EP3440227B1 - Composition et procédé de tannage basé sur des aldéhydes sous forme des acétals comme agent de tannage - Google Patents

Composition et procédé de tannage basé sur des aldéhydes sous forme des acétals comme agent de tannage Download PDF

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Publication number
EP3440227B1
EP3440227B1 EP17715042.2A EP17715042A EP3440227B1 EP 3440227 B1 EP3440227 B1 EP 3440227B1 EP 17715042 A EP17715042 A EP 17715042A EP 3440227 B1 EP3440227 B1 EP 3440227B1
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Prior art keywords
acetal
weight
tanning
leather
aldehydic
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German (de)
English (en)
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EP3440227A1 (fr
Inventor
Catherine Gabagnou
Nina SCHULTE
Grigore Daniel HERTA
Jens Fennen
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TFL Ledertechnik GmbH and Co KG
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TFL Ledertechnik GmbH and Co KG
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Priority to EP19167730.1A priority Critical patent/EP3561081A1/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
    • C14C3/16—Chemical tanning by organic agents using aliphatic aldehydes

Definitions

  • the invention relates to a composition containing a tanning agent for tanning hides and / or pelts.
  • the invention also relates to a method for tanning hides and / or pelts for the production of leather.
  • the invention relates to a composition and a method for pretanning and / or retanning, preferably for pretanning.
  • the tanning and, in particular, the pretanning of hides and / or pelts by aldehyde tanning agents is generally known and is used commercially, for example in the so-called "wet white” process.
  • the main aldehydic tanning agents used are formaldehyde, propionaldehyde, glyoxal and, in the most common cases, glutaraldehyde.
  • a major disadvantage of these previously known compositions and methods which are based on the use of the tanning agents mentioned is, however, that the tanning agents have too high a reactivity towards the proteins of the skin to be tanned. Frequently, therefore, particularly in the case of relatively thick hides and / or pelts, insufficient penetration of the tanning agents into deeper layers of the skin to be tanned and / or of the hide to be tanned can occur. This can lead to inhomogeneous tanning, which can negatively affect the quality of the leather produced.
  • aldehydic tanning agents generally have a very high toxicity and a pungent odor. Inhaling aldehydic vapors and direct contact with these aldehydic tanning agents are, however, often unavoidable with known compositions and processes based on them, so that people who use them for tanning hides and / or pelts are exposed to an increased health risk. In this context, there is therefore a need to improve occupational safety when tanning with aldehydic tanning agents.
  • the object is therefore to create a composition and / or a method of the type mentioned at the outset in which the aforementioned disadvantages do not occur.
  • composition according to the invention has the advantage over previously known compositions based on aldehydic tanning agents that acetals of aldehydic tanning agents are not or hardly reactive towards the proteins of the hide and / or pelts to be tanned. Such acetals are particularly stable in a neutral and alkaline medium and for this reason do not react with the proteins mentioned when the composition according to the invention is applied to the skin and / or the fur at this pH value. In addition, acetals from aldehydic tanning agents are less toxic than the aldehydic tanning agent itself, i.e. the aldehyde.
  • composition according to the invention Another hitherto completely unknown, surprising effect is shown in the composition according to the invention in that when the composition according to the invention is used for tanning, improved penetration into deeper layers of the skin to be tanned and / or of the fur to be tanned can be achieved.
  • a more homogeneous tanning can thereby be achieved compared with previously known compositions which are based on aldehydic tanning agents.
  • the pH value can be lowered after an exposure time in such a way that the aldehydic tanning agent is released and becomes reactive as a result.
  • the composition according to the invention is applied in non-reactive form to a skin and / or a fur, which can be made available, for example, in a closable container.
  • the aldehydic tanning agent of the composition can be activated by subsequent acidification, that is to say lowering the pH value, this being possible, for example, within the closed vessel by adding an acid.
