EP3049541A2 - Verfahren zum gerben von leder mit triazinderivaten - Google Patents

Verfahren zum gerben von leder mit triazinderivaten

Info

Publication number
EP3049541A2
EP3049541A2 EP14790355.3A EP14790355A EP3049541A2 EP 3049541 A2 EP3049541 A2 EP 3049541A2 EP 14790355 A EP14790355 A EP 14790355A EP 3049541 A2 EP3049541 A2 EP 3049541A2
Authority
EP
European Patent Office
Prior art keywords
water
skin
tanning
container
collagen
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
EP14790355.3A
Other languages
English (en)
French (fr)
Other versions
EP3049541B1 (de
Inventor
Aurora ZANCANARO
Giorgio POZZA
Valentina BEGHETTO
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.)
GRUPPO MASTROTTO SpA
Original Assignee
GRUPPO MASTROTTO SpA
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Publication of EP3049541A2 publication Critical patent/EP3049541A2/de
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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

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 dimetossitriazin-N-metilmorfolinio salts, such as, for example, the 4- (4 , 6-dimethoxy- 1, 3 , 5-triazin-2-il) -4 -metilmorfolinio chloride (DMTMM) .
  • DTMM dimetossitriazin-N-metilmorfolinio salts
  • 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) .
  • the leather 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 .
  • 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.
  • 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 1 -dicyclohexylurea
  • 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-l , 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-l , 3 , 5-triazine
  • DMTMM A further advantage of the 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-l, 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-l, 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. It is important to underline that both the EDC/NHS and the DMTMM allow the condensation but they do not remain chemically bonded to the substrate at the end of the reaction.
  • 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 dimetossitriazin-N-metilmorfolinio and in particular with the 4- (4 , 6-dimethoxy-l, 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.
  • Tg 72-75°C.
  • Tg 73°C.
  • EXAMPLE 5 EDC/NHS WITH pH CONTROL AND DENDRIMERS.
  • 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 then the DMTMM is added (at different concentrations, from 22% to 5.5%, with respect to the pelt weight); the DMTMM is dissolved in 200 ml of water. No control of pH or temperature. After 4 hours, the bath is drained and the system is washed 2 times with water. Result:
  • Tg 83°C.
  • 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 system is rotated and the pH is measured and, if necessary, is corrected at regular intervals of 30 minutes. After 4 hours the bath is drained and the system is washed 2 times with water. Result:
  • Tg 84°C.
  • the leather samples are then pressed and split, re- tanned and fattened according to the industrial practice .

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)
EP14790355.3A 2013-09-24 2014-08-27 Verfahren zum gerben von leder mit triazinderivaten Active EP3049541B1 (de)

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 true EP3049541A2 (de) 2016-08-03
EP3049541B1 EP3049541B1 (de) 2020-08-19

Family

ID=49486609

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14790355.3A Active EP3049541B1 (de) 2013-09-24 2014-08-27 Verfahren zum gerben von leder mit triazinderivaten

Country Status (3)

Country Link
EP (1) EP3049541B1 (de)
IT (1) ITVI20130233A1 (de)
WO (1) WO2015044971A2 (de)

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” .
MA50851B1 (fr) * 2018-02-16 2021-07-29 Huntsman Adv Mat Switzerland Procédé de tannage et de teinture simultanés de matériau fibreux contenant du collagène
WO2020002979A1 (en) 2018-06-28 2020-01-02 Gruppo Mastrotto S.P.A. Thermally dispersing and electrically conductive processed leather

Family Cites Families (5)

* Cited by examiner, † Cited by third party
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
AU2003205255B2 (en) * 2002-01-25 2007-12-06 Biomedical Design, Inc. Calcification-resistant fixation
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
US8679195B2 (en) * 2009-05-14 2014-03-25 Clariant Finance (Bvi) Limited Tanning process and tanning composition
WO2012055482A1 (en) * 2010-10-28 2012-05-03 Clariant International Ltd Non-metal tanning process

Also Published As

Publication number Publication date
WO2015044971A3 (en) 2015-07-16
ITVI20130233A1 (it) 2015-03-25
EP3049541B1 (de) 2020-08-19
WO2015044971A2 (en) 2015-04-02

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