EP0563139B1 - Verfahren zur behandlung von häuten oder leder durch einsatz von methansulfonationen. - Google Patents

Verfahren zur behandlung von häuten oder leder durch einsatz von methansulfonationen. Download PDF

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Publication number
EP0563139B1
EP0563139B1 EP92901323A EP92901323A EP0563139B1 EP 0563139 B1 EP0563139 B1 EP 0563139B1 EP 92901323 A EP92901323 A EP 92901323A EP 92901323 A EP92901323 A EP 92901323A EP 0563139 B1 EP0563139 B1 EP 0563139B1
Authority
EP
European Patent Office
Prior art keywords
hides
leathers
methanesulfonic acid
tanning
skins
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP92901323A
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English (en)
French (fr)
Other versions
EP0563139A1 (de
Inventor
Mireille Kerneis
Louis Gaches
Michel Delmas
Antoine Gaset
Jacques Vigouroux
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.)
GACHES CHIMIE SA
Original Assignee
GACHES CHIMIE SA
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 GACHES CHIMIE SA filed Critical GACHES CHIMIE SA
Publication of EP0563139A1 publication Critical patent/EP0563139A1/de
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Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C1/00—Chemical treatment prior to tanning
    • C14C1/08—Deliming; Bating; Pickling; Degreasing
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/04—Mineral tanning
    • C14C3/06—Mineral tanning using chromium compounds
    • 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
    • D06P1/623—Aliphatic, aralophatic or cycloaliphatic
    • 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
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/32—Material containing basic nitrogen containing amide groups leather skins