  • composition according to the invention can also be applied to a pickled pelt.
  • the acetal of an aldehyde tanning agent is an acetal of formaldehyde, propionaldehyde, glutaraldehyde and / or glyoxal.
  • the composition contains two or more of the acetals mentioned.
  • the acetal is glutaraldehyde.
  • the acetals mentioned of aldehydic tanning agents have a particularly good tanning effect.
  • an alcohol component of the acetal of an aldehyde tanning agent is methanol, ethanol, diethylene glycol and / or triethylene glycol.
  • the alcohol component of the acetal is preferably methanol.
  • the acetal of an aldehydic produced with previously known processes can also be purified by using other previously known purification processes, such as, for example, column chromatography, in particular flash chromatography, in order to obtain an even purer acetal.
  • the composition according to the invention has at least one saccharide, in particular a reducing saccharide.
  • the composition according to the invention contains at least one saccharide with a dextrose equivalent of 10 to 100.
  • the proportion of the at least one saccharide in the composition is 0.1% by weight to 30% by weight, in particular 2.5% by weight to 15% by weight , amounts to. This allows the reactivity of the released aldehydic tanning agent to be further reduced and thus a slower and gentler tanning process due to improved penetration (also during the actual tanning process) into the deeper layers of the skin.
  • the composition has at least one or the at least one previously mentioned saccharide which is selected from the group of glucose, sucrose or a mixture of glucose and sucrose.
  • saccharide which is selected from the group of glucose, sucrose or a mixture of glucose and sucrose.
  • the composition contains a proportion of polyoxaalkylene glycol.
  • the proportion of polyoxaalkylene glycol is selected from the group of polyoxaethylene diol, polyoxa-1,2-propylene diol or a mixture of polyoxaethylene diol and polyoxa-1,2-propylene diol.
  • the composition contains two or more of the polyoxaalkylene glycols mentioned.
  • one or the aforementioned proportion of polyoxaalkylene glycol in the composition contains one or more polyoxaalkylene glycols with a molecular weight M R of 120 to 1,000. It can be particularly expedient here if one or the aforementioned proportion of polyoxaalkylene glycol / s in the composition is 2.5 to 15% by weight.
  • composition according to the invention additionally contains an aldehyde, in particular where a proportion of the aldehyde in the composition is 0.1% by weight to 50% by weight, in particular 5% by weight to 50% by weight , in particular 10% by weight to 40% by weight, in particular 20% by weight to 30% by weight.
  • the solvent of the composition according to the invention can have one selected from the group consisting of water, water-soluble organic solvents or a mixture of water and water-soluble organic solvents.
  • Glycerol and / or a monoetherified polyoxaalkylene glycol for example, can be suitable as water-soluble organic solvents.
  • the water-soluble organic solvent has a molecular weight M R of greater than or equal to 100 and / or of less than or equal to 2,000.
  • the pH-regulating buffer component can set a pH of 7.5 to 10.5 for the composition.
  • the aldehydic tanning agent is stable and therefore not reactive with the proteins of the hide to be tanned and / or of the fur to be tanned. In this way, particularly good penetration of the composition into deeper layers can be achieved.
  • Suitable pH-regulating buffer components can be, for example, one or more selected from the group consisting of carbonate buffer, borate buffer and / or phosphate buffer.
  • the same advantages apply as have already been explained above for the composition according to the invention.
  • the method according to the invention can be used for tanning, pretanning and / or retanning of pelts.
  • a skin that has been fleshed and / or depilated after the pimple and / or the stain can be defined as nakedness, but which has not yet been tanned.
  • an acetal of formaldehyde, propionaldehyde, glutaraldehyde, glyoxal and / or one according to formula A and / or formula B can be used as the acetal of an aldehyde tanning agent.
  • it can be useful if two or more of the aforementioned acetals are used. It can be particularly useful if at least one acetal of glutaraldehyde is used.
  • Particularly good tanning can be achieved by using methanol, ethanol, diethylene glycol and / or triethylene glycol or two or more of the alcohol components mentioned as an alcohol component of the acetal.
