EP3049541B1 - Process for tanning leathers with triazine derivatives - Google Patents
Process for tanning leathers with triazine derivatives Download PDFInfo
- 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
- European Patent Office
- Prior art keywords
- tanning
- collagen
- skin
- mmol
- water
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 23
- 230000008569 process Effects 0.000 title claims description 17
- 150000003918 triazines Chemical class 0.000 title claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- BMTZEAOGFDXDAD-UHFFFAOYSA-M 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholin-4-ium;chloride Chemical compound [Cl-].COC1=NC(OC)=NC([N+]2(C)CCOCC2)=N1 BMTZEAOGFDXDAD-UHFFFAOYSA-M 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 17
- 241001465754 Metazoa Species 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- SDLZQJOXVQBYNN-UHFFFAOYSA-N 2,3-dimethoxy-4-methyl-3-(triazin-4-yl)morpholine Chemical class COC1C(N(CCO1)C)(C1=NN=NC=C1)OC SDLZQJOXVQBYNN-UHFFFAOYSA-N 0.000 claims description 3
- 230000002500 effect on skin Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 1
- 102000008186 Collagen Human genes 0.000 description 31
- 108010035532 Collagen Proteins 0.000 description 31
- 229920001436 collagen Polymers 0.000 description 31
- 239000010985 leather Substances 0.000 description 20
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 18
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 17
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 11
- 239000000412 dendrimer Substances 0.000 description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- 229920000736 dendritic polymer Polymers 0.000 description 9
- 229920001864 tannin Polymers 0.000 description 9
- 239000001648 tannin Substances 0.000 description 9
- 235000018553 tannin Nutrition 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 102000004169 proteins and genes Human genes 0.000 description 6
- 108090000623 proteins and genes Proteins 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 150000001718 carbodiimides Chemical class 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- -1 for example Chemical class 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ADFXKUOMJKEIND-UHFFFAOYSA-N 1,3-dicyclohexylurea Chemical compound C1CCCCC1NC(=O)NC1CCCCC1 ADFXKUOMJKEIND-UHFFFAOYSA-N 0.000 description 2
- GPIQOFWTZXXOOV-UHFFFAOYSA-N 2-chloro-4,6-dimethoxy-1,3,5-triazine Chemical compound COC1=NC(Cl)=NC(OC)=N1 GPIQOFWTZXXOOV-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000357 carcinogen Toxicity 0.000 description 2
- 239000003183 carcinogenic agent Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 231100000433 cytotoxic Toxicity 0.000 description 2
- 230000001472 cytotoxic effect Effects 0.000 description 2
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- 235000019253 formic acid Nutrition 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000003204 osmotic effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 108091034117 Oligonucleotide Proteins 0.000 description 1
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical class [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- JLCPHMBAVCMARE-UHFFFAOYSA-N [3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[5-(2-amino-6-oxo-1H-purin-9-yl)-3-[[3-[[3-[[3-[[3-[[3-[[5-(2-amino-6-oxo-1H-purin-9-yl)-3-[[5-(2-amino-6-oxo-1H-purin-9-yl)-3-hydroxyoxolan-2-yl]methoxy-hydroxyphosphoryl]oxyoxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxyoxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methyl [5-(6-aminopurin-9-yl)-2-(hydroxymethyl)oxolan-3-yl] hydrogen phosphate Polymers Cc1cn(C2CC(OP(O)(=O)OCC3OC(CC3OP(O)(=O)OCC3OC(CC3O)n3cnc4c3nc(N)[nH]c4=O)n3cnc4c3nc(N)[nH]c4=O)C(COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3CO)n3cnc4c(N)ncnc34)n3ccc(N)nc3=O)n3cnc4c(N)ncnc34)n3ccc(N)nc3=O)n3ccc(N)nc3=O)n3ccc(N)nc3=O)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)n3cc(C)c(=O)[nH]c3=O)n3cc(C)c(=O)[nH]c3=O)n3ccc(N)nc3=O)n3cc(C)c(=O)[nH]c3=O)n3cnc4c3nc(N)[nH]c4=O)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)O2)c(=O)[nH]c1=O JLCPHMBAVCMARE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910052782 aluminium Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 210000000845 cartilage Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229920002674 hyaluronan Polymers 0.000 description 1
- 229960003160 hyaluronic acid Drugs 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 210000003660 reticulum Anatomy 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000008054 sulfonate salts Chemical group 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- YIEDHPBKGZGLIK-UHFFFAOYSA-L tetrakis(hydroxymethyl)phosphanium;sulfate Chemical compound [O-]S([O-])(=O)=O.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO YIEDHPBKGZGLIK-UHFFFAOYSA-L 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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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Description
- 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. According to a general known tanning process, 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. According to the tanning agent which is used, 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. In some substantial cases 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).
- 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.
- In the case of 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.
- In practice, the above values may be subject to slight changes according to the particular formulation and to the characteristics of the leather to be made.
