[go: up one dir, main page]

WO2009115487A1 - Procédé de fabrication de cuir - Google Patents

Procédé de fabrication de cuir Download PDF

Info

Publication number
WO2009115487A1
WO2009115487A1 PCT/EP2009/053071 EP2009053071W WO2009115487A1 WO 2009115487 A1 WO2009115487 A1 WO 2009115487A1 EP 2009053071 W EP2009053071 W EP 2009053071W WO 2009115487 A1 WO2009115487 A1 WO 2009115487A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
alkali metal
tanning
polycarboxylic acid
corresponding ammonium
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.)
Ceased
Application number
PCT/EP2009/053071
Other languages
German (de)
English (en)
Inventor
Stephan Hüffer
Sebastien Garnier
Michael Kluge
Markus Brym
Franz Glocknitzer
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.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to BRPI0909178-5A priority Critical patent/BRPI0909178A2/pt
Priority to EP09722872A priority patent/EP2257650A1/fr
Priority to CN2009801100165A priority patent/CN101978077A/zh
Publication of WO2009115487A1 publication Critical patent/WO2009115487A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • C14C3/18—Chemical tanning by organic agents using polycondensation products or precursors thereof
    • C14C3/20—Chemical tanning by organic agents using polycondensation products or precursors thereof sulfonated
    • 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
    • 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