  • methanol can be provided as an alcohol component.
  • the acetal is added with a composition which comprises further components.
  • the acetal is added with the composition according to the invention, as described and claimed herein.
  • a particularly good tanning effect can be achieved if a proportion of the added acetal based on the total weight of the fur and / or hide is 0.25% by weight to 10% by weight, in particular 1.0% by weight to 6 , 0% by weight, in particular 1.5% by weight to 5% by weight, preferably 2.0% by weight or 4.5% by weight.
  • the pH is adjusted to 6 to 9, in particular to 7.5 to 8.5, before the addition of the acetal.
  • the aldehydic tanning agent is not released, so that the acetal remains stable. Therefore, the aldehydic tanning agent cannot (yet) react with the proteins of the skin and / or the fur.
  • the acetal is added after a pickling process has been carried out and / or after a pickling step has been carried out.
  • the skin and / or the fur can be treated with an acid and / or with common salt.
  • the aldehydic tanning agent can be provided that after the addition of the acetal into the liquor, the pH of the liquor is set to 1 to 2.5, in particular to 1.8 to 2.5, is set. After the aldehydic tanning agent has been released, it can react with the proteins of the hide to be tanned and / or of the hide to be tanned.
  • a temperature of the liquor at least during the tanning step i.e. after activation of the aldehyde tanning agent, is between 10 ° C and 50 ° C, in particular between 20 ° C and 30 °, in particular 25 ° C.
  • Particularly good tanning can be achieved at the temperatures mentioned.
  • acetals provided for tanning are provided in combination with other tanning agents in the composition according to the invention and / or the method according to the invention. Further suitable tanning agents for this purpose are given below in the examples.
  • the invention also relates to a leather which is produced by the method according to the invention, as described and claimed herein and / or by using the composition according to the invention, as described and claimed here.
  • the leather according to the invention can be a pretanned leather.
  • the invention also relates to the use of the aforementioned leather according to the invention for producing a sanded and / or full-grain crust leather by one or more steps selected from the group of retanning, fatliquoring, filling and / or dyeing.
  • the invention therefore also relates to a crust leather, in particular a sanded and / or full-grain crust leather, produced by the treatment according to the invention of the leather, as mentioned above, by one or more of the steps selected from the group consisting of retanning, fatliquoring, filling and / or dyeing.
  • the invention also relates to the use of the leather according to the invention, as described and claimed herein and / or the crust leather according to the invention, as described and claimed herein, for the production of finished leather, in particular for the production of an automobile, furniture, clothing, glove , Leather goods, aircraft, lining and / or shoe upper leather articles.
  • the invention thus relates to a composition containing an acetal of an aldehydic tanning agent for tanning hides and / or hides and a method for tanning hides and / or hides for producing leather, an acetal of an aldehydic tanning agent being used.
  • the aldehydic tanning agent can be released by lowering the pH value, which initiates a tanning step.
  • the composition according to the invention and the method according to the invention are distinguished by a lower toxicity compared to conventional compositions and tanning processes which are based on aldehydic tanning agents. Furthermore, an improved penetration of the tanning agents into deeper layers of the hide and / or the fur is possible, so that a particularly homogeneous tanning is achieved.
  • Acetals of aldehydic tanning agents can, as described and claimed herein, be used for pretanning and / or retanning of hides, in particular animal hides, and / or pelts can, for example, come from an animal from the group consisting of cattle, pigs, goats, deer, sheep and / or deer.
  • acetals of aldehydic tanning agents mentioned and their use, as described and claimed herein, can also be used for pretanning and / or retanning of hides, in particular animal hides, and / or pelts which have been pretreated by known, conventional methods.
  • Suitable methods for pretreatment can be, for example, liming, deliming, bating, pickling and / or mechanical treatment.
