EP3049541B1 - Process for tanning leathers with triazine derivatives - Google Patents

Process for tanning leathers with triazine derivatives Download PDF

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Publication number
EP3049541B1
EP3049541B1 EP14790355.3A EP14790355A EP3049541B1 EP 3049541 B1 EP3049541 B1 EP 3049541B1 EP 14790355 A EP14790355 A EP 14790355A EP 3049541 B1 EP3049541 B1 EP 3049541B1
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EP
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Prior art keywords
tanning
collagen
skin
mmol
water
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EP14790355.3A
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German (de)
English (en)
French (fr)
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EP3049541A2 (en
Inventor
Aurora ZANCANARO
Giorgio POZZA
Valentina BEGHETTO
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Gruppo Mastrotto SpA
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Gruppo Mastrotto SpA
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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
    • C14C3/08—Chemical tanning by organic agents

Definitions

  • the present invention relates to a process for treating high molecular weight proteins, particularly proteins deriving from the rough skin of animals, which allows to raise their hydrothermal stability and their resistance to rot, thus obtaining a tanned leather. More specifically, the invention describes a process for tanning leathers with triazine derivatives, in particular with dimethoxytriazinyl-N-methylmorpholine salts, such as, for example, the 4-(4,6-dimethoxy-1,3,5-triazin-2-il)-4-metilmorpholine chloride (DMTMM).
  • the tanning process of leathers consists of different steps, in order to transform the animal skin, which is easily subjected to bacterial attacks, into a stable and resistant to rot material.
  • the rough skin is normally renewed, calcined, shaved, de-calcined and soaked.
  • the combination of said processes traditionally referred to as the "Riviera method" allows to remove unwanted substances (dirt, grease, blood, interfibrillary proteins, hyaluronic acid, etc.) from the skin and to open the dermal fibers in a controlled way.
  • the only component of the skin which is useful for performing a tanning operation is the collagen, i.e. the protein constituting the fibrous reticulum of the leather.
  • the de-calcined and soaked skin is normally subjected to a specific treatment before the tanning phase, in order to minimize the reactivity of the collagen-tanning agent and to support the penetration of said agent through the whole thickness of the leather.
  • said treatment consists in an acidification, technically called “pickling", which is made by using an electrolyte which raises the osmotic pressure of the bath. Said effect is performed in order to remove the swelling of the skin which would otherwise occur together with the lowering of the pH below the isoelectric point of collagen (the "pickling" treatment is carried out by using the formic acid and the sulfuric acid as pH regulators and the sodium chloride as an osmotic electrolyte).
  • tanning agent When the leather is impregnated with tanning agent in conditions of low reactivity, it is possible to change the pH, thus obtaining the fixing of the tanning agent to the collagen matrix. It is very important that a molecule of the tanning agent has, in addition to a high affinity towards the organic substrate, also a good ability to penetrate into the fibers of the skin, in order to avoid wrinkling, over-tanning or other unwanted effects.
  • chrome tanning after a suitable pickling process, the chromium salt is added and, once the tanning agent is penetrated into the leather, is the pH of the bath is raised from 2.8 up to 3.8-4.2, thus obtaining the final fixing.
  • the overall duration of the tanning process depends on the type of skin to be treated up to a maximum of 20-24 hours.
  • the above values may be subject to slight changes according to the particular formulation and to the characteristics of the leather to be made.
  • tanning for leathers At present there are different types of tanning for leathers; however, those the types of tanning which are of most interest for industry are the following:
  • the hydrothermal stability is indicated by the gelatinization temperature, Tg, which in this case easily exceeds 100°C.
  • Tg gelatinization temperature
  • the leathers tanned with chrome are characterized by an intrinsic blue-gray coloration due to the presence of trivalent chromium which is incorporated in the fibers and which adversely affects the brightness of the dyes and consequently limits the range of colors.
  • the tanning By using the tanning with aldehydes it is possible to obtain leathers with good performances but rather spongy, with low fullness and characterized by a yellowish color.
  • the aldehydes are very rarely used as the sole tanning agent, but are suitably combined with other substances thus obtaining a mixed tanning.
  • the synthetic tannins while presenting significant advantages over natural tannins, give rise to a leather characterized by both a low gelatinization temperature and a reduced dyeability.
  • the tanning with synthetic tannins also requires, as well as the natural tannins, high amounts of the tanning agent; therefore, the synthetic tannins, as well as the aldehydes, are almost always employed for obtaining a mixed tanning.
  • the vegetable tannins when used as first-tanning agents, give to the leather a high fullness and are used almost always for producing soles and heavy leathers.
  • document US2012/058357A1 discloses the tanning of delimed and bated animal hides with a water-soluble triazine compound containing a sulfonate salt group
  • document US2013/198974A1 discloses delimed and bated bovine hides which are treated (i.e. by drumming) in a drum containing fresh water at 20°C with non-metal tanning agent compositions being based on a water-soluble triazine compound.
  • a common feature of the known tanning agents is to interact with the collagen of the skin/leather, so as to permanently remain inside its structure.