Definitions

  • the present invention relates to a process for the production of leather, characterized in that the pretanning, main tanning or retanning in the presence of (a) at least one compound of general formula I.
  • R 1 is selected from methyl, ethyl, phenyl, benzyl, hydroxymethyl, isopropyl, isobutyl and sec-butyl.
  • the present invention relates to mixtures of
  • Bright leather is in demand in many applications. In particular, if you want a brilliant color of the leather, black, brown or dark gray spots are undesirable. In conventional tanning processes, however, such unwanted stains are often observed.
  • iron compounds especially iron oxides and iron hydroxide, F ⁇ 2 ⁇ 3-aq
  • iron stains typical of Fe when using vegetable tannins.
  • Such stains are formed, for example, by separating chips from knives or other metal parts from folding machines having rotating blades made of steel, and dissolving them in the aqueous tanning liquor to form iron compounds.
  • iron oxide and / or iron hydroxide can then be deposited on the leather.
  • Vegetable tannins usually contain gallic acid or gallate.
  • Gallic acid forms complexes with iron, these have a deep black Color and have been known as an ingredient of inks since the Middle Ages.
  • EDTA ethylenediaminetetraacetate
  • the process according to the invention is a process for pretanning, main tanning-which also includes tanning-or retanning, preferably the process according to the invention is a retanning process.
  • the inventive method is based on pretreated hides of dead animals such as cattle, pigs, goats or deer. It is not essential for the method according to the invention, whether the animals were killed, for example, by slaughtering or huntsman or died of natural causes.
  • Conventional methods of pre-treatment include, for example, liming, descaling, pickling and pimpling, as well as mechanical operations, for example, for fleshing out the hides, and in particular folding.
  • the process according to the invention is carried out as a retanning process.
  • the tanning can be carried out with any known tanning substances, for example with Cr (III) compounds, with polymer tanning agents, with aldehyde tanning agents, with vegetable tanning agents or with syntans.
  • the semi-finished products used may be wet blue or wet white.
  • Suitable flotation lengths can be, for example, 50 to 250%.
  • alkali metal is selected from lithium, rubidium, cesium, preferably potassium and more preferably sodium, and
  • R 1 is selected from methyl, ethyl, phenyl, benzyl, hydroxymethyl, isopropyl, isobutyl and sec-butyl.
  • R 1 is selected from methyl and hydroxymethyl, in particular methyl.
  • the nitrogen atom in compound of the general formula I may be unprotonated or protonated.
  • ammonium or alkali metal salts of compound of the general formula I are mono-, di and triammonium salts or mono-, di- and Trialkalimetallsalze of compound of general formula I to understand where in the case of di- and Trialkalimetallsalze also mixed salts for example, the monosodium monopotassium salt, the disodium monopotassium salt and the monosodium monoammonium salt.
  • Compound of the general formula I can be present as a racemate or in the form of one or the other enantiomer.
  • oxalic acid (b) or a corresponding ammonium or alkali metal salt is used.
  • Corresponding ammonium or alkali metal salts of oxalic acid are understood as meaning mono- and diammonium salts or mono- and dialkali metal salts of oxalic acid, and in the case of dialkali metal salts also mixed salts are included, for example monosodium monokoxaloxalate and monosodium monoammonium oxalate.
  • alkali metal is selected from lithium, rubidium, cesium, preferred
  • the process according to the invention is additionally carried out in the presence of (d) at least one di- or polycarboxylic acid or in each case the corresponding ammonium or alkali metal salts, alkali metal being selected from lithium, rubidium, cesium, preferably potassium and particularly preferably Sodium.
  • mixed di- or polyalkali metal salts are also included, and also those ammonium and alkali metal salts are included, which are attributable to a partial neutralization of di- or polycarboxylic acid (d).
  • Dicarboxylic acid (d) is different from oxalic acid.
  • dicarboxylic acid (d) may be a C3-C12 dicarboxylic acid.
  • Dicarboxylic acid (d) may have a straight or branched C chain, and it may be cyclic or preferably non-cyclic. Dicarboxylic acid (d) may have an aromatic or alicyclic ring, and dicarboxylic acid (d) may have a bicyclic or polycyclic carbon skeleton. Dicarboxylic acid (d) may have one or more ethylenically unsaturated double bonds.
  • dicarboxylic acids (d) are phthalic acid, terephthalic acid, isophthalic acid, maleic acid, fumaric acid, itaconic acid, cyclohexanedicarboxylic acid, in particular the isomeric 1,4-cyclohexanedicarboxylic acids, norbornanedicarboxylic acid and norbornenedicarboxylic acid.
  • dicarboxylic acid (d) is preferably one or more aliphatic dicarboxylic acids, unsubstituted or mono- or polysubstituted by hydroxycarboxylic acids. xyl distr (s).
  • dicarboxylic acid (d) is a mono- or dihydroxydicarboxylic acid.
  • aliphatic dicarboxylic acids are tartaric acid, malic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, pimellic acid; preferred are tartaric acid, succinic acid, glutaric acid and adipic acid and binary and ternary mixtures of succinic acid, glutaric acid and adipic acid.
  • Polycarboxylic acid (d) may have a straight or branched C chain.
  • polycarboxylic acid (d) is a compound having three to five carboxylic acid groups per molecule, particularly preferably aliphatic polycarboxylic acids, unsubstituted or mono- or polysubstituted with hydroxyl group (s).
  • Butane-1, 2,3,4-tetracarboxylic acid is preferred, citric acid is particularly preferred.
  • the process according to the invention is additionally carried out in the presence of ascorbic acid (s).
  • the implementation is also included in the presence of ammonium ascorbate or one or more alkali metal ascorbates.
  • Ascorbic acid can be present as a racemate or in the form of one of its enantiomers, in particular as (L) -ascorbic acid.
  • the process according to the invention is carried out in the presence of
  • C optionally a total of 0.001 to 0.75 wt .-%, preferably 0.03 to 0.175 wt .-% of di- or polycarboxylic acid (s) (d), optionally 0.001 to 0.3 wt .-%, preferably 0 , 05 wt .-% ascorbic acid (s), wherein in wt .-% are based on the shaved weight.
  • the process according to the invention is carried out, for example, by reacting at least one compound of the general formula I and oxalic acid (b) optionally in admixture with alkali metal formate (c), di- or polycarboxylic acid (d) or ascorbic acid (e) in one or more portions Add portions immediately before or during a tanning step.
  • the process according to the invention is then preferably carried out at a pH of 2.5 to 4, it being frequently observed that the pH during the performance of the process according to the invention increases by about 0.3 to three units. It is also possible to increase the pH by about 0.3 to three units by adding blunting agents.
  • the inventive method is generally carried out at temperatures ranging from 10 to 45 ° C, preferably in the range 20-30 0 C from. A duration of 10 minutes to 12 hours has proven useful, a duration of up to 3 hours is preferred.