  • the method according to the invention for pretanning, (main) tanning and / or retanning of hides, in particular animal hides, and / or pelts, as described and claimed herein, can be carried out in an aqueous medium, in particular in an aqueous liquor.
  • the pH can be adjusted to values from 1 to 10.
  • a suitable temperature for carrying out the process according to the invention can be between 10.degree. C. and 50.degree.
  • the temperature is preferably between 15 ° C and 35 ° C, in particular 25 ° C.
  • a suitable duration of the actual tanning step that is to say an incubation time of the hides and / or the pelts with the released aldehyde (corresponds to the aldehydic tanning agent), can be from 10 minutes to 12 hours.
  • a hide to be tanned and / or a hide to be tanned can be provided in a conventional tanning vessel. All further steps of the method according to the invention can then be carried out, for example, in this vessel and / or a drum.
  • tanning agents for pretanning and / or retanning of hides, in particular animal hides, and / or pelts .
  • suitable further tanning agents can be mineral tanning agents such as chromium, aluminum, zirconium, titanium and iron salts, synthetic tanning agents (syntans), polymer tanning agents and / or vegetable tanning agents (vegetable tanning agents).
  • the percentages by weight in the specific examples below relate to a total weight of the hide to be tanned and / or of the fur to be tanned.
  • the skin to be tanned and / or the fur to be tanned are provided in 3000 mL of water (hereinafter referred to as aqueous liquor) with a set pH of 7.5 to 8.5 and a temperature of 25 ° C in a suitable vessel .
  • an acetal of an aldehydic tanning agent for example acetal of glutaraldehyde
  • the acetal was here, as it is in U.S. 2,885,443 and or U.S. 4,448,977 is described.
  • the liquor with the acetal is allowed to act on the skin and / or the fur, for example in a rotatable drum provided for this purpose.
  • An exposure time can be freely selected, for example, depending on the thickness of the skin and / or the fur. The thicker the skin and / or fur, the longer the exposure time should be selected in order to achieve adequate penetration of the acetal into deeper skin layers.
  • the exposure time can be between 2 hours and 7 hours.
  • a preferred exposure time here is 5 hours.
  • the aldehydic tannin for example in the form of glutaraldehyde, is released.
  • the released aldehydic tanning agent can then react with the proteins of the skin and / or the fur, in particular with collagen. This initiates the actual tanning process.
  • the released aldehyde is then allowed to act on the skin and / or the hide in a tanning step, for example in the rotating drum.
  • a suitable exposure time here can be between 1.5 hours and 5 hours, preferably 3 hours.
  • 2% by weight of sodium hydrogen carbonate are added.
  • the aqueous liquor is then allowed to act on the pretanned skin and / or the pretanned hide in order to fix the aldehyde as completely as possible.
  • An exposure time can be, for example, between 1.5 and 4.5 hours, in particular 3 hours.
  • the pH is then adjusted to 4.0 to 4.2.
  • the liquor is discarded and the pre-tanned skin and / or the pre-tanned hide is washed with water, in particular with approx. 3000 ml of water.
  • the pretanned hide and / or the pretanned hide can then be dried and, for example, brought to a thickness of 1.1 to 1.3 mm.
  • the skin to be tanned and / or the fur to be tanned are provided in 3000 mL water (hereinafter referred to as aqueous liquor) with a set pH of 3.0 to 3.2 and a temperature of 25 ° C in a suitable vessel .
  • aqueous liquor 3000 mL water
  • no penetration step is provided in which the aldehydic tanning agent in the form of acetal first acts on the skin and / or the fur without reacting with proteins.
  • an acetal of an aldehydic tanning agent for example acetal of glutaraldehyde
  • an aldehydic tanning agent for example acetal of glutaraldehyde
  • 1% by weight of a mixture, in particular a 1: 1 mixture, of sodium formate and sodium hydrogen carbonate is added.
  • the pH is then adjusted to 4.0 to 4.2.
  • the liquor is then left to act for 1.5 hours to 4.5 hours, in particular for 3 hours.
  • 2% by weight of sodium hydrogen carbonate are then added, the liquor again being allowed to act for 2 hours to 6 hours, in particular for 4 hours.
  • the pH is then readjusted to 4.0 to 4.2.
  • the liquor is discarded and the pre-tanned skin and / or the pre-tanned hide is washed with water, in particular with approx. 3000 ml of water.
  • the pretanned hide and / or the pretanned hide can then be dried and, for example, brought to a thickness of 1.1 to 1.3 mm.

