95.0 parts of ZrOCl2 ⁇ 8H2O or 106 parts of Zr (SO4) 2 ⁇ 4H2O (all corresponding to 26.82 parts of zirconium) are used.
  • 100 parts of decalcified veal pellet are treated with 150 parts of water and 15 parts of the composition prepared according to Example 1 for 24 hours at 20 ° C. in a rolling barrel. After neutralizing, washing, greasing, stretching, drying, conditioning, studs and sperm, you get a tanned, lightly covered leather that has a full grain and a soft feel.
  • 100 parts of folded chrome grain calf leather are treated with 150 parts of water and 10 parts of the composition prepared according to Example 1 for 2 hours at 50 ° C. in a rolling barrel.
  • the leather is neutralized with sodium formate and sodium bicarbonate using customary methods, washed, dyed with 1 part of the leather dye CI Acid Brown 189 and aftertreated with a commercially available fatliquor based on sulfonated fish oil.
  • a tanned, brown-colored, brilliant leather is obtained, which also has a full grain and a soft handle.

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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)
  • Coloring (AREA)

Claims (17)

  1. Procédé pour la préparation d'une composition aqueuse pour le tannage de peaux en tripe ou pour le retannage du cuir, caractérisé en ce que d'abord on mélange en refroidissant à 60-90°C une solution aqueuse (A) d'un produit de réaction obtenu à partir de phénol et d'un agent de sulfonation, avec un rapport molaire (phénol):(SO₃) valant de 1:1,1 à 1:2,2, et éventuellement (D) un sel alcalin de l'acide éthylènediaminetétraacétique ou d'un pyrophosphate, avec (B) une alkyl(C₁-C₄)-amine, alcanol(C₂-C₃)-amine ou alkylène(C₂-C₆)diamine primaire, secondaire ou tertiaire, soluble dans l'eau, une polyalkylène(C₂-C₃)-polyamine ayant de 3 à 5 atomes d'azote ou une amine hétérocyclique, au maximum 0,2 partie en poids du composant (B) étant utilisée par partie en poids du composant (A), et ensuite on ajoute au mélange obtenu (C) un solution aqueuse d'un sel de chrome, aluminium, fer ou zirconium ou de mélanges de ceux-ci, éventuellement préchauffée à 60-90°C.
  2. Procédé selon la revendication 1, caractérisé en ce que l'on utilise, en tant que composant (A), un produit de réaction obtenu à partir de phénol et d'oléum, avec un rapport molaire (phénol):(SO₃) valant de 1:1,4 à 1:1,8.
  3. Procédé selon la revendication 1, caractérisé en ce que l'on utilise, en tant que composant (B), de la mono-, di- ou triéthanolamine, diméthyléthanolamine, éthylènediamine, N-hydroxyéthyléthylènediamine, N,N-diméthylpropylènediamine, pentaméthylènediamine, hexaméthylènediamine, triéthylènetétramine, tétraéthylènepentamine ou morpholine.
  4. Procédé selon la revendication 1, caractérisé en ce que l'on utilise, en tant que composant (C), du chlorure ou sulfate chromique basique, un alun de chrome, du chlorure ou sulfate d'aluminium éventuellement basique, un alun, du chlorure ou sulfate ferrique, de l'oxychlorure de zirconium ou du sulfate de zirconium éventuellement basique, ou des mélanges des sels de chrome et des sels d'aluminium cités.
  5. Procédé selon la revendication 4, caractérisé en ce que l'on utilise, en tant que composant (C), [CrCl₂(OH₂)₄]Cl·2H₂O, [Cr(OH₂)₆]Cl₃, Cr(OH)SO₄, Cr₂(OH)₄SO₄, KCr(SO₄)₂·12H₂O, AlCl₃·6H₂O, Al₂(SO₄)₃·16H₂O, Al₂(OH)₄SO₄, Al(OH)₂Cl, Al(OH)Cl₂, KAl(SO₄)₂·12H₂O, Fe₂(SO₄)₃·9H₂O, Zr(OH)₂SO₄, ZrOCl₂·8H₂O ou Zr(SO₄)₂·4H₂O.
  6. Procédé selon la revendication 1, caractérisé en ce que l'on utilise, en tant que composant facultatif (D), le sel tétrasodique de l'acide éthylènediaminetétraacétique ou le pyrophosphate de sodium neutre ou acide.
  7. Procédé selon la revendication 1, pour la préparation d'une composition qui, sous forme de solution aqueuse à 1 % par rapport à la matière sèche des composants (A), (B), (C) et éventuellement (D), présente un pH de 5 au maximum.
  8. Procédé selon la revendication 1, pour la préparation d'une composition qui contient les composants (A) et (B) en un rapport pondéral (A):(B) allant de 1:0,05 à 1:0,18.
  9. Procédé selon la revendication 8, pour la préparation d'une composition qui, sous forme de solution aqueuse à 1 % par rapport à la matière sèche des composants (A), (B), (C) et éventuellement (D), présente un pH de 0 à 3,5.
  10. Procédé selon la revendication 1, pour la préparation d'une composition qui contient les composants (A) et (C) en un rapport pondéral (A):(C) allant de 1:0,03 à 1:0,5, par rapport à l'atome métallique du composant (C), au maximum 0,375 partie de chrome étant présente.
  11. Procédé selon la revendication 10, caractérisé en ce que les composants (A) et (C) sont contenus en un rapport pondéral (A):(C) allant de 1:0,3 à 1:0,375.
  12. Procédé selon la revendication 1, caractérisé en ce que les composants (A) et (D) sont contenus en un rapport pondéral (A): (D) allant de 1:0 à 1:0,04.
  13. Procédé selon l'une des revendications 1 à 12, pour la préparation d'une composition qui présente une teneur en eau de 40 à 80 % en poids.
  14. Procédé pour le tannage de peaux en tripe ou pour le retannage du cuir, caractérisé en ce que l'on utilise une composition préparée par le procédé selon l'une des revendications 1 à 13.
EP87810273A 1986-05-05 1987-04-29 Composition aqueuse constituée par un phénol sulfoné, une amine et un sel tannant, sa préparation et son utilisation comme agent de tannage Expired - Lifetime EP0245205B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH182586 1986-05-05
CH1825/86 1986-05-05

