EP4112748B1 - Agent de tannage, utilisation d'un agent de tannage, procédé de tannage de peaux d'animaux et de fourrure et cuir ainsi obtenu - Google Patents

Agent de tannage, utilisation d'un agent de tannage, procédé de tannage de peaux d'animaux et de fourrure et cuir ainsi obtenu Download PDF

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Publication number
EP4112748B1
EP4112748B1 EP21183144.1A EP21183144A EP4112748B1 EP 4112748 B1 EP4112748 B1 EP 4112748B1 EP 21183144 A EP21183144 A EP 21183144A EP 4112748 B1 EP4112748 B1 EP 4112748B1
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Prior art keywords
tanning
weight
tanning agent
leather
reaction solution
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EP21183144.1A
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German (de)
English (en)
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EP4112748A1 (fr
EP4112748C0 (fr
Inventor
Siegfried Nagel
Andy Schweizer
Wolfgang Armbruster
Stefan Schelle
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Schill and Seilacher GmbH
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Schill and Seilacher GmbH
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Priority to ES21183144T priority Critical patent/ES2975566T3/es
Priority to EP21183144.1A priority patent/EP4112748B1/fr
Priority to PL21183144.1T priority patent/PL4112748T3/pl
Publication of EP4112748A1 publication Critical patent/EP4112748A1/fr
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Publication of EP4112748C0 publication Critical patent/EP4112748C0/fr
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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
    • 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
    • C14C3/18—Chemical tanning by organic agents using polycondensation products or precursors thereof
    • C14C3/20—Chemical tanning by organic agents using polycondensation products or precursors thereof sulfonated

Definitions

  • the invention relates to a tanning agent and the use of such a tanning agent for tanning animal skins and skins, a process for tanning animal skins and skins to produce leather, and leather obtained therefrom.
  • animal collagen in hides is changed in such a way that the leather resulting from tanning is resistant to heat, environmental influences and microorganisms, and the suppleness of the tanned skin is retained after the resulting leather has dried.
  • mineral tanning in particular chrome tanning
  • vegetable tanning for example with tare, mimosa, quebracho or chestnut
  • synthetic tanning in particular with glutaraldehyde, which are based on different strategies.
  • Chrome tanning is of greatest economic importance. Hydrated chromium complexes, which are located between the carboxyl groups of glutamic acid and aspartic acid of the skin's collagen peptide structure, result in a resilient and soft leather. In addition to the good leather quality that can be achieved, a fast and cost-effective process was established with chrome tanning. Other mineral tanning agents, such as those based on aluminum or zirconium, also work according to the same principle.
  • chromium(VI) can trigger allergic reactions when it comes into contact with the skin.
  • Chromium(III) sulfates are usually used in the tanning process.
  • chromium (VI) can be formed from chromium (III) through oxidation or enters the tanning process via tannin impurities.
  • Further disadvantages of tanning containing (heavy) metals are that it is complex Treatment of the wastewater via a plant for the recovery of chromium and other heavy metals as well as the expensive disposal of leather residues such as shavings using landfill processes or incineration.
  • Vegetable tanning uses tannins that are extracted from plants. However, vegetable tanning requires long and complex tanning processes, which is why vegetable tanning has largely been replaced by chrome tanning.
  • Another widely used tanning method is synthetic tanning with glutaraldehyde, in which the bifunctionality of glutaraldehyde serves to cross-link the peptide fibers of the skin.
  • the mode of action is mainly due to the reactivity to the nitrogen functionalities of the underlying amino acids.
  • the glutaraldehyde reacts on two different fibers and permanently connects them by forming a covalent bond.
  • composition for tanning leather which comprises a zeolite treated with a concentrated monocarboxylic acid.
  • the composition is intended in particular to provide an alternative to chrome tanning.
  • the complex production and post-treatment of the zeolite is still necessary, which has a negative impact on the overall ecological balance of the composition.
  • a process for producing leather is known in which a composition is used as a tanning agent, which is a Polysaccharide obtained from starch by oxidation.
  • a composition is used as a tanning agent, which is a Polysaccharide obtained from starch by oxidation.