  • the methods of tanning listed above have important critical aspects both from an environmental point of view and from a toxicologically point of view, mainly due to the disposal of waste (both solid and liquid) and to the presence of substances which are harmful to health inside the leather.
  • waste both solid and liquid
  • the presence of substances which are harmful to health inside the leather it is known that under certain conditions it is possible to have, in chrome-tanned leathers, a leakage of hexavalent chromium, which is a noxious and carcinogenic chemical substance.
  • the chrome tanning raises a particular interest because of the excellent features that causes to the leather.
  • the transformation of the collagen which is performed during the chrome tanning is due to the reaction between polynuclear complexes of trivalent chromium and carboxyl groups of the collagen chain, with the formation of chemical bonds having a partially covalent character that interconnect in a very stable way different sites of the molecules of collagen.
  • a chemical substance has best tanning properties as the number of bridge covalent bonds, which are formed between adjacent chains of collagen, increases. That's why the tanning agent (or a derivative product in situ) becomes an integral part of the collagen matrix and remains embedded inside the leather at the end of the tanning reaction.
  • the terminal and lateral functional groups of collagen that are usually involved in the tanning reaction may react together and form stable bonds even without the use of a tanning molecule.
  • the carboxy and amino functionality of the collagen it is possible to generate a high degree of intramolecular cross-linking through the formation of amide bonds. Consequently, the search for new chemical species that stabilize the collagen may also extend to condensing agents which do not remain permanently incorporated inside the collagen matrix.
  • An activating agent that leads to the formation of a group including acylchloride, acilazide, acilimidazolo, anhydride, etc. is generally employed in order to obtain the amide (or ester).
  • Carbodiimides are organic molecules having basic characteristics thanks to the presence of two nitrogen atoms, which react with an acid, thus generating the O-acilisourea, i.e. an intermediate reactive substance which, by using an amine, gives the desired peptide bond through ammonolysis.
  • DCC dicyclohexylcarbodiimide
  • DCU N,N'-dicyclohexylurea
  • EDC 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride
  • the EDC/NHS system is generally employed as a co-reagent in presence of macromolecules with a high number of amine groups capable of reacting with the carboxyl groups of collagen by increasing the cross-linking degree and consequently the Tg with respect to what is obtained only by using the EDC/NHS system.
  • Normally dendritic amines are used (synthetic polymers obtained by convergent or divergent reaction), which, by reacting with the carboxyl groups of collagen, can be inserted permanently within the collagen structure by changing its properties in an irreversible way.
  • the 2-chloro-4,6-dimethoxy-1,3,5-triazine (CDMT) is employed as an alternative to carbodiimidi, thus allowing to obtain the condensation of a carboxylic acid with an amine in bland conditions and to easily recover the product.
  • CDMT 2-chloro-4,6-dimethoxy-1,3,5-triazine
  • DTMM 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-metilmorpholine chloride
  • DMTMM is constituted by the possibility of being regenerated at the end of the reaction. Indeed, the final co-product of the reaction [2-hydroxy-4,6-dimethoxy-1,3,5-triazine (DMT-OH)] is very soluble in an aqueous phase and may be removed from the mother liquor for concentration.
  • DMT-OH 2-hydroxy-4,6-dimethoxy-1,3,5-triazine
  • the DMTMM as well as the EDC/NHS, has found wide use in recent years in the medical field for the reconstruction of tissues and for the synthesis of oligonucleotides that are used in the medical field.
  • the solution according to the present invention which aims to treat proteins of high molecular weight so as to give a high hydrothermal stability and high resistance against the putrefaction.
  • An object of the present invention is therefore to provide a process for tanning leathers with the salts of dimethoxytriazinyl-N-methylmorpholine and in particular with the 4-(4,6-dimethoxy-1,3,5-triazin-2-)-4-metilmorfolinio chloride, which allows to obtain the previously described technical results.
  • a further object of the invention is to provide a process for tanning leathers which can be performed with substantially reduced cost with respect to the known tanning methods.
  • Another object of the invention is to provide a process for tanning leathers which is simple and safe and which provides for an easy standardization.
  • the present invention provides for a process for tanning leathers by using the triazine derivatives according to the enclosed claim 1. It is clear the effectiveness of the process of the present invention, which allows to obtain leathers with high resistance to rot, high hydrothermal stability and excellent dyeability thanks to the characteristic white color, due to the absence of intrinsic colors.
  • the method of tanning implemented according to the present invention does not have problems about the disposal of solid waste and does not use substances harmful to health in the finished product, such as carcinogens and/or cytotoxic substances.
  • tanning reagent which is not retained within the collagen support, whose chemical composition remains unchanged.
  • EXAMPLE 5 EDC/NHS WITH pH CONTROL AND DENDRIMERS not according to the invention.
  • a piece of decalcined leather of about 100 g is placed in a drum containing 100 ml of water at room temperature.
  • the system is rotated and the pH is controlled with formic acid/ammonia in a range between 5.0 and 5.5.
  • EDC and NHS are added (14% EDC and 8% NHS, with respect to the pelt weight); EDC and NHS are dissolved in 200 ml of water.
  • the leather samples are then pressed and split, retanned and fattened according to the industrial practice.