- 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:
- a) mineral tanning (almost exclusively performed with basic salts of trivalent chromium; salts of titanium, zirconium and aluminum are also used),
- b) tanning with aldehydes,
- c) tanning with synthetic tannins (syntan),
- d) tanning with vegetable tannins (exclusively for sole leather).
- Over 85% of the leather produced in the world is made of chrome tanning, due to the high stability to heat, moisture, and to the physical and technical features of the finished product. In particular, the hydrothermal stability is indicated by the gelatinization temperature, Tg, which in this case easily exceeds 100°C. However, 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.
- 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. For these and other reasons, 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.
- For example, document
US2012/058357A1 discloses the tanning of delimed and bated animal hides with a water-soluble triazine compound containing a sulfonate salt group, while documentUS2013/198974A1 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. For this reason, 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. In particular, 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. Even the aldehyde tanning (THPS, oxazolidine I and II) by the time release appreciable amounts of formaldehyde (a carcinogen substance), while the synthetic tannins can release formaldehyde and phenol (cytotoxic substances). Therefore, in recent years, both as a result of environmental regulations and health protection and to improve awareness by consumers, is increasingly felt the need for alternative tanning agents.
- In theory the chrome tanning raises a particular interest because of the excellent features that causes to the leather. In the search for new tanning molecules, it is therefore useful to consider the mechanisms of said chrome tanning in an attempt to reproduce them with other chemical substances. Specifically, 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.
- The force and the thermodynamics inertia of the chemical bond is one of the reasons why the chrome tanning gives the leather the higher gelatinization temperatures (Tg).
- In practice, 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.
- However, 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. In fact, exploiting the reactivity of 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.
- A wide range of studies on the formation of amide or ester, which are obtained, respectively, from the condensation between a carboxylic acid and an amine or an alcohol, are also known; said products are of great commercial interest as are often used in the field of drugs, polymers, biomolecules, etc.
- Thanks to their acid-base characteristics, a carboxylic acid (RCOOH) and an amine (R'NH2) initially react to form the corresponding quaternary ammonium salt, according to the formula:
R-COOH + R'-NH2 → R-COO- +H3N-R'
- The subsequent formation of the amide bond requires the elimination of a water molecule, as shown in the following equation:
R-COO- +H3N-R' ↔ R-CONH-R' + H2O
- 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).
- A method which makes use of carbodiimides is widely employed for the condensation of amino acids with formation of peptide bonds. 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.
- One of carbodiimides most used for this purpose is the dicyclohexylcarbodiimide (DCC), which gives rise to the formation of N,N'-dicyclohexylurea (DCU) as a co-product of the reaction, which must be removed by purification at the end of the synthesis.
- Until a short time ago, the coupling reactions between amines and carboxylic acids in aqueous solvent were only conducted in the presence of water-soluble carbodiimides, such as the 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC), which gives the formation of the 1-(3-(dimethylamino) propyl)-3-etilurea, which is in turn water-soluble and therefore easily removable at the end of the reaction. A considerable disadvantage in the use of EDC is constituted by its poor stability, which requires storage at low temperature (ca. -20°C).
- In 1996 Luyn et al. have reported a first example of the use of EDC in the presence of N-hydroxysuccinimide (NHS) as an activator for the cross-linking of lyophilized collagen, thus obtaining, at the best reaction conditions, a maximum value of Tg=82°C. However, in order to obtain the maximum value of Tg, high concentrations of reagents are required (up to five times the moles of EDC with respect to the moles of COOH which are present in the collagen).
- Therefore, 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.
- In recent years, dendrimers have received considerable interest because of their possible use in the medical field as drug delivery systems.
- Repeating cyclically a given sequence of reactions, it is possible to obtain subsequent generations of dendrimers with increasing molecular weight and number of terminal functional groups (G0, G1, G2, etc.). However, the cross-linking reaction between the collagen and dendrimers requires the use of high amounts of EDC/NHS so as to make this procedure of little practical interest except that for specific medical applications, such as the reconstruction of corneal tissue, cartilage, skin, etc.
- Among the known various condensing agents, 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. More recently, the synthesis of the 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-metilmorpholine chloride (DMTMM) has been performed and said substance, unlike the CDMT, can also be used in watery environment.
- 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-1,3,5-triazine (DMT-OH)] is very soluble in an aqueous phase and may be removed from the mother liquor for concentration. One study reports that about 70% of DMT-OH can be recovered as described and converted into DMTMM.
- Moreover, 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.
- In this context it is included 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.
- These and other results are obtained according to the present invention by proposing a set of operating conditions for obtaining, starting from the rough animal skin, a tanned leather with a high temperature of gelatinization in the presence of triazine derivatives and, in particular, in the presence of a well-determined derivative substance. The stabilization of the structure is due to the increase of the cross-linking degree of the collagen, thanks to the formation of new amide bonds, which is carried out under mild conditions of reaction and without the incorporation of the reagent within the protein structure.
- 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.
- Therefore, it is an object of the present invention to provide 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.
- In fact, an important feature of this process is the use of a tanning reagent, which is not retained within the collagen support, whose chemical composition remains unchanged.