  • the method shown there is only suitable for use on pimples.
  • the WO 2012/163823 A1 describes graft copolymers which were obtained by means of free radical polymerization, wherein a first monomer A), which is a (meth) acrylic acid or a mixture of a (meth) acrylic acid and mono and/or polyethylenically unsaturated monomers, and a second Monomer B) is used, which is produced by breaking down a polysaccharide or polypeptide.
  • a first monomer A which is a (meth) acrylic acid or a mixture of a (meth) acrylic acid and mono and/or polyethylenically unsaturated monomers
  • a second Monomer B is used, which is produced by breaking down a polysaccharide or polypeptide.
  • the production of such graft copolymers is complex and requires a lot of chemicals.
  • the graft copolymers described cannot achieve sufficient cross-linking of the collagen fibers.
  • the graft copolymers are therefore only suitable for retanning and require
  • the WO 02/40436 A1 discloses a process for producing glycolaldehyde by thermolysis of an aqueous sugar solution, using glucose or sucrose as the sugar.
  • the WO 2009/10068 A1 describes a process for producing glycerose from glycerin, which was produced as a byproduct of large-scale processes such as the production of biodiesel and natural soap production.
  • tanning agents should be able to be produced from globally available, biodegradable and/or renewable raw materials.
  • the object of the invention is achieved by a tanning agent according to claim 1.
  • a tanning agent comprising a reaction solution which contains a tanning component which is selected from the group consisting of glyceraldehyde, glycolaldehyde, acetals of these compounds, hemiacetals of these compounds and combinations thereof, the reaction solution being obtained by partial oxidation and/or pyrolysis of an organic substance with a vicinal diol group.
  • organic substances that occur naturally and/or from renewable raw materials can be used as starting products can be produced.
  • the use of fossil raw materials, for example crude oil and/or natural gas-based raw materials, in the production of tanning agents can be avoided or at least reduced.
  • the tanning component is also hydrophilic and quickly penetrates the skin layers to be tanned. This means that the exposure time of the tanning liquor can be shortened compared to conventional tanning agents. In addition, an even distribution of the active tanning component in the skin layers is achieved, so that an evenly tanned leather with a consistent shrinkage temperature across all skin layers can be obtained.
  • the organic substance having a vicinal diol group is, in particular, an aliphatic substance having a vicinal diol group.
  • the organic substance with a vicinal diol group is selected from the group consisting of glycerol, ethylene glycol, monosaccharides, oligosaccharides, polysaccharides and combinations thereof.
  • organic substances occur, for example, as a by-product in large-scale industrial processes, such as in the production of biodiesel or in the production of natural soap, and/or can be obtained from renewable raw materials.
  • the organic substance with a vicinal diol group is glycerin and/or ethylene glycol.
  • the organic substance is selected from the group consisting of monosaccharides, oligosaccharides, polysaccharides and combinations thereof,
  • Monosaccharides according to the invention are in particular monosaccharides with four to seven carbon atoms and oligosaccharides and polysaccharides according to the invention are in particular oligosaccharides or polysaccharides of these monosaccharides.
  • the reaction solution is obtained in particular by partial oxidation.
  • the partial oxidation produces in particular a reaction solution which contains glyceraldehyde, an acetal of glyceraldehyde and/or a hemiacetal of glyceraldehyde as the tanning component.
  • the partial oxidation takes place according to the WO 2009/100068 A1 described method, whereby adjustments in the reaction procedure are possible to optimize the composition of the reaction solution.
  • This process uses glycerin as a starting product, with the glycerin used preferably being produced as a by-product of large-scale processes such as the production of biodiesel and natural soap production, in which renewable raw materials are used.
  • the catalyst in particular the iron catalyst, can be used in a proportion of up to 10 percent by weight, preferably up to 5 percent by weight, based on the total weight of the reaction solution.
  • Good results can be achieved with 750 to 5000 ppm iron, based on the total weight of the reaction solution, preferably from 1500 to 5000 ppm, particularly preferably from 3500 to 5000 ppm.
  • the partial oxidation takes place in particular at a temperature of 35 to 90 °C, preferably from 40 to 70 °C, particularly preferably from 45 to 50 °C.