  • the process of the invention can be carried out in any conventional tanning vessels, for example, by walking in barrels or in rotatable drums with internals.
  • At least one compound of the general formula I and oxalic acid (b), optionally in admixture with alkali metal formate (c), di- or polycarboxylic acid (d) or ascorbic acid (e) together with one or more conventional tanning agents For example, with chrome tanning agents, mineral tannins, Syntanen, polymer tanning or especially vegetable tanning agents, as described for example in Ullmann's Encyclopedia of Industrial Chemistry, Volume A15, pages 259 to 282 and in particular page 268 ff., 5th edition, (1990), Verlag Chemistry Weinheim.
  • Particularly preferred vegetable tannins are quebracho extracts and mimosa.
  • At least one compound of the general formula I and oxalic acid (b) is present as a mixture with alkali metal formate (c), di- or polycarboxylic acid (d) or ascorbic acid (e) in one portion or in several portions during the Vorgerbens, in a special variant already in the pimple.
  • At least one compound of the general formula I and oxalic acid (b) is optionally present as a mixture with alkali metal formate (c), di- or polycarboxylic acid (d) or ascorbic acid (e) in one or more portions or during a retanning step.
  • This variant will also be referred to below as a post-treatment process according to the invention.
  • the Nachgerb vide invention is based on pre-tanned hides.
  • the retanning process according to the invention can be carried out under otherwise customary conditions. It is expedient to choose one or more, for example 2 to 6, action steps and to be able to rinse with water between the interaction steps.
  • the temperature during the individual treatment steps is in each case from 5 to 60 0 C, preferably 20 to 45 ° C. It is possible to use one or more further agents customarily used during the retanning, for example fatliquors, one or more conventional retanning agents, for example chromium tanning agents, mineral tanning agents, syntans, polymer tanning agents or, in particular, vegetable tanning agents, furthermore leather dyes, pH-dulling agents or emulsifiers.
  • At least one compound of the general formula I and oxalic acid (b), if appropriate alkali metal formate (c), di- or polycarboxylic acid (d) or ascorbic acid (e), are used separately in the tanning, prebirth or retanning to.
  • the inventive method gives - optionally after a workup by conventional methods - stain-free leather with excellent mechanical properties. Furthermore, effluents are obtained which are generally readily workable and whose chemical and biological oxygen demand can be obtained by combining the general formula I and oxalic acid (b) optionally together with alkali metal formate (c), di- or polycarboxylic acid (d) or ascorbic acid (e). , is not unduly increased.
  • Another object of the present invention are mixtures comprising (a) at least one compound of general formula I.
  • R 1 is selected from methyl, ethyl, phenyl, benzyl, hydroxymethyl, isopropyl, isobutyl and sec-butyl.
  • R 1 is selected from methyl and hydroxymethyl, especially methyl.
  • the nitrogen atom in compound of the general formula I may be unprotonated or protonated.
  • mixtures according to the invention additionally contain (c) an alkali metal formate.
  • mixtures according to the invention additionally comprise
  • polycarboxylic acid (d) is a tri- or tetracarboxylic acid or a corresponding ammonium or alkali metal salt.
  • di- or polycarboxylic acid is a mono- or dihydroxydi- or polycarboxylic acid.
  • mixtures according to the invention additionally comprise
  • mixtures according to the invention may further comprise water.
  • mixtures according to the invention may also contain a salt which improves the flowability, for example sodium sulfate.
  • a salt which improves the flowability for example sodium sulfate.
  • mixtures according to the invention may contain from 5 to 30% by weight of salt, in particular sodium sulfate.
  • mixtures according to the invention contain
  • Mixtures according to the invention are particularly suitable for carrying out the process according to the invention.
  • Another object of the present invention is the use of the mixtures according to the invention for carrying out the method according to the invention.
  • Another object of the present invention is a process for the production of leather using at least one mixture according to the invention. In one embodiment, from 0.1 to 1, 5 wt .-% mixture according to the invention, preferably 0.2 to 0.5 wt .-%, based on the shaved weight, for carrying out the method according to the invention.
  • Mixtures according to the invention can be prepared by processes known per se, in particular by mixing compound of general formula I with oxalic acid (b), optionally an alkali metal formate (c), optionally at least one di- or polycarboxylic acid (d) and optionally ascorbic acid (e), in particular by stirring.
  • Bovine wet blue (short: wb, US-Packer) and bovine wet white (short: ww) were folded to 1, 8 mm and cut to the core area. Then they were distributed to two separate barrels. The mixture was then neutralized by allowing to work at 20 ° C. and a liquor length of 100% by weight of water, 0.7% by weight of sodium formate and 0.2% by weight of NaHCO 3 over a period of 60 minutes. At the end of the treatment, a pH of 4.8 to 5.0 was measured. Subsequently, the semi-finished products were washed twice with 100 wt .-% water and cut into 10 strips (wb and ww), each about 400 g.
  • the semifinished strips were sprinkled evenly with 0.5 g of iron granulated powder per dm 2 (50 ⁇ m average diameter). Then you put the semi-finished strips for 8 hours with a plastic film covered over Bock. The semifinished strips were then distributed to 20 separate rotatable drums and treated with 60 wt .-% water and treated with 6 wt .-%% of the sulfone Fongerbstoffs from EP-B 0 459 168, Example K1. After a walk time of 20 minutes at 30 0 C was metered 0.9 wt .-% sodium formate and further 30 minutes (30 0 C).
  • reaction was carried out for a further 20 minutes and then 2% by weight of a naphthalenesulfonic acid-formaldehyde condensation product prepared according to US 5,186,846, example "Dispersant 1.” The reaction was continued for a further 120 minutes, after which the liquor was drained off.
  • the pieces of leather obtained were washed twice with 100% by weight of water each time.
  • the leather pieces were covered with a foil, stored for at least 6 hours over Bock.
  • the pieces of leather were then dried at 60 to 70 0 C over a period of 4 minutes in vacuo.
  • the conditioning prior to visual inspection was carried out at 40 0 C in a conditioned room for 12 hours, or alternatively by insertion into moistened sawdust.
  • the comparative leathers VL.1 to VL.10 and the leathers L.1 1 to L.20 produced according to the invention were obtained.
  • the leathers according to the invention and the comparative leathers were evaluated according to a grading system of 1 to 5.
  • Note 1 in this case means based on the color number no discoloration beyond the intrinsic color of Crust leather (wet blue or wet white) and correspondingly neither iron stains nor inhomogeneities in the appearance of the leather.
  • Grade 5 corresponds to a gray-black leather.
  • Table 2 Test results of comparative leather V-L.1 to V-L.10 and leathers L.11 to L.20 produced according to the invention
  • V-L.3 and V-L.4 had extremely unfavorable COD (chemical oxygen demand) and contained unused EDTA.