Definitions

  • the invention relates to a method of treating tanneries or tannery made from collagenous fabrics such as skins or leathers, with a view to achieving a loosening effect on the fibers of the fabrics and internal distribution of fats, leading to an increase in surface area. skins and a homogenization of their thickness, and also an improvement in the surface qualities of the articles (feel, appearance, regularity, ...) and their flexibility.
  • the existing treatment agents which lead to a certain improvement in the leathers are generally specific to such or such operation (for example acetic acid and adjuvant for the pickling of skins, cationic / anionic products or surfactants for the food of leathers ...) and cannot be used at any other stage of production.
  • One of the essential defects of the skins resides in the thickness irregularities which they present: currently, no treatment process is capable of making it possible to obtain a uniform thickness of the skins and to increase the surface thereof, while preserving their integrity. It is important to emphasize that most skins are sold on the surface and that a significant gain in surface area, associated with a more uniform thickness represents a considerable industrial advantage.
  • the present invention proposes to provide a new process for the treatment of skins or hides made up of collagenous tissues with a view to homogenizing their thickness and increasing their surface area while preserving their integrity.
  • An objective of the invention is to obtain this result without adding an external product to the collagen structure, in particular without adding fat.
  • Another objective is to concomitantly improve the surface qualities of the skins (feel, appearance) and their flexibility, and this, in a more pronounced manner than the known methods.
  • Another objective is to provide a cost process compatible with the valuation of lower quality skins under good profitability conditions.
  • Another objective is to provide a process capable of being implemented at different stages of the manufacture of leather (in particular at the stages which involve a lowering of the pH).
  • the process according to the invention for treating tanneries and tanning articles made up of collagenous fabrics such as skins and leather consists in bringing the skins or leathers in contact with methanesulfonic acid CH3 SO3H or methanesulfonate ions CH3 SO3 ⁇ In an acid medium.
  • the skins can in particular be brought into contact with methanesulfonic acid in an aqueous medium or a mixed water / organic solvent medium.
  • the term "mixed medium” will mean a medium containing one or more organic solvents and water, even if the latter remains in very small proportion).
  • the minimum quantity of methanesulfonic acid or of methanesulfonate ions in acid medium necessary to lead to a sensitive result is of the order of 0.05 mol per kg of dry skins or hides. (By a weight of "dry skins”, we mean the weight of the skins at the start of the treatment, minus the weight of bound water).
  • the invention was born from the chance observation of an unexpected and remarkable phenomenon: when skins or leathers are brought into contact with methanesulfonic acid or methanesulfonate ions in an acid medium, whatever the stage of manufacture where this contacting is practiced, there is an effect of loosening of the fibers of the collagen tissues and internal distribution of clean fats: the thickness of the skins is made more uniform, while the surface of these is significantly increased (by about 5%). Methanesulfonic acid or methanesulfonate ions are found almost entirely at the end of treatment in the bath, so that no contribution has been made in the skin.
  • the mechanism of action is difficult to explain at present: it seems that the methanesulfonate ions temporarily bind to the clean fats of the skin to increase mobility and allow migration of fats from the thickest parts of the skin. (therefore the fatty ones) to produce a spreading effect, leading to an increase in the surface and a homogenization of the thickness; this fixation is then destroyed for reasons that are not well known and the methanesulfonate returns to the bath where it is recovered.
  • the total amount of methanesulfonic acid or methanesulfonate ions is preferably between 0.1 and 2 moles per kg of dry skin: this amount therefore remains very small compared to the amount of clean fat of the skin, so that the actions above mentioned are catalytic type.
  • methanesulfonic acid or methanesulfonate ions contain a single carbon and are not surfactants: they have properties completely different from those of the long chain sulfonates used to nourish skins thanks to the fats that they bring to these.
  • the effects on the skin of the process of the invention are very different from those of a food operation since, in the case of the invention, the compound is almost completely recovered and is not definitively fixed in or on the skin: it acts on its own fats and preserves the integrity of the skins without external material supply in their texture, which is not the case with the above-mentioned surfactants.
  • Methanesulfonate ions are closer, by their chemical structure and known properties, to sulfate ions; the latter have been used for a long time in tanning operations for hides and skins without leading to the results provided by the ions of the process targeted by the invention (namely: action on the clean fats of the skin leading to homogenization of thickness and increase in surface).
  • the methanesulfonic acid which leads in an aqueous medium to methanesulfonate ions is a strong organic acid, well known in itself.
  • US Patent 2,297,722 describes a manufacturing process. It is currently used essentially as a substitute for fluoroboric acid in electroplating baths, as a trapping agent for heavy metals in petroleum derivatives, as a corrosion inhibitor against magnesium alloys, or as a catalyst for certain reactions ( esterification, alkylation, polymerization of olefins ).
  • the tests also made it possible to note that the process of the invention made it possible to obtain a reproducible, very significant improvement in the surface condition of the skins and their suppleness.
  • all the metallic methanesulfonates being very soluble in water, the process of the invention avoids any risk of precipitation of insoluble salts (calcium sulfate for example) capable of being deposited on or in the skins during the cycle of manufacturing and cause a degradation of their surface qualities or flexibility.