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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 (18)

  1. Composition pour le tannage de peaux et/ou de fourrures comprenant
    de 5 % en poids à 95 % en poids d'un acétal d'un agent de tannage aldéhydique,
    de 1 % en poids à 5 % en poids d'un composant tampon régulant la valeur du pH et
    de 4 % en poids à 90 % en poids d'un solvant, une valeur du pH de la composition de 7,5 à 10,5 étant obtenue par le biais du composant tampon régulant la valeur du pH.
  2. Composition selon la revendication 1, caractérisée en ce que l'acétal d'un agent de tannage aldéhydique est un acétal de formaldéhyde, de propionaldéhyde, de glutaraldéhyde et/ou de glyoxal, en particulier de glutaraldéhyde.
  3. Composition selon la revendication 1 ou 2, caractérisée en ce qu'un composant alcoolique de l'acétal d'un agent de tannage aldéhydique est du méthanol, de l'éthanol, du diéthylène glycol et/ou du triéthylène glycol, de préférence du méthanol.
  4. Composition selon une des revendications 1 à 3, caractérisée en ce que cette composition contient une proportion de polyoxyalkylène glycol, choisi en particulier parmi le groupe composé du polyoxyéthylène diol, du polyoxy-1,2-propylène diol ou d'un mélange de polyoxyéthylène diol et de polyoxy-1,2-propylène diol.
  5. Composition selon une des revendications 1 à 4, caractérisée en ce que l'acétal d'un agent de tannage aldéhydique est l'acétal selon la formule A
    et/ou la formule B,
    la formule A étant
    Figure imgb0013
     la formule B étant
    Figure imgb0014
     où
    x = 0 à 8,
    y = 2 à 6 et
    R1 = -H, -CH2, -CHO,
    Figure imgb0015
     et
    où
    z = 2 à 6 et
    R2, R3, R4 et R5 sont choisis indépendamment les uns des autres parmi
    Figure imgb0016
     et où
    m = 0 à 8,
    n = 0 à 8 et
    o = 0 à 8.
  6. Composition selon une des revendications 1 à 5, caractérisée en ce que le solvant est choisi parmi le groupe composé de l'eau, de solvants organiques hydrosolubles ou d'un mélange d'eau et de solvants organiques hydrosolubles, en particulier dans laquelle le solvant organique hydrosoluble est de la glycérine et/ou un polyoxyalkylène glycol monoéthérifié, de préférence avec une masse moléculaire MR supérieure ou égale à 100 et/ou inférieure ou égale à 2000.
  7. Composition selon une des revendications 1 à 6, caractérisée en ce que le composant tampon régulant la valeur du pH est un ou plusieurs composants choisis parmi le groupe composé d'un tampon carbonate, d'un tampon borate et/ou d'un tampon phosphate.
  8. Procédé pour le prétannage et/ou le post-tannage de peaux et/ou de fourrures, en particulier de peaux apprêtées, dans un bain, comprenant les étapes suivantes :
    - préparation d'une peau et/ou d'une fourrure dans un bain ayant une valeur de pH située entre 1 et 10,
    - ajustage de la valeur du pH de 6 à 9 avant l'ajout d'un acétal d'un agent de tannage aldéhydique,
    - ajout de l'acétal d'un agent de tannage aldéhydique sur la peau et/ou la fourrure dans le bain,
    - action de l'acétal ajouté dans le bain sur la peau et/ou la fourrure dans une étape de pénétration,
    - ajustage de la valeur du pH du bain entre 1 et 3,6 dans une étape d'activation au cours de laquelle l'agent de tannage aldéhydique est libéré,
    - action de l'agent de tannage aldéhydique libéré dans le bain sur la peau et/ou la fourrure dans une étape de tannage et
    - ajustage de la valeur du pH du bain entre 3,8 et 5 pour fixer l'agent de tannage aldéhydique dans une étape de fixation.
  9. Procédé selon la revendication 8, caractérisé en ce qu'en guise d'acétal d'un agent de tannage aldéhydique est utilisé un acétal de formaldéhyde, de propionaldéhyde, de glutaraldéhyde, de glyoxal et/ou d'un aldéhyde selon la formule A et/ou la formule B, en particulier de glutaraldéhyde et/ou qu'en guise de bain est utilisé un bain aqueux.
  10. Procédé selon une des revendications précédentes, caractérisé en ce qu'en guise de composant alcoolique de l'acétal est utilisé du méthanol, de l'éthanol, du diéthylène glycol et/ou du triéthylène glycol, de préférence du méthanol.
  11. Procédé selon une des revendications précédentes, caractérisé en ce que l'acétal doté d'une composition comprenant d'autres composants et/ou doté d'une composition selon une des revendications 1 à 11 est ajouté.
  12. Procédé selon une des revendications précédentes, caractérisé en ce qu'une proportion de l'acétal ajouté par rapport à un poids total de la fourrure et/ou de la peau est de 0,25 % en poids à 10 % en poids.
  13. Procédé selon une des revendications précédentes, caractérisé en ce qu'avant l'ajout de l'acétal, la valeur du pH est ajustée entre 7,5 et 8,5.
  14. Procédé selon une des revendications précédentes, caractérisé en ce qu'après l'ajout de l'acétal, la valeur du pH du bain est ajustée entre 1 et 2,5.
  15. Procédé selon une des revendications précédentes, caractérisé en ce qu'une température du bain pendant le tannage est située entre 10 °C et 50 °C, en particulier entre 20 °C et 30 °C, en particulier de 25 °C.
  16. Cuir, en particulier cuir prétanné, fabriqué selon un procédé selon une des revendications 8 à 15 et/ou en utilisant la composition selon une des revendications 1 à 7.
  17. Cuir en croûte, en particulier cuir en croûte lissé et/ou pleine fleur, fabriqué par le bais du traitement du cuir selon la revendication 16, par le biais d'une ou plusieurs des étapes choisies parmi le groupe composé du post-tannage, du graissage, du remplissage et/ou de la coloration.
  18. Utilisation du cuir selon la revendication 16 et/ou du cuir en croûte selon la revendication 17 pour la fabrication de cuirs finis, en particulier pour la fabrication d'un article d'automobile, de mobilier, d'habillement, de ganterie, de maroquinerie, d'aéronautique, d'alimentation animale et/ou de tiges de chaussures.
EP17715042.2A 2016-04-06 2017-03-29 Composition et procédé de tannage basé sur des aldéhydes sous forme des acétals comme agent de tannage Active EP3440227B1 (fr)