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)

Abstract

La présente invention concerne un procédé de fabrication de cuir, caractérisé en ce que l’on exécute le prétannage, le tannage et le retannage en présence (a) d’au moins un composé de la formule générale (I) et (b) d’oxyde oxalique ou chaque fois des sels d’ammonium ou de métaux alcalins correspondants, R1 étant choisi parmi le méthyle, l’éthyle, le phényle, le benzyle, l’hydroxyméthyle, l’isopropyle, l’isobutyle et le sec-butyle.
PCT/EP2009/053071 2008-03-20 2009-03-16 Procédé de fabrication de cuir Ceased WO2009115487A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
BRPI0909178-5A BRPI0909178A2 (pt) 2008-03-20 2009-03-16 Processo para a produção de couro, mistura, e, uso da mesma.
EP09722872A EP2257650A1 (fr) 2008-03-20 2009-03-16 Procédé de fabrication de cuir
CN2009801100165A CN101978077A (zh) 2008-03-20 2009-03-16 生产皮革的方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP08153056 2008-03-20
EP08153056.0 2008-03-20

Publications (1)

Publication Number Publication Date
WO2009115487A1 true WO2009115487A1 (fr) 2009-09-24

Family

ID=40932073

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2009/053071 Ceased WO2009115487A1 (fr) 2008-03-20 2009-03-16 Procédé de fabrication de cuir

Country Status (4)

Country Link
EP (1) EP2257650A1 (fr)
CN (1) CN101978077A (fr)
BR (1) BRPI0909178A2 (fr)
WO (1) WO2009115487A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3670675A1 (fr) * 2018-12-21 2020-06-24 LANXESS Deutschland GmbH Adjuvants dans la fabrication du cuir pour le travail de rivière