  • the leather manufacturing cycle from raw hides generally includes a pickling operation consisting in acidifying these hides. Bringing raw or tripe skins into contact with methanesulfonate ions can be carried out during this pickling operation using methanesulfonic acid optionally combined with another acid (in particular sulfuric acid).
  • the manufacturing cycle also includes a tanning operation.
  • the contacting can be carried out during this operation by introducing the methanesulfonate ions into the tanning bath.
  • the tanning agent for this bath can be of any known type, mineral, vegetable and / or synthetic and the bath then contains a mixture of this agent and methanesulfonic acid or a salt of this acid.
  • chromium tanning with a specific agent consisting of chromium methanesulfonate in an aqueous or mixed medium. This compound releases both the metal ions ensuring the tanning and the methanesulfonate ions leading to the abovementioned results.
  • the leather manufacturing cycle also includes a dyeing operation, bringing the dye into contact is generally ensured at a pH close to neutral and fixing it at a lower pH.
  • the methanesulfonate ions can be brought into contact during this operation by using methanesulfonic acid optionally combined with another organic acid (in particular formic acid or acetic acid).
  • the skins can be brought into contact with the methanesulfonate ions several times and in particular at the three aforementioned manufacturing stages: pickling, tanning and dyeing.
  • This mode of implementation leads in particular to the following practical advantage: to obtain a given quality, the concentration of methanesulfonate ions is lower at each operation (compared to a single contacting), which avoids too great a reduction pH, which could be detrimental to the quality of the skins.
  • the total optimal quantity of methanesulfonate ions which should be brought into contact with the skins in one or more stages during the manufacturing cycle to obtain a marked improvement in their qualities without wasting product , seems to be understood, as already indicated, between 0.1 and 2.0 moles per kg of dry skins or hides.
  • This process consists in reacting methanesulfonic acid on a barium salt, then reacting the barium methanesulfonate obtained with chromium sulfate and eliminating the precipitate by centrifugation filtration in order to isolate the chromium methanesulfonate in solution.
  • This process can be carried out at room temperature and at atmospheric pressure. When precipitating, barium sulfate shifts the balance and leads to chromium methanesulfonate without any special precautions.
  • the chromium content of the chromium methanesulfonate solution thus prepared is determined by atomic absorption: 35 g Cr / l.
  • This solution can be used directly in tanning or else the chromium salt can be isolated in crystallized form by precipitation with acetone.
  • the quantities of added products are expressed as a percentage by weight of the weight of the pickled skins.
  • the skins are removed from the tanning bath and left to stand for 48 hours (extended skins stacked on top of each other).
  • the tanned hides obtained are subjected to a visual analysis: the chromium is uniformly distributed and fixed; the hides have a shrinking temperature of more than 100 ° C, which characterizes a good quality of tanning.
  • the quantities of products added are given as a percentage by weight of the weight of the tripe skins.
  • the two batches of skins a) and b) are fed, then dyed in a conventional manner.
  • an industrial pass of one tonne of skins made it possible to quantify the increase in surface area.
  • a reference pass measures approximately 8000 ft2 (approximately 743 m2).
  • a pass treated with methanesulfonic acid measures approximately 8,400 square feet (approximately 780 m2), a considerable increase in surface area of 5%.
  • the quantities of added products are expressed as a percentage by weight of the weight of the pickled skins.
  • chromium sulphate (basicity 33 ° chromium content: 26%) is then added to the bath, an operation which is followed by the addition after 1 hour, of 1% of sodium formate and then of 4% of sodium hydrogen carbonate. in four times in three hours; the end of tanning pH is 4.1. Still in the tanning bath, the skins are heated for one hour at 50 ° C.
  • the dye is uniformly distributed, as is the chromium, as evidenced by a temperature of this retraction greater than 100 ° C.
  • the quantities of products added are given as a percentage by weight of the weight of dry tanned hides.
  • the dyed skins are then put in the wind and dried.
  • the quantities of added products are given as a percentage by weight of the weight of the pickled skins.
  • the skins are placed in a water bath (250%) to which are added 30% of quebracho extract in 3 times in 2 hours. The skins are left in the bath with stirring overnight, then rinsed, bleached and nourished.
  • bleaching and nourishment are carried out in the conventional way: it is placed in a bath of 200% water at 50 ° C. to which 1% of oxalic acid is added, then 3% of sodium thiosulfate, and finally 3% food.
  • the other two skins undergo the same treatment supplemented by the addition of 1% methanesulfonic acid to 70% in two batches, after the action of oxalic acid (0.21 mole of CH3 SO3 ⁇ ion per kg of dry skin ).
  • the three dry skins have a shrink temperature of 80-85 ° C, characteristic of good vegetable tanning and are, as before, subject to the appreciation of professionals.
  • the two skins treated with methanesulfonic acid have greater flexibility and above all a particularly silky feel, compared to the skin treated in a conventional manner.
  • Tripe lambskins are picked with methanesulfonic acid according to Example 2, chrome tanned in the traditional way, then dyed with fixing of the dye by methanesulfonic acid according to Example 4.
  • Example 2 As in Example 2, an increase in surface area of the order of 5% is measured, accompanied by a homogenization of the fat content and therefore of the thickness.
  • Example 7 Use of chromium methanesulfonate in mixed medium
  • the quantities of products added are expressed as a percentage by weight relative to the weight of the pickled skins.
  • Two skins (1000 g) of degreased and pickled lambs are placed in 400% brine bath at 8 ° Baumé (ie 88.24 g / l NaCl) for one hour; by spinning), the humidity of the skins is reduced to 200% of water relative to the dry weight.
  • Dry tanned hides are subjected to a visual analysis: the chromium is uniformly distributed and fixed; the hides have a shrinking temperature above 100 ° C, characteristic of good tanning.