  • the reaction solution is obtained in particular by pyrolysis.
  • pyrolysis takes place as aqueous thermolysis as in WO 02/40436 A1 described.
  • a finely dispersed aqueous solution of the organic substance is sprayed into a reactor which has a temperature in the range of 500 to 600 °C.
  • the pyrolysis product formed in the reactor, which is still in the form of finely divided droplets, is then condensed out to obtain the reaction solution.
  • the tanning component is obtained from the organic substance by means of thermal fragmentation, in particular a low salt content of 200 ppm or less being set in the reaction solution in order to increase the yield of tanning active component.
  • the thermal fragmentation takes place in particular at a temperature of 300 ° C or higher, for example at a temperature in the range from 350 to 800 ° C, preferably from 400 to 600 ° C, particularly preferably from 500 to 600 ° C.
  • the reaction solution according to the invention contains, in addition to the tanning-active component, at least one further tanning-promoting component.
  • the tanning-promoting component like the tanning-active component, also has a penetration effect into a skin to be tanned or a substrate to be tanned, but, in contrast to the tanning-active component, does not carry out any tanning itself.
  • the tanning-promoting component promotes the penetration effect of the tanning-active component into the nakedness to be tanned. into the substrate to be tanned or increases the proportion of the active tanning component remaining in the nakedness.
  • the tanning-promoting component serves in particular to reduce the additional chemical consumption, in that a comparable tanning result can be achieved with a lower use of tanning-active components.
  • the tanning-promoting component can have a positive effect on the biodegradability of a leather obtained as well as the tanning and/or process liquors used in the production of the leather, on the coloring of the leather and/or the durability of pre-tanned material.
  • the tanning-promoting substance is preferably selected from the group consisting of (poly)hydroxycarboxylic acids, carboxylic acids, ketones, acetals, hemiacetals and ketals, each with 1 to 8 carbon atoms, and mixtures thereof.
  • the tanning-promoting substance is preferably also biodegradable and environmentally friendly.
  • the tanning-promoting substance is preferably produced as a by-product in the reaction solution from the organic substance, so that no additional addition of tanning-promoting substance is necessary and the production process of the tanning agent is further simplified.
  • the tanning-promoting substance can be added to the tanning agent in addition to the reaction solution.
  • the reaction solution can contain a solvent, preferably water and glycols such as polyethylene glycol and mixtures thereof.
  • the proportion of the solvent in the reaction solution is preferably at most 80 percent by weight, more preferably at most 65 percent by weight, particularly preferably 20 to 50 percent by weight.
  • the tanning agent consists of the reaction solution.
  • substances are used that are obtained directly from partial oxidation and/or pyrolysis.
  • the organic substance used is naturally occurring and/or was made from a renewable raw material, In this way it can be ensured that the production of the tanning agent avoids the use of fossil raw materials as much as possible and is as environmentally friendly and biodegradable as possible.
  • the tanning agent may comprise a first tanning component and a second tanning component, the first tanning component being the tanning component of the reaction solution and the second tanning component being selected from the group consisting of synthetic tannins, vegetable tannins and mineral tannins , especially glutardialdehyde and/or chromium salts.
  • mixtures of conventional tanning agents and the tanning-active component from the reaction solution can also be used according to the invention.
  • the disadvantages of conventional tanning agents can at least be minimized, in particular the tanning agent can be optimized with regard to environmental compatibility and consumption of fossil raw materials, while at the same time the physical and chemical properties of the tanning agent can be adapted with regard to the specific requirements of the intended tanning process.
  • the first tanning component is preferably present in the tanning agent in a higher proportion (w/w) than the second tanning component.
  • the first tanning component is preferably the main tanning component.
  • the second tanning component is, for example, a syntan (synthetic auxiliary tanning agent), a vegetable tanning agent such as hydrolyzable tanning agents (pyrogallol tanning agents), a condensable tanning agent (pyrocatechol tanning agent), a phenolic or non-phenolic tanning agent, a polycondensation or polymerization compound or a combination of that.
