EP2956558A1 - Procédé de fabrication de cuir - Google Patents

Procédé de fabrication de cuir

Info

Publication number
EP2956558A1
EP2956558A1 EP14703867.3A EP14703867A EP2956558A1 EP 2956558 A1 EP2956558 A1 EP 2956558A1 EP 14703867 A EP14703867 A EP 14703867A EP 2956558 A1 EP2956558 A1 EP 2956558A1
Authority
EP
European Patent Office
Prior art keywords
leather
acid
methanesulfonic acid
weight
tanning
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.)
Granted
Application number
EP14703867.3A
Other languages
German (de)
English (en)
Other versions
EP2956558B1 (fr
Inventor
Robert Orth
Yu Mei
Walter Bertkau
Thomas Schneider
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 EP14703867.3A priority Critical patent/EP2956558B1/fr
Publication of EP2956558A1 publication Critical patent/EP2956558A1/fr
Application granted granted Critical
Publication of EP2956558B1 publication Critical patent/EP2956558B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • 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
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring

Definitions

  • the present invention relates to a process for producing leather comprising a plurality of steps, characterized in that methanesulfonic acid is used in at least one step.
  • Processes for making leather typically involve a variety of steps. Many steps of leather production are carried out in aqueous medium at a certain pH. The adjustment of the optimum pH is of great importance and influences the properties of the produced leather.
  • the choice of a suitable acid to neutralize the leather has a significant influence on the quality of the leather produced. This is the case, for example, in the deliming step.
  • too much acid can negatively affect the optical and physical properties of the leather, possibly because the raw hides swell too much. If one chooses a too weak acid, this can mean that the adjustment of the pH is slow or the acid or other substances needed for the production of the leather do not completely penetrate the rawhide. In addition to the pH, the properties of the leather are often influenced by the materials used and the manufacturing process in a way that is not always predictable.
  • conventional leather production methods in the deliming step remove the lime residues adhering to the liming, for example with about 1% lactic acid, dilute acetic acid, formic acid or other organic acids.
  • suitable acids are, for example, ammonium salts such as ammonium sulfate or ammonium chloride, boric acid, phosphoric acid or carbonic acid. Also possible is the use of hydrochloric acid or sulfuric acid.
  • EP 563,139 describes the use of methanesulfonic acid for pimpling leather.
  • the object of the present invention was to provide a process for producing leather which does not have the disadvantages of the prior art which gives soft and attractive leather and is efficient to perform.
  • the object has been achieved by a process for producing leather comprising a plurality of steps, characterized in that methanesulfonic acid is used in at least one step.
  • Animal skins are the skins of any dead animals such as beef, veal, pork, goat, sheep, kangaroo, fish, ostrich or game. It is irrelevant to the present invention whether the animals whose hides one wishes to treat were slaughtered, were huntmännisch killed or have died from natural causes.
  • Processes for making leather typically involve a variety of steps.
  • the hair is removed from the animal skin.
  • This step is also referred to as a shearing step.
  • the animal skin is usually treated with basic substances such as lime. Frequently, sodium hydroxide, sodium carbonate, sulfides or organic sulfur compounds are also added.
  • the deboning step for example, meat remnants and subcutaneous connective tissue are mechanically removed from the animal skin.
  • the deliming step also: descaling, English: deliming
  • the basic components from the depilatory step are partially or completely neutralized.
  • the animal skin is loosened and prepared for the absorption of tannin and thus on the actual tanning.
  • a step of stroking is performed, in which the stroking of the skins, for example, by means of chisel on the tanner tree.
  • the actual tanning steps are done with the addition of a tanning agent.