- The invention will be described below for illustrative, but not limitative, purpose and with particular reference to some illustrative examples.
- In a beaker of 50 ml containing a solution of 42 ÷ 166 mg (from 0.15 to 0.60 mmol) of DMTMM and 25 mL of distilled water, 250 mg (corresponding to 0.3 mmol of carboxyl groups) of collagen powder are added. The becker is placed under stirring and the pH is monitored every 60 minutes. After 4 hours the suspension is filtered on Buchner and washed with 50 ml of distilled water. The collagen thus treated is then analyzed through DSC. The results are the following:
- 0.15 mmol → Tg = 85°C
- 0.30 mmol → Tg = 84°C
- 0.60 mmol → Tg = 81°C
- In a beaker of 50 ml containing a solution of 42 mg (0.15 mmol) of DMTMM, 20 ml of distilled water and 5 ml of buffer sodium acetate/acetic acid (pH = 5.5), 250 mg (corresponding to 0.3 mmol of carboxyl groups) of collagen powder are added. The system is placed under stirring and the pH is monitored every 30 minutes and corrected if necessary with addition of buffer or acetic acid in a range from 5.3 to 5.9. After 4 hours the suspension is filtered on Buchner and washed with 50 ml of distilled water. The collagen thus treated is then analyzed through DSC. Results:
Tg = 72-75°C. - In a beaker of 50 ml containing a solution of 115 mg (0.6 mmol) of EDC, 69 mg (0.6 mmol) of NHS and 25 ml of distilled water, 250 mg (corresponding to 0.3 mmol of carboxyl groups) of collagen powder are added. The system is placed under stirring and the pH is monitored every 30 minutes and possibly corrected with HCl/NaOH. After 4 hours the suspension is filtered and washed with 50 ml of distilled water. The collagen thus treated is then analyzed through DSC. Results:
Tg = 73°C. - In a beaker of 50 ml containing a solution of 42 mg (0.15 mmol) of DMTMM and 25 ml of distilled water, 250 mg (corresponding to 0.3 mmol of carboxyl groups) of collagen powder and 5 ml of an aqueous solution of a dendrimer, corresponding to 0.3 mmol of amine groups (in case of dendrimer G.0 0.075 mmol, while in case of dendrimer G.1 0.0375 mmol) are added. The system is placed under stirring and the pH is monitored every 60 minutes. After 4 hours the suspension is filtered on Buchner and washed with 50 ml of distilled water. The collagen thus treated is then analyzed through DSC. The results obtained with dendrimers are reported below:
- 1) with 0.15 mmol of DMTMM: (no pH control)
2G0: Tg = 68°C
3G0: Tg = 67°C
4G0: Tg = 67°C
3G1: Tg = 65°C - 2) with 0.30 mmol of DMTMM: (no pH control)
4G0: Tg = 70°C on wet sample
4G0: Tg = 82°C on dry sample - 3) with 0.30 mmol of DMTMM: (pH = 5.5)
4G0: Tg = 75°C - In a beaker of 50 ml containing a solution of 115 mg (0.6 mmol) of EDC, 69 mg (0.6 mmol) of NHS and 25 ml of distilled water, 250 mg (corresponding to 0.3 mmol of carboxyl groups) of collagen powder and 5 ml of a solution of dendrimer corresponding to 0.3 mmoles of amine groups (dendrimer G.0: 0,075 mmol) are added. The system is placed under stirring and the pH is monitored every 30 minutes and possibly corrected with HCl/NaOH. After 4 hours the suspension is filtered on Buchner and washed with 50 ml of distilled water. The collagen thus treated is then analyzed through DSC. Results:
- 2G0: Tg = 79°C
- 3G0: Tg = 77°C
- 4G0: Tg = 85°C
- A piece of leather of about 100 g revived and calcined/decalcined in accordance with normal industry practices, it is treated as follows according to the chosen tanning system.
- 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. Then, 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, retanned and fattened according to the industrial practice.
- The above description makes clear the technical characteristics of the process for tanning leathers with triazine derivatives, as well as clear are the related advantages.
Claims (2)
- Process for tanning leathers comprising at least the following steps:- converting a raw animal skin into a calcium-removed skin, eliminating unwanted substances and controlled opening of the dermal fibers of said skin;- placing the calcium-removed skin inside a container with water at room temperature;- rotating said container;- adding a water-soluble triazine derivative in a weight concentration ranging between 5.5% and 22% of said calcium-removed skin;- draining and washing the skin with water, characterized in that said triazine derivative is formed by salts of dimethoxytriazinyl-N-methylmorpholine.
- Process according to claim 1, characterized in that said salts include the 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM).
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PCT/IT2014/000226 WO2015044971A2 (en) | 2013-09-24 | 2014-08-27 | Process for tanning leathers with triazine derivatives |
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US20210002735A1 (en) * | 2018-02-16 | 2021-01-07 | Huntsman Advanced Materials (Switzerland) Gmbh | Process for the Simultaneous Tanning and Dyeing of Collagen Containing Fibrous Material |
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