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  • 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 (10)

  1. Verfahren zur Behandlung von kollagene Gewebe wie Häute und Leder umfassenden Produkten der Weißgerberei bzw. Gerberei, um zu einer Vergrößerung der Oberfläche der Häute und Vergleichmäßigung ihrer Dicke führende Entspannung der Gewebefasern und interne Verteilung der Fette zu bewirken, dadurch gekennzeichnet, daß man die Häute oder Leder in sauerem Medium mit Methansulfonsäure CH₃SO₃H oder Methansulfonationen CH₃SO₃⁻ in Kontakt bringt, und zwar in einem Maße von mindestens 0,05 Mol je kg Trockenhäute bzw. Trockenleder.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Häute bzw. Leder in wässerigem Medium oder einem aus einem Gemisch von Wasser und organischem Lösungsmittel bestehenden Medium mit Methansulfonsäure in Kontakt bringt.
  3. Verfahren nach Anspruch 2 zur Herstellung von Ledern aus Rohhäuten, bei dem im Laufe des Herstellungszyklus die Rohhäute einem Pökelvorgang unterzogen werden, dadurch gekennzeichnet, daß die Häute mit der Methansulfonsäure während des Pökelvorgangs in Kontakt gebracht werden, wobei die besagte Methansulfonsäure möglicherweise in Verbindung mit einer anderen Säure als Pökelmittel dient.
  4. Verfahren nach einem der Ansprüche 1 oder 2 zur Herstellung von Ledern aus Häuten, bei dem während des Herstellungszyklus die Häute einem Gerbvorgang unterzogen werden, dadurch gekennzeichnet, daß der Vorgang des Inkontaktbringens mit der Methansuifonsäure bzw. den Methansulfonationen mit dem Gerbvorgang verbunden wird, indem die besagten Ionen in das Gerbbad eingeführt werden.
  5. Verfahren nach Anspruch 4 zur Herstellung von Ledern, dadurch gekennzeichnet, daß man von einem Gerbbad Gebrauch macht, das in gemischter Form einerseits mindestens ein mineralisches, pflanzliches und/oder synthetisches Gerbmittel und andererseits Methansulfonsäure bzw. ein Salz dieser Säure enthält.
  6. Verfahren nach Anspruch 4 zur Herstellung von Ledern, dadurch gekennzeichnet, daß von einem wässerigen oder gemischten Gerbbad, das Chrommethansulfonat enthält, Gebrauch gemacht wird.
  7. Verfahren nach Anspruch 6 zur Herstellung von Ledern, dadurch gekennzeichnet, daß das dem Bad beigemischte Chrommethansulfonat dadurch zubereitet wird, daß man die Methansulfonsäure mit einem Bariumsalz zur Reaktion bringt, das erzielte Bariummethansulfonat dann mit Chromsulfat zur Reaktion bringt und den Niederschlag durch Filtrieren oder Zentrifugieren abscheidet, um das in Lösung befindliche Chrommethansulfonat zu isolieren.
  8. Verfahren nach einem der Ansprüche 1 oder 2 zur Herstellung von Ledern aus gegerbten Häuten, bei dem während des Herstellungszyklus die gegerbten Häute einem Färbvorgang unterzogen werden, in dessen Verlauf sie mit dem Farbstoff bei einem nahezu neutralen pH-Wert in Kontakt gebracht werden, worauf der besagte Farbstoff bei einem geringeren pH-Wert fixiert wird, dadurch gekennzeichnet, daß der Vorgang des Inkontaktbringens der Methansulfonsäure im Zuge des Färbens durchgeführt wird, wobei zwecks Senkung des pH-Werts von der besagten Methansulfonsäure möglicherweise in Verbindung mit einer anderen Säure Gebrauch gemacht wird.
  9. Verfahren nach den Ansprüchen 3, 4 und 8 gemeinsam zur Herstellung von Ledern, dadurch gekennzeichnet, daß die Häute mit der Methansulfonsäure mindestens dreimal, und zwar während des Pökelns, während des Gerbens in dem Gerbbad und während des Färbvorgangs, in Kontakt gebracht werden.
  10. Verfahren nach einem der Ansprüche 3 bis 9 zur Herstellung von Ledern, dadurch gekennzeichnet, daß die Häute mit der Methansulfonsäure so in Kontakt gebracht werden, daß der Gesamtanteil dieser Säure zwischen 0,1 und 2,0 Mol je kg Trockenhäute beträgt.
EP92901323A 1990-12-19 1991-12-06 Verfahren zur behandlung von häuten oder leder durch einsatz von methansulfonationen. Expired - Lifetime EP0563139B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9016520 1990-12-19
FR9016520A FR2670800B1 (fr) 1990-12-19 1990-12-19 Procede de traitement de peaux ou cuirs, agents de tannage et procede de fabrication.
PCT/FR1991/000979 WO1992011391A1 (fr) 1990-12-19 1991-12-06 Procede de traitement de peaux ou cuirs, agents de tannage et procede de fabrication