  • Suitable tanning methods include the use of mineral salts (chromium-ill, aluminum, zirconium or iron salts), vegetable tanning with vegetable tannins (tannins in leaves, barks, woods and fruits), tanning (synonymously tanning) with fish and marine oils ( Trane) or with fats of the brain, synthetic tanning with synthetically produced tanning substances (syntans, resin tannins, polymer tanning agents, polyphosphates, paraffinsulfochloride), aldehyde tannin (formerly formaldehyde, today mainly glutaraldehyde). It is also possible to combine different tanning procedures.
  • the leather After tanning, the leather is usually mechanically dehydrated (withering) and brought to a uniform thickness with folding machines.
  • the final leather Shadows such as softness, color, fullness, structure, elasticity, water absorption etc. are determined by the wet finish.
  • the coloring is often done with dyes that form a chemical bond with the leather fiber.
  • Advantageous dyes are distinguished not only by the good dyeing properties (for example, tacking properties on the leather, combinability, large color palette) and fastness properties, but also by low environmental impact.
  • the natural leather color depends, among other things, on the tanning agent used. Chrome tannins often give a light, greyish-green intrinsic color, vegetable oils can, for example, yellow-brown - reddish brown. Aluminum salts and synthetic tannins often yield white to light beige leather. Glutaraldehyde and fatty tanning agents usually color the leathers yellowish.
  • a pH of 4 to 6.5 is usually set, preferably from 4.5 to 6.
  • a more acidic pH is set to ensure uniform fixation of the fatliquoring agent through the leather cross section to reach.
  • a pH of from 2 to 6, preferably from 2.5 to 5, particularly preferably from 3 to 4 and especially preferably from 3.2 to 3.5 is set towards the end of the fatliquoring step.
  • processes for producing leather may include other steps in addition to the aforementioned steps.
  • methanesulfonic acid is used in at least one of the steps for the production of leather.
  • Methanesulfonic acid serves primarily to adjust the pH.
  • Methanesulfonic acid is preferably added to the animal skin at the beginning of the actual working step.
  • the operation consists essentially of the neutralization of basic components with acids, which according to the invention methanesulfonic acid include.
  • the use of methanesulfonic acid in a particular step is also understood to mean the addition of methanesulfonic acid before the actual working step or after the preceding working step, if this serves to prepare the actual working step.
  • Methanesulfonic acid is preferably used in at least one of the following steps: deliming, pickling, pickling, brushing, tanning, retanning, dyeing, fatliquoring.
  • Methanesulfonic acid is particularly preferably used at least in the case of deliming and / or pickling and / or pickling and / or fatliquoring.
  • methanesulfonic acid is used at least in the decarburization step. In another preferred embodiment, methanesulfonic acid is used at least in the fatliquoring step.
  • Methanesulfonic acid is used according to the invention usually as an aqueous solution.
  • methanesulfonic acid is used as 0.05 to 0.5% strength by weight aqueous solution, preferably 0.07 to 0.2% by weight and particularly preferably 0.08 to 0.15% by weight.
  • methanesulfonic acid is used together with salts and / or other acids and / or acid derivatives.
  • Suitable acid derivatives are, for example, esters or acid anhydrides.
  • methanesulfonic acid is used with salts of methanesulfonic acid.
  • Suitable salts of methanesulfonic acid include, for example, alkali metal or alkaline earth metal salts such as sodium, potassium, magnesium or calcium salts of methanesulfonic acid.
  • methanesulfonic acid is used together with inorganic salts.
  • suitable inorganic salts are, for example, salts of sulfuric acid, hydrohalic acids, phosphoric acid, boric acid, carbonic acid, nitric acid.
  • suitable inorganic salts are, for example, ammonium sulfate, sodium sulfate, sodium chloride, ammonium chloride.
  • methanesulfonic acid is used together with salts of organic acids.
  • Suitable salts of organic acids are, for example, ammonium, alkali metal or alkaline earth metal salts of organic acids, such as ammonium, sodium, potassium or magnesium salts of organic acids.