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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)
EP14790355.3A 2013-09-24 2014-08-27 Process for tanning leathers with triazine derivatives Active EP3049541B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT000233A ITVI20130233A1 (it) 2013-09-24 2013-09-24 Procedimento per la concia del pellame con derivati della triazina
PCT/IT2014/000226 WO2015044971A2 (en) 2013-09-24 2014-08-27 Process for tanning leathers with triazine derivatives

Publications (2)

Publication Number Publication Date
EP3049541A2 EP3049541A2 (en) 2016-08-03
EP3049541B1 true EP3049541B1 (en) 2020-08-19

Family

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EP14790355.3A Active EP3049541B1 (en) 2013-09-24 2014-08-27 Process for tanning leathers with triazine derivatives

Country Status (3)

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EP (1) EP3049541B1 (it)
IT (1) ITVI20130233A1 (it)
WO (1) WO2015044971A2 (it)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITUA20164602A1 (it) * 2016-06-22 2017-12-22 Crossing S R L 31100 Treviso “uso delle 2,4-dialo-6-sostituite-1,3,5-triazine, e loro derivati, come agenti di condensazione, reticolazione, concia, grafting e curing” .
WO2019158341A1 (en) * 2018-02-16 2019-08-22 Huntsman Advanced Materials (Switzerland) Gmbh Process for the simultaneous tanning and dyeing of collagen containing fibrous material
WO2020002979A1 (en) 2018-06-28 2020-01-02 Gruppo Mastrotto S.P.A. Thermally dispersing and electrically conductive processed leather

Family Cites Families (5)

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Publication number Priority date Publication date Assignee Title
US2599142A (en) * 1949-08-12 1952-06-03 American Cyanamid Co Tanning and bleaching leather with a sulfoaromaticmelamine-formaldehyde resin
ES2488766T3 (es) * 2002-01-25 2014-08-28 Biomedical Design, Inc. Fijación resistente a la calcificación
CN101314058A (zh) * 2007-05-28 2008-12-03 江阴奔翔生物科技有限公司 一种动物皮胶原本体改性的方法
BRPI1012854B1 (pt) * 2009-05-14 2020-03-03 Stahl International B.V. Processo para produção de couro curtido, composição de curtimento aquosa e curtimento aquosa/orgânica, couro curtido e seu uso
KR101849065B1 (ko) * 2010-10-28 2018-04-17 스탈 인터내셔날 비.브이. 비-금속 태닝 방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
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Also Published As

Publication number Publication date
WO2015044971A3 (en) 2015-07-16
ITVI20130233A1 (it) 2015-03-25
WO2015044971A2 (en) 2015-04-02
EP3049541A2 (en) 2016-08-03

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