Publications (3)

Publication Number Publication Date
EP0245205A2 EP0245205A2 (fr) 1987-11-11
EP0245205A3 EP0245205A3 (en) 1989-05-10
EP0245205B1 true EP0245205B1 (fr) 1992-09-02

Family

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Application Number Title Priority Date Filing Date
EP87810273A Expired - Lifetime EP0245205B1 (fr) 1986-05-05 1987-04-29 Composition aqueuse constituée par un phénol sulfoné, une amine et un sel tannant, sa préparation et son utilisation comme agent de tannage

Country Status (9)

Country Link
US (1) US4830632A (fr)
EP (1) EP0245205B1 (fr)
JP (1) JP2886161B2 (fr)
AU (1) AU604697B2 (fr)
BR (1) BR8702226A (fr)
DE (1) DE3781453D1 (fr)
ES (1) ES2033920T3 (fr)
MX (1) MX167001B (fr)
PT (1) PT84821B (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE58905881D1 (de) * 1988-06-06 1993-11-18 Ciba Geigy Wässrige Lösungen von synthetischen Gerbstoffen.
US5264000A (en) * 1988-06-06 1993-11-23 Ciba-Geigy Corporation Aqueous solutions of synthetic tanning agents
EP0428481B1 (fr) * 1989-11-13 1994-12-14 Ciba-Geigy Ag Moyens pour le traitement de cuir ou de fourrures
DE4025344A1 (de) * 1990-08-10 1992-02-13 Bayer Ag Verfahren zum nachgerben mineralisch gegerbter leder mit aromatischen sulfonsaeuren
DE59303282D1 (de) * 1992-01-28 1996-08-29 Ciba Geigy Ag Verfahren zum Pickeln von Hautblössen
DK0554216T3 (da) * 1992-01-28 1996-08-19 Ciba Geigy Ag Fremgangsmåde til pickling og forgarvning af ugarvede læderhuder
US5490865A (en) * 1994-07-25 1996-02-13 Scheiwiller; Jurg P. Method of treating and dyeing animal fibers
DE10140551A1 (de) 2001-08-17 2003-02-27 Basf Ag Verfahren zur Herstellung sulfonhaltiger Gerbstoffe
AU2002348767B2 (en) * 2002-12-23 2006-11-23 Council Of Scientific And Industrial Research Process for preparing a synthetic aluminium tanning agent
US7169191B2 (en) * 2003-03-20 2007-01-30 Council Of Scientific And Industrial Research Process for preparing a synthetic aluminium tanning agent
CN102747172B (zh) * 2012-07-05 2015-04-01 湖南省怀其皮革集团制革有限公司 一种无铬无醛鞣猪皮鞋里革的制造方法
CN110117905B (zh) * 2019-04-29 2022-02-01 陕西科技大学 一种基于多金属盐处理羽绒得到高蓬松度羽绒的方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE429249A (fr) * 1936-03-10
GB683084A (en) * 1949-06-20 1952-11-19 Geigy Ag J R Manufacture of new condensation products, being more especially improved tanning agents and their application
DE2508195A1 (de) * 1974-03-08 1975-09-11 Sandoz Ag Lederzubereitungsmittel, insbesondere chrom- und zirkongerbmittel
CH603796A5 (fr) * 1976-04-22 1978-08-31 Ciba Geigy Ag

Also Published As

Publication number Publication date
EP0245205A3 (en) 1989-05-10
BR8702226A (pt) 1988-02-17
US4830632A (en) 1989-05-16
DE3781453D1 (de) 1992-10-08
PT84821B (pt) 1989-12-29
JPS62267400A (ja) 1987-11-20
EP0245205A2 (fr) 1987-11-11
JP2886161B2 (ja) 1999-04-26
MX167001B (es) 1993-02-22
AU604697B2 (en) 1991-01-03
PT84821A (en) 1987-06-01
AU7246887A (en) 1987-11-12
ES2033920T3 (es) 1993-04-01

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