  • Suitable salts of organic acids are, for example, salts of monocarboxylic acids or dicarboxylic acids. Examples of suitable salts of organic acids are, for example, salts of formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, tartaric acid, lactic acid, phthalic acid, terephthalic acid, maleic acid, fumaric acid.
  • methanesulfonic acid is used together with other acids.
  • Suitable other acids may be inorganic acids or organic acids.
  • Suitable inorganic acids are, for example, sulfuric acid, hydrochloric acid, boric acid, carbonic acid, phosphoric acid.
  • Suitable organic acids are, for example, monocarboxylic acids or dicarboxylic acids. Examples of suitable organic acids are formic, acetic, lactic, formic, propionic, oxalic, malonic, succinic, glutaric, adipic, tartaric, lactic, phthalic, terephthalic, maleic and fumaric acids.
  • methanesulfonic acid is used in combination with ammonium sulfate.
  • methanesulfonic acid is used in combination with formic acid.
  • methanesulfonic acid is used in combination with one or more ammonium salts of dicarboxylic acids.
  • methanesulfonic acid is used in combination with one or more aliphatic dicarboxylic acids.
  • methanesulfonic acid is used in combination with one or more carboxylic acid esters.
  • the amount of salts, other acids or acid derivatives can vary widely.
  • an aqueous solution containing 0.05 to 0.2% by weight of methanesulfonic acid and 0.5 to 2% by weight of ammonium sulfate is used.
  • a pH of 4 to 9, preferably 6 to 8.5 and particularly preferably 7.5 to 8.5 is set.
  • the deliming step lasts from 30 minutes to 4 hours, in exceptional cases shorter or longer.
  • the deliming step is completed in 45 to 90 minutes.
  • Processes according to the invention are characterized in that they are simple to carry out and permit an efficient and rapid adjustment of the pH in the individual process steps.
  • inventive methods allow the production of leather, which are characterized by advantageous optical and haptic properties.
  • they are characterized by pleasant softness and do not swell so much, do not swell so much as leather, which are produced by conventional methods.
  • the leathers produced according to the invention are characterized by a good softness and have a pleasant, appealing, fine and clean grain. In addition, they have good dyeing properties such as high uniformity and color brilliance.
  • the physical properties such as tensile strength, tensile strength at break, elongation at break or curvature of the leather produced by the process according to the invention are comparable or better than those of leather, which have been prepared according to the prior art.
  • leather produced according to the invention which has been prepared by using methanesulfonic acid in the deliming step, is distinguished, in addition to the advantages described above, by the fact that calcium ions can be removed from the leather very efficiently. As a result, in particular the softness and tear strength of the leather is advantageously influenced.
  • Another object of the present invention is leather, which has been produced by the process according to the invention.
  • Decalta 'RN Acid-reacting mixture of ammonium salts of inorganic acids and organic dicarboxylic acids
  • Decalta 'Pic S Mixture of weak, water-soluble aliphatic dicarboxylic acids
  • Decalta 'ESN liquid mixture of carboxylic acid esters Examples 1.1 to I.6
  • a rawhide of beef was depilated and fleshed. The depilation took place with the addition of quick lime and sodium sulfide.
  • the leathers were treated with decalcifier according to example 1.1 to I.6 in order to set a pH of 8. The skins were first treated at room temperature for 20 minutes with a mixture A and then for 60 minutes with a mixture B. Subsequently, the skins were subjected to tanning and retanning with identical chromium-tanning formulations.
  • Mixture A aqueous solution containing 0.1% by weight of sodium hydrogen sulfite and 0.5% by weight of ammonium sulfate.
  • Mixture B aqueous solution containing 0.1 wt% sodium bisulfite, 0.14 wt% methanesulfonic acid (70 wt% in water) and 1, 5 wt% of an acid-reacting mixture of Decalta) RN.
  • Example I.2 aqueous solution containing 0.1% by weight of sodium hydrogen sulfite and 0.5% by weight of ammonium sulfate.
  • Mixture B aqueous solution containing 0.1 wt% sodium bisulfite, 0.14 wt% methanesulfonic acid (70 wt% in water) and 1, 5 wt% of an acid-reacting mixture of Decalta) RN.