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB590834A (en) * 1945-01-13 1947-07-30 Richard Hodgson And Sons Ltd Improvements in and relating to vegetable-tanned leathers
DE2061898A1 (de) * 1969-12-17 1971-06-24 W R Grace & Co , Cambridge, Mass (V St A) Gerbmittel
US3855286A (en) * 1971-10-01 1974-12-17 Ciba Geigy Corp N-carboxymethyl-n-(2-hydroxybenzyl) aspartic acid and derivatives thereof
DE3114768A1 (de) * 1980-04-29 1982-02-25 Sandoz-Patent-GmbH, 7850 Lörrach "eisen-ii-gerbmittel und verfahren zum gerben von tierischen haeuten und fellen"

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1312387A (zh) * 2001-03-23 2001-09-12 山东省博兴县立鑫皮艺有限公司 牛、马裘革的生产方法
CN101050308A (zh) * 2007-04-29 2007-10-10 温州大学 利用废弃皮革制备新型皮革的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB590834A (en) * 1945-01-13 1947-07-30 Richard Hodgson And Sons Ltd Improvements in and relating to vegetable-tanned leathers
DE2061898A1 (de) * 1969-12-17 1971-06-24 W R Grace & Co , Cambridge, Mass (V St A) Gerbmittel
US3855286A (en) * 1971-10-01 1974-12-17 Ciba Geigy Corp N-carboxymethyl-n-(2-hydroxybenzyl) aspartic acid and derivatives thereof
DE3114768A1 (de) * 1980-04-29 1982-02-25 Sandoz-Patent-GmbH, 7850 Lörrach "eisen-ii-gerbmittel und verfahren zum gerben von tierischen haeuten und fellen"

Also Published As

Publication number Publication date
CN101978077A (zh) 2011-02-16
BRPI0909178A2 (pt) 2015-08-25
EP2257650A1 (fr) 2010-12-08

Similar Documents

Publication Publication Date Title
EP2215274A1 (fr) Agent et procédé de tannage de peaux et de cuirs
EP1904658B1 (fr) Procede de fabrication de cuir
EP0429830A2 (fr) Procédé de tannage des peaux et de retannage du cuir tanné au chrome
EP0304677B1 (fr) Procédé de tannage au chrome avec épuisement de bain élevé
DE2626429A1 (de) Verfahren zum gerben von haeuten
EP2257650A1 (fr) Procédé de fabrication de cuir
DE4430290A1 (de) Verfahren zur Herstellung von Leder und Pelzfellen durch Vorgerben mit einem Aldehydgerbstoff und Ausgerben mit einem mineralischen Gerbstoff
EP0533011A1 (fr) Procédé pour la production du cuir tanné au chrome
CH691062A5 (de) Wässrige Zusammensetzung zum Vorgerben von Hautblössen oder Nachgerben von Leder.
DE1230170B (de) Gerbverfahren
EP0265657B1 (fr) Procédé de tannage du cuir
EP0808908A1 (fr) Cuir et sa fabrication
DE2424301C3 (de) Verfahren zum Chromgerben und Gerbmischung dafür
DE2424300B2 (de) Verfahren zum chromgerben und gerbmischung dafuer
DE639787C (de) Verfahren zur Herstellung von Eisenledern
DE2755087A1 (de) Verfahren zum gerben von leder
EP0574800B1 (fr) Procédé de tannage du cuir et fourrures
DE582253C (de) Verfahren zum Behandeln von Bloessen und Leder
DE3632638A1 (de) Verfahren zur gerbung von leder
DE975207C (de) Gerben von Fellen und Haeuten
DE1241032B (de) Verfahren zur Herstellung von Leder
EP0554218A1 (fr) Procédé pour piquage de peaux
DE1494841A1 (de) Verfahren zum Schnellgerben von Leder
DE281484C (de) Verfahren zum gerben tierischer häute
DE686655C (de) Verfahren zur Herstellung voller und reissfester Leder

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200980110016.5

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09722872

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2009722872

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 6622/CHENP/2010

Country of ref document: IN

ENP Entry into the national phase

Ref document number: PI0909178

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20100913