Publications (2)

Publication Number Publication Date
EP0563139A1 EP0563139A1 (de) 1993-10-06
EP0563139B1 true EP0563139B1 (de) 1995-03-01

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP92901323A Expired - Lifetime EP0563139B1 (de) 1990-12-19 1991-12-06 Verfahren zur behandlung von häuten oder leder durch einsatz von methansulfonationen.

Country Status (9)

Country Link
EP (1) EP0563139B1 (de)
CN (1) CN1063312A (de)
AR (1) AR248051A1 (de)
AU (1) AU9112491A (de)
ES (1) ES2069988T3 (de)
FR (1) FR2670800B1 (de)
MA (1) MA22365A1 (de)
PT (1) PT99843A (de)
WO (1) WO1992011391A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2607499A3 (de) * 2013-02-14 2013-07-10 Basf Se Verfahren zur Herstellung von Leder

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7320793B2 (en) 2001-01-19 2008-01-22 Cytos Biotechnology Ag Molecular antigen array
KR100556504B1 (ko) * 2002-12-18 2006-03-03 엘지전자 주식회사 전기 오븐 레인지의 안전 장치
WO2017009867A1 (en) * 2015-07-13 2017-01-19 Council Of Scientific & Industrial Research A dispersing agent composition for tanning of hides/skins and a process for the preparation thereof
ES2927983T3 (es) * 2016-06-14 2022-11-14 Basf Se Un procedimiento para producir cuero
CN106755647B (zh) * 2017-03-16 2018-10-30 林建武 一种皮革制造用皮料浸泡药水制备装置
CN114540558A (zh) * 2021-12-14 2022-05-27 浙江中辉裘革科技有限公司 一种捕获-洗脱-固定联用的除去毛皮游离甲醛方法

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IT1002971B (it) * 1973-11-07 1976-05-20 Schill And Seilacher Procedimento per la produzione e l impiego di una sostanza conciante al cromo ingrassante
SU1057544A1 (ru) * 1982-07-28 1983-11-30 Джамбулский технологический институт легкой и пищевой промышленности Способ обработки голь овчин

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
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R.C. PAUL et al, Indian J. Chem. (12), 825-6 (1974) *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2607499A3 (de) * 2013-02-14 2013-07-10 Basf Se Verfahren zur Herstellung von Leder
WO2014124951A1 (de) * 2013-02-14 2014-08-21 Basf Se Verfahren zur herstellung von leder
KR20150119203A (ko) * 2013-02-14 2015-10-23 바스프 에스이 피혁의 제조 방법

Also Published As

Publication number Publication date
ES2069988T3 (es) 1995-05-16
AU9112491A (en) 1992-07-22
AR248051A1 (es) 1995-05-31
CN1063312A (zh) 1992-08-05
FR2670800A1 (fr) 1992-06-26
WO1992011391A1 (fr) 1992-07-09
MA22365A1 (fr) 1992-07-01
FR2670800B1 (fr) 1994-05-20
PT99843A (pt) 1992-12-31
EP0563139A1 (de) 1993-10-06

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