  • Example I.2 aqueous solution containing 0.1% by weight of sodium hydrogen sulfite and 0.5% by weight of ammonium sul
  • Mixture A aqueous solution containing 0.1% by weight of sodium hydrogen sulfite and 0.5% by weight of ammonium sulfate.
  • Mixture B aqueous solution containing 0.1% by weight of sodium hydrogen sulfite and 0.3% by weight of decaltal ⁇ R > Pic S and 1.5% by weight of ammonium sulfate.
  • Mixture A aqueous solution containing 0.1% by weight of sodium hydrogen sulfite and 0.5% of decaltal ⁇ R > RN.
  • Mixture B aqueous solution containing 0.1% by weight of sodium hydrogen sulfite, 0.14% by weight of methanesulfonic acid (70% strength by weight in water) and 1.5% of Decalta® RN.
  • Mixture A aqueous solution containing 0.1% by weight of sodium hydrogen sulfite and 0.5% of decaltal ⁇ R > RN.
  • Mixture B aqueous solution containing 0.1 wt% sodium hydrogen sulfite, 0.3 wt% methane sulfonic acid (70 wt% in water) and 1, 5% by weight Decaltal ⁇ R> RN.
  • Mixture A aqueous solution containing 0.1% by weight of sodium hydrogen sulfite and 0.14% by weight of methanesulfonic acid (70% by weight in water).
  • Mixture B aqueous solution containing 0.1 wt% sodium bisulfite, 0.14 wt% methanesulfonic acid (70 wt% in water) and 1, 2% by weight Decaltal ⁇ R> ESN.
  • Mixture A aqueous solution containing 0.1% by weight of sodium hydrogen sulfite and 0.25% by weight of Decalta ) Pic S.
  • Mixture B aqueous solution containing 0.1% by weight of sodium hydrogen sulfite, 0.25% by weight of decalta ) Pic S and 1.2% by weight of Decaltal ⁇ R > ESN.
  • methanesulfonic acid made it possible to adjust the pH in a shorter time and gave clean and flat raw skins which were not so much swollen as skins which were subjected to deliming without methanesulfonic acid.
  • the leathers made using methanesulfonic acid in the deleting step are softer than leathers made according to the prior art and have them nice, fine and clean scars.
  • the physical properties are comparable to or better than those of leathers made according to the prior art.
  • cowhide rawhide Four pieces of cowhide rawhide were depilated and fleshed. The depilation took place with the addition of quick lime and sodium sulfide. For deliming, the skins were first washed at room temperature for 20 minutes with water and then first with a 1, 2 wt% solution of ammonium sulfate and then with a 3.5
  • Table 1 pH and calcium ion concentration in ppm in the deliming solution for Examples 11.1 and II.2, Ca 2+ concentration determined by means of atomic emission spectroscopy
  • the pH of the deliming solutions for Examples 11.1 and II.2 was between 8.3 and 8.43 in both cases and was very similar.
  • the content of free calcium ions in the deliming solution to Example 11.1 and II.2 was significantly higher with the addition of methanesulfonic acid than without the addition of methanesulfonic acid.
  • the leathers of Examples 11.1 and II.2 were dried prior to or after completion of the deliming. 0.15 g of leather was placed in a 50 ml Erlenmeyer flask and 4 ml of a mixture of nitric acid and hydrochloric acid (mass ratio 1.3) were added. So- When the mixture was again cooled to room temperature, 1 ml of hydrogen peroxide was added thereto (32% by weight in water). The mixture was heated to 120 ° C for 180 min. The mixture was cooled to room temperature and made up to 50 ml volume with water. The content of calcium ions in the leather was determined by determining the concentration of calcium ions in the solution by atomic absorption spectrometer.
  • the leathers of Examples 11.1 and II.2 were washed twice with water for 10 minutes. Subsequently, the skins were subjected to tanning and retanning with identical chromium-tanning formulations.
  • Example II.2 (with the addition of methanesulfonic acid) were less swollen and softer than the leathers of Example 11.1 (without methanesulfonic acid).
  • Chromium-tanned wet-blue leather (beef) was cut into 1-by-1 cm pieces and 25 g each was placed in a 250-ml glass flask.
  • 25 g each was placed in a 250-ml glass flask.
  • 5 g of fatliquoring agent according to Table 2 were given and in each case so much fully demineralized (VE) water that the amount of liquid in the flask including fatliquoring agent was 75 ml.
  • the flasks were heated to 40 ° C for three hours.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Abstract