  • a syntan synthetic auxiliary tanning agent
  • a vegetable tanning agent such as hydrolyzable tanning agents (pyrogallol tanning agents), a condensable tanning agent (pyrocatechol tanning agent), a phenolic or non-phenolic tanning agent, a polycondensation or polymerization compound or a combination of that.
  • Suitable synthetic auxiliary tanning agents can be produced by sulfonation and condensation of aromatic products.
  • the main compounds used here are mostly polynuclear hydrocarbons (naphthalene, anthracene, phenantrene) or in the form of monohydric phenols (phenol, Naphthol, cresol, etc.) are processed as quinoid substances (quinone, antraquinone), amino compounds (aniline, naphthylamine, carbazole).
  • the second tanning component can also be a chemically treated lignin sulfonic acid or a chemically treated lignin extract. Natural resins, bitumen and petroleum fractions of any kind can also be used.
  • the second tanning component can also be or include a synthetically produced component which is selected from the group consisting of glyceraldehyde, glycolaldehyde, acetals of these compounds, hemiacetals of these compounds and combinations thereof.
  • the structurally identical substances can be used as the second tanning component as for the first tanning component, but these do not come from a reaction solution that was obtained by partial oxidation and/or pyrolysis of the organic substance with a vicinal diol group.
  • glycolaldehyde can be produced synthetically from formaldehyde, hydrogen, carbon monoxide and a suitable catalyst and added as a second tanning component in the tanning agent.
  • the synthetic production of glycolaldehyde can be carried out according to the method described in the WO 2005/058788 A1 described method, in which a rhodium catalyst and a phosphine ligand are used.
  • tanning-active components which do not occur naturally, cannot be produced from renewable raw materials and/or are not biodegradable, but are minimized in the tanning agent according to the invention.
  • the object of the invention is further achieved by the use of a tanning agent as described above for tanning animal hides and skins for the production of leather.
  • reaction solution as obtained from the partial oxidation and/or pyrolysis, is directly suitable for use as or in the tanning agent and an excellent tanning effect can be achieved can, while at the same time environmentally friendly materials are preferably used.
  • the object of the invention is achieved by a process for tanning animal hides and skins to produce leather, comprising the following steps: First, a nakedness is created. In addition, a tanning liquor is provided which comprises the tanning agent as described above. The nakedness is then treated with the tanning liquor to produce leather.
  • ammonium salt or salts are, for example, ammonium chloride and/or ammonium sulfate.
  • the nakedness can be pickled. This is based on animal skins which have been stained using pancreatic proteases or other enzymes in a slightly alkaline pH range from 7.0 to 10.0, preferably from 8.0 to 9.0.
  • the nakedness can be pickled, i.e. the pH value of the nakedness can be specifically lowered in order to subsequently improve the effect of the tanning agent.
  • Pickling can be done using a mixture of formic acid and sulfuric acid.
  • the tanning liquor can have a content of tanning-active substance in the range from 1 to 10 percent, preferably from 2 to 4 percent, based on the reference weight of the pelt.
  • the naked weight or the pimple weight serves as a reference weight.
  • sufficient tanning cannot be expected, while higher levels would result in a higher use of chemicals.
  • the tanning agent comprises a first tanning component and a second tanning component
  • the aforementioned contents apply to the total content of the first and second tanning components.
  • the treatment of the nakedness with the tanning liquor is carried out in particular at a temperature in the range of 10 to 60 ° C.
  • a temperature in the range of 10 to 60 ° C Several temperature levels can also be used, for example treatment can initially be carried out at room temperature and then fixed at an elevated temperature, for example at 40 ° C.
  • Treating the nakedness with the tanning liquor is carried out in a tanning vessel.
  • the pelt can be moved in the tanning vessel.
  • the exposure time of the tanning liquor to the nakedness can be shortened to 15 to 60 minutes, preferably 15 to 30 minutes, compared to an exposure time of up to about two hours when tanning with glutaraldehyde.
  • the tanning agent can be fixed by increasing the pH value in order to cross-link the skin fibers.
  • the pH value of the Tanning liquor increased by adding one or more alkalis, for example by adding sodium carbonate and / or sodium bicarbonate.