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DE102016004192.7A DE102016004192A1 (de) 2016-04-06 2016-04-06 Zusammensetzung und Verfahren zur Gerbung basierend auf einem Acetal eines aldehydischen Gerbstoffes
PCT/EP2017/000381 WO2017174181A1 (fr) 2016-04-06 2017-03-29 Composition et procédé de tannage à base d'un acétal d'une substance aldehydique

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EP19167730.1A Division-Into EP3561081A1 (fr) 2016-04-06 2017-03-29 Composition et procédé de tannage à base d'un acétal d'un agent de tannage aldéhydique

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EP (2) EP3440227B1 (fr)
CN (1) CN108884500B (fr)
BR (1) BR112018067719B1 (fr)
DE (1) DE102016004192A1 (fr)
ES (1) ES2906793T3 (fr)
MX (1) MX2018011665A (fr)
PT (1) PT3440227T (fr)
WO (1) WO2017174181A1 (fr)

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DE102017123020A1 (de) 2017-10-04 2019-04-04 Tfl Ledertechnik Gmbh Zusammensetzung und Verfahren zur Gerbung
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US20190106758A1 (en) 2019-04-11
EP3561081A1 (fr) 2019-10-30
PT3440227T (pt) 2022-03-03
MX2018011665A (es) 2019-01-10
WO2017174181A1 (fr) 2017-10-12
CN108884500B (zh) 2022-08-19
ES2906793T3 (es) 2022-04-20
US10604813B2 (en) 2020-03-31
BR112018067719A2 (pt) 2019-01-08
CN108884500A (zh) 2018-11-23
EP3440227A1 (fr) 2019-02-13
BR112018067719B1 (pt) 2022-11-29
DE102016004192A1 (de) 2017-10-12

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