L'invention concerne un procédé de fabrication de cuir comportant plusieurs étapes, caractérisé en ce que dans au moins une étape, de l'acide méthane sulfonique est utilisé.
EP14703867.3A 2013-02-14 2014-02-12 Procédé pour la fabrication de cuir Active EP2956558B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP14703867.3A EP2956558B1 (fr) 2013-02-14 2014-02-12 Procédé pour la fabrication de cuir

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP13155256.4A EP2607499A3 (fr) 2013-02-14 2013-02-14 Procédé destiné à la fabrication de cuir
PCT/EP2014/052691 WO2014124951A1 (fr) 2013-02-14 2014-02-12 Procédé de fabrication de cuir
EP14703867.3A EP2956558B1 (fr) 2013-02-14 2014-02-12 Procédé pour la fabrication de cuir

Publications (2)

Publication Number Publication Date
EP2956558A1 true EP2956558A1 (fr) 2015-12-23
EP2956558B1 EP2956558B1 (fr) 2016-11-16

Family

ID=47720387

Family Applications (2)

Application Number Title Priority Date Filing Date
EP13155256.4A Withdrawn EP2607499A3 (fr) 2013-02-14 2013-02-14 Procédé destiné à la fabrication de cuir
EP14703867.3A Active EP2956558B1 (fr) 2013-02-14 2014-02-12 Procédé pour la fabrication de cuir

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP13155256.4A Withdrawn EP2607499A3 (fr) 2013-02-14 2013-02-14 Procédé destiné à la fabrication de cuir

Country Status (12)

Country Link
US (1) US11001902B2 (fr)
EP (2) EP2607499A3 (fr)
KR (1) KR102230317B1 (fr)
CN (1) CN104981549A (fr)
AR (1) AR094785A1 (fr)
AU (1) AU2014218021B2 (fr)
BR (1) BR112015019537A2 (fr)
ES (1) ES2616043T3 (fr)
MX (1) MX377941B (fr)
TW (1) TWI653341B (fr)
WO (1) WO2014124951A1 (fr)
ZA (1) ZA201506725B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022124892A1 (fr) 2020-12-09 2022-06-16 Stahl International B.V. Procédé de déchaulage de cuirs, de peaux ou de fourrures

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Publication number Priority date Publication date Assignee Title
US10131831B2 (en) 2014-04-11 2018-11-20 Basf Se Process for acidizing using retarded acid formulations
CN104313199B (zh) * 2014-10-28 2016-03-09 北京泛博化学股份有限公司 小液比制备绵羊皮服装毛革的方法
EP3469104B1 (fr) * 2016-06-14 2022-09-28 Basf Se Procédé de préparation de cuir
CN109485562B (zh) * 2017-09-13 2022-11-25 斯塔尔国际有限公司 脱灰剂及其用途和脱灰方法
WO2020126855A1 (fr) * 2018-12-21 2020-06-25 Basf Se Mélange comprenant de l'acide méthanesulfonique et de l'acide sulfurique
EP3670675A1 (fr) * 2018-12-21 2020-06-24 LANXESS Deutschland GmbH Adjuvants dans la fabrication du cuir pour le travail de rivière
IL286137B2 (en) * 2019-02-13 2025-09-01 DEBx Medical Holding BV Preparations for removing dead or contaminated tissues from body surface injuries and the oral cavity
IT202000017719A1 (it) * 2020-07-22 2022-01-22 Beken Italia S R L Processo a ridotto impatto ambientale per la concia di pelli

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
WO2022124892A1 (fr) 2020-12-09 2022-06-16 Stahl International B.V. Procédé de déchaulage de cuirs, de peaux ou de fourrures
NL2027083B1 (en) 2020-12-09 2022-07-07 Stahl Int B V Process for deliming of hides, skins or pelts

Also Published As

Publication number Publication date
TW201441374A (zh) 2014-11-01
EP2956558B1 (fr) 2016-11-16
WO2014124951A1 (fr) 2014-08-21
BR112015019537A2 (pt) 2017-07-18
US11001902B2 (en) 2021-05-11
AU2014218021A1 (en) 2015-09-03
ZA201506725B (en) 2017-09-27
MX2015010584A (es) 2016-05-31
CN104981549A (zh) 2015-10-14
EP2607499A3 (fr) 2013-07-10
MX377941B (es) 2025-03-11
KR102230317B1 (ko) 2021-03-19
NZ710857A (en) 2020-09-25
EP2607499A2 (fr) 2013-06-26
US20150376726A1 (en) 2015-12-31
AU2014218021B2 (en) 2017-03-16
KR20150119203A (ko) 2015-10-23
TWI653341B (zh) 2019-03-11
ES2616043T3 (es) 2017-06-09
AR094785A1 (es) 2015-08-26

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