  • the leather is moved in the tanning vessel for at least 60 minutes to balance the pH over its entire cross section.
  • Suitable temperatures are in the range from 20 to 50 °C, with temperatures between 30 and 45 °C being preferred.
  • a leather with a shrinkage temperature of 70 ° C or more is preferably obtained.
  • glycolaldehyde When glycolaldehyde is used as a tanning component, leather with a shrinkage temperature in the range of 75 to 80 ° C is obtained.
  • the invention therefore also relates to a leather obtainable by the method described above using the tanning agent according to the invention.
  • Example 1 Tanning with partially oxidized glycerin (with pimples)
  • a reaction solution obtained by partial oxidation of glycerin is used as a tanning agent.
  • the tanning agent consists of 50% by weight water, 30% by weight glyceraldehyde, 9% by weight dihydroxyacetone, 5% by weight formic acid, 3% by weight glyceric acid, 2% by weight of hydroxyacetic acid and 1% by weight of glycerin formal, each based on the total weight of the tanning agent.
  • the tanning agent is used on a pimple in a watery liquor.
  • the drained pimple nakedness is weighed to determine the pimple weight in order to calculate the quantities of chemicals to be used based on the pimple weight, i.e. the pimple weight is used as a reference weight.
  • 50% to 100% water and 10% of the tanning agent are added to the split or unsplit pimple nakedness in a tanning vessel, corresponding to 3% by weight of glyceraldehyde, based on the reference weight.
  • the tanning vessel is moved throughout the entire process.
  • the tanning liquor is left to act for 120 minutes to guarantee even and complete penetration.
  • the pH value is then gradually increased to a pH value in the range of 6.0 to 6.5.
  • Sodium hydrogen carbonate is used for this.
  • the amount added depends on the acid capacity of the tanning liquor.
  • the work continues as follows or the folding begins directly, that is to say by reducing the thickness of the skin substance, if necessary already to the thickness of the end product.
  • the tanning liquor is drained and 100% water is added to the pre-tanned material.
  • 3% of a naphthalene sulfone-formaldehyde-urea condensate and 3% wheat fume are added to this liquor and left to act on the leather for 2 hours.
  • the percentages refer to the reference weight.
  • the leather After washing again with water, the leather can be processed equivalent to glutaraldehyde wet white.
  • Example 2 Tanning with partially oxidized glycerin (without pimples)
  • a reaction solution obtained by partial oxidation of glycerin is used as a tanning agent.
  • the tanning agent consists of 50% by weight of water, 30% by weight of glyceraldehyde, 9% by weight of dihydroxyacetone, 5% by weight of formic acid, 3% by weight of glyceric acid, 2% by weight of hydroxyacetic acid and 1% by weight of % glycerin formal, based on the total weight of the tanning agent.
  • the tanning agent is used on a delimed and pickled skin in an aqueous liquor.
  • the nakedness is weighed, the reference weight in this case referring to the weight obtained after splitting, i.e. the nakedness weight.
  • the pH value is measured and, if necessary, adjusted to a pH value below 8 with formic acid or dilute sulfuric acid.
  • the acid contained in the tanning agent lowers the pH value.
  • the tanning vessel is moved throughout the entire process.
  • the tanning liquor is left to act for 120 minutes to guarantee even and complete penetration.
  • the pH value is then gradually increased to pH 6.0.
  • Sodium hydrogen carbonate is used for this.
  • the amount added depends on the acid capacity of the tanning liquor.
  • the temperature is gradually increased to 40 °C within 2 hours in order to fix the tannin.
  • a sample of the tanned material is cut off and the shrinkage temperature is checked. If the shrinkage temperature is above around 70 °C to 75 °C, the process can continue.
  • the tanning liquor is drained and 100% water is added to the pre-tanned material.
  • 3% of a naphthalene sulfone-formaldehyde-urea condensate and 3% wheat fume are added to this liquor and left to act on the leather for 2 hours.
  • the percentages refer to the reference weight.
  • the leather After washing again, the leather can be processed equivalent to glutaraldehyde wet white.
