WO2010043680A1 - Procédé de production de cuir - Google Patents

Procédé de production de cuir Download PDF

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Publication number
WO2010043680A1
WO2010043680A1 PCT/EP2009/063499 EP2009063499W WO2010043680A1 WO 2010043680 A1 WO2010043680 A1 WO 2010043680A1 EP 2009063499 W EP2009063499 W EP 2009063499W WO 2010043680 A1 WO2010043680 A1 WO 2010043680A1
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WO
WIPO (PCT)
Prior art keywords
oxide
glycol
formulation
different
solvent
Prior art date
Application number
PCT/EP2009/063499
Other languages
German (de)
English (en)
Inventor
Edward Bohres
Sebastien Garnier
Original Assignee
Basf Se
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Publication of WO2010043680A1 publication Critical patent/WO2010043680A1/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
    • C14C3/28—Multi-step processes

Definitions

  • the present invention relates to a process for the production of leather, characterized in that animal hides or semi-finished products with a formulation of at least one compound of general formula I
  • n is an integer in the range of zero to 5
  • t is an integer in the range of one to four
  • m is different or equal and chosen from 1 to 20
  • AO is different or the same alkylene oxide, selected from propylene oxide, 1, 2-butylene oxide, 1, 4-butylene oxide, 2,3-butylene oxide, 1, 2-pentenoxide and 1, 2-
  • Hexene oxide wherein a total of up to 20 mol% of AO may be ethylene oxide.
  • the present invention relates to formulations of compounds of the general formula I in a solvent or a solvent mixture comprising at least one polyhydric alcohol.
  • soft leathers which are leathers that feel soft and full, but nevertheless have sufficient strength.
  • resin tanning agents which contain a melamine resin as the active substance are used to produce such softer and stronger leathers.
  • Such melamine resins in most cases comprise melamine reacted with one or more equivalents of formaldehyde and optionally aminalized with one or more equivalents of a monohydric or polyhydric alcohol.
  • melamine or melamine resins are incompatible with other tanning agents. This incompatibility can be expressed in the fact that melamine precipitates during tanning or retanning and accordingly does not come into effect.
  • a further object was to provide tanning agent formulations which are suitable for producing particularly soft and full leathers which have good strength and exhibit good processability in the folding machine without releasing formaldehyde.
  • the object was to provide particularly soft and full leather, which have good strength and good processability in folding machines, and to provide uses.
  • Animal skins are the skins of any dead animals such as beef, veal, pork, goat, sheep, kangaroo