  • Example 3 Tanning with pyrolysis products of sugars (with pickles)
  • a reaction solution obtained through sugar pyrolysis is used as a tanning agent.
  • the tanning agent is used on a pimple in a watery liquor.
  • the drained pimple nakedness is weighed to determine the pimple weight in order to calculate the quantities of chemicals to be used based on the pimple weight, i.e. the pimple weight is used as a reference weight.
  • the reference weight then refers to the split or unsplit nakedness.
  • the tanning vessel is moved throughout the entire process.
  • the product is left on for 120 minutes to guarantee even and complete penetration.
  • the pH value is then gradually increased to a pH value of 6.0.
  • Sodium hydrogen carbonate is used for this.
  • the amount added depends on the acid capacity of the tanning liquor.
  • the temperature is gradually increased from room temperature (25°C) to a temperature of 40°C over 2 hours in order to fix the tannin.
  • the tanning liquor is drained and 100% water is added to the pre-tanned material.
  • 3% of a naphthalene sulfone-formaldehyde-urea condensate and 3% wheat fume are added to this liquor and left to act on the leather for 2 to 4 hours.
  • the percentages refer to the reference weight.
  • the leather After washing again with water, the leather can be processed equivalent to glutaraldehyde wet white.
  • Example 4 Tanning with a mixture of pyrolysis products of sugars and partial glycerol oxidation products (with pickles)
  • the tanning agent used is a mixture of a reaction solution obtained by partial oxidation of glycerol and a reaction solution obtained by sugar pyrolysis. In other words, two partial reaction solutions are used in the tanning agent.
  • the tanning agent consists of 40% by weight water, 20% by weight glycolaldehyde, 15% by weight glyceraldehyde, 8% by weight invert sugar syrup, 5% by weight dihydroxyacetone, 5% by weight formic acid, 2% by weight % glyceric acid, 2 wt.% hydroxyacetic acid, 2 wt.% acetic acid and 1 wt.% glycerol formal.
  • the tanning agent is used on a pimple in a watery liquor.
  • the drained pimple nakedness is weighed to determine the pimple weight in order to calculate the quantities of chemicals to be used based on the pimple weight, i.e. the pimple weight is used as a reference weight.
  • the reference weight then refers to the split or unsplit nakedness.
  • the tanning vessel is moved throughout the entire process.
  • the product is left on for 120 minutes to guarantee even and complete penetration.
  • the pH value is then gradually increased to a pH value of 6.0.
  • Sodium hydrogen carbonate is used for this.
  • the amount added depends on the acid capacity of the tanning liquor.
  • the temperature is gradually increased from room temperature (25°C) to a temperature of 40°C over 2 hours in order to fix the tannin.
  • the tanning liquor is drained and 100% water is added to the pre-tanned material.
  • 3% of a naphthalene sulfone-formaldehyde-urea condensate and 3% wheat fume are added to this liquor and left to act on the leather for 2 to 4 hours.
  • the leather After washing again with water, the leather can be processed equivalent to glutaraldehyde wet white.
  • Example 5 Tanning with acetals and hemiacetals of glyceraldehyde (with pimples)
  • a mixture of a reaction solution, which was obtained by partial oxidation of glycerin, and butyl diglycol is used as a tanning agent.
  • the tanning agent consists of 40% by weight of water, 20% by weight of glyceraldehyde, 15% by weight of glyceraldehyde butyl diglycol acetal, 15% by weight of butyl diglycol and 10% by weight of dihydroxyacetone and its ketal with butyl diglycol.
  • the tanning agent is used on a pimple in a watery liquor.
  • the drained pimple nakedness is weighed to determine the pimple weight in order to calculate the quantities of chemicals to be used based on the pimple weight, i.e. the pimple weight is used as a reference weight.
  • the reference weight then refers to the split or unsplit nakedness.
  • the tanning vessel is moved throughout the entire process.
  • the product is left on for 120 minutes to guarantee even and complete penetration.
  • the pH value is then gradually increased to a pH value of 7.0.
  • Sodium hydrogen carbonate is used for this.
  • the amount added depends on the acid capacity of the tanning liquor.
  • the temperature is gradually increased from room temperature (25 °C) to a temperature of 40 °C over 4 hours in order to fix the tannin.
  • shrinkage temperature is checked. If the shrinkage temperature is above about 70°C to 75°C, the process can continue.
  • the tanning liquor is drained and 100% water is added to the pre-tanned material.
  • 3% of a naphthalene sulfone-formaldehyde-urea condensate and 3% wheat fume are added to this liquor and left to act on the leather for 2 to 4 hours.
  • the percentages refer to the reference weight.
  • the leather After washing again with water, the leather can be processed equivalent to glutaraldehyde wet white.
  • Example 6 Tanning with acetals and hemiacetals of glycolaldehyde (with pimples)
  • a mixture of a reaction solution obtained by sugar pyrolysis and butyl diglycol is used as a tanning agent.
  • the tanning agent consists of 30% by weight of water, 15% by weight of glycolaldehyde, 20% by weight of glycolaldehyde butyl diglycol acetal, 15% by weight of butyl diglycol and 20% by weight of invert sugar syrup.
  • the tanning agent is used on a pimple in a watery liquor.
  • the drained pimple nakedness is weighed to determine the pimple weight in order to calculate the quantities of chemicals to be used based on the pimple weight, i.e. the pimple weight is used as a reference weight.
  • the reference weight then refers to the split or unsplit nakedness.
  • the tanning vessel is moved throughout the entire process.
  • the product is left on for 120 minutes to guarantee even and complete penetration.
  • the pH value is then gradually increased to a pH value of 7.0.
  • Sodium hydrogen carbonate is used for this.
  • the amount added depends on the acid capacity of the tanning liquor.
  • the temperature is gradually increased from room temperature (25°C) to a temperature of 40°C over 4 hours in order to fix the tannin.
  • the tanning liquor is drained and 100% water is added to the pre-tanned material.
  • 3% of a naphthalene sulfone-formaldehyde-urea condensate and 3% wheat fume are added to this liquor and left to act on the leather for 2 to 4 hours.
  • the percentages refer to the reference weight.
  • the leather After washing again with water, the leather can be processed equivalent to glutaraldehyde wet white.

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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)

Claims (13)

  1. Agent tannant comprenant une solution de réaction contenant un composant actif au tannage choisi dans le groupe constitué par le glycéraldéhyde, le glycolaldéhyde, les acétals de ces composés, les hémiacétals de ces composés et leurs combinaisons,
    dans laquelle la solution de réaction contient au moins un autre composant favorisant le tannage en plus du composant actif au tannage, et
    dans laquelle la solution de réaction est obtenue par oxydation partielle et/ou par pyrolyse d'une substance organique ayant un groupe diol vicinal.
  2. Agent tannant selon la revendication 1, dans lequel la substance organique ayant un groupe diol vicinal est choisie dans le groupe constitué par le glycérol, l'éthylène glycol, les monosaccharides, les oligosaccharides, les polysaccharides et leurs combinaisons.
  3. Agent tannant selon la revendication 1 ou 2, dans lequel la substance favorisant le tannage est choisie dans le groupe constitué par les acides (poly)hydroxycarboxyliques, les acides carboxyliques, les cétones, les acétals, les hémiacétals et les cétals, chacun ayant de 1 à 8 atomes de carbone, et leurs mélanges.
  4. Agent tannant selon l'une quelconque des revendications précédentes, dans lequel la solution de réaction contient un solvant, de préférence de l'eau, des glycols et leurs mélanges.
  5. Agent tannant selon l'une des revendications précédentes, dans lequel l'agent tannant est constitué de la solution de réaction.
  6. Agent tannant selon l'une quelconque des revendications 1 à 4, dans lequel l'agent tannant comprend un premier composant actif au tannage et un second composant actif au tannage, et dans lequel le premier composant actif au tannage est le composant actif au tannage de la solution de réaction et le second composant actif au tannage est choisi dans le groupe constitué par les agents tannants synthétiques, les agents tannants végétaux et les agents tannants minéraux.
  7. Utilisation d'un agent tannant selon l'une des revendications précédentes pour le tannage des peaux d'animaux destinées à la fabrication du cuir.
  8. Procédé de tannage de peaux d'animaux pour la fabrication du cuir, comprenant les étapes suivantes:
    - utiliser une peau,
    - fournir un bain de tannage comprenant l'agent tannant selon l'une quelconque des revendications 1 à 6,
    - traiter la peau avec le bain de tannage afin d'obtenir un cuir.
  9. Procédé selon la revendication 8, dans lequel le bain de tannage a une teneur en substance active au tannage comprise entre 1 et 10 pour cent en poids, de préférence de 2 à 4 pour cent en poids, par rapport au poids de référence de la peau.
  10. Procédé selon la revendication 8 ou 9, caractérisé en ce que le bain de tannage est appliqué sur une peau sans picklage.
  11. Procédé selon l'une quelconque des revendications 8 à 10, caractérisé en ce que la peau est traitée avec le bain de tannage pendant 15 à 60 min, de préférence pendant 15 à 30 min.
  12. Procédé selon l'une quelconque des revendications 8 à 11, dans lequel on obtient un cuir avec une température de rétraction de 70 °C ou plus.
  13. Cuir susceptible d'être obtenu par un procédé selon l'une quelconque des revendications 8 à 12, utilisant un agent tannant selon l'une quelconque des revendications 1 à 6.
EP21183144.1A 2021-07-01 2021-07-01 Agent de tannage, utilisation d'un agent de tannage, procédé de tannage de peaux d'animaux et de fourrure et cuir ainsi obtenu Active EP4112748B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
ES21183144T ES2975566T3 (es) 2021-07-01 2021-07-01 Agente curtiente, uso de un curtiente y procedimiento de curtido de pieles de animales y del cuero obtenido a partir de las mismas
EP21183144.1A EP4112748B1 (fr) 2021-07-01 2021-07-01 Agent de tannage, utilisation d'un agent de tannage, procédé de tannage de peaux d'animaux et de fourrure et cuir ainsi obtenu
PL21183144.1T PL4112748T3 (pl) 2021-07-01 2021-07-01 Środek garbujący, zastosowanie środka garbującego i metoda garbowania skór zwierzęcych i futer oraz pozyskiwanych z nich skór

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP21183144.1A EP4112748B1 (fr) 2021-07-01 2021-07-01 Agent de tannage, utilisation d'un agent de tannage, procédé de tannage de peaux d'animaux et de fourrure et cuir ainsi obtenu

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EP4112748C0 EP4112748C0 (fr) 2024-01-03
EP4112748B1 true EP4112748B1 (fr) 2024-01-03

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Publication number Priority date Publication date Assignee Title
CN116622919B (zh) * 2023-07-06 2024-05-24 四川大学 一种采用无铬鞣革坯制备透明皮革的方法

Family Cites Families (7)

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Publication number Priority date Publication date Assignee Title
CA2326471A1 (fr) 2000-11-20 2002-05-20 Resource Transforms International Ltd. Production de glycolaldehyde par la thermolyse hydrique de glucides
US7449607B2 (en) 2003-12-16 2008-11-11 Shell Oil Company Process of preparing glycolaldehyde
US20090198048A1 (en) 2008-02-05 2009-08-06 Lignotech Usa, Inc. Glycerose synthesis
PT2714756T (pt) 2011-06-02 2018-07-16 Lanxess Deutschland Gmbh Polímeros de enxerto à base de polissacárido e/ou polipéptido como taninos sintéticos
PT2574682E (pt) 2011-09-30 2014-01-21 Kemira Oyj Composição amiga do meio ambiente, adequada para curtimenta de couro, compreendendo zeólito
EP2607500A1 (fr) 2011-12-23 2013-06-26 Hermes Sellier Procédé de fabrication de cuivre utilisant un polysaccharide dérivé d'amidon oxydé et compositions le contenant
RU2759538C2 (ru) 2016-12-08 2021-11-15 Хальдор Топсёэ А/С Получение гликолевого альдегида термолитической фрагментацией

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PL4112748T3 (pl) 2024-04-08
EP4112748A1 (fr) 2023-01-04
EP4112748C0 (fr) 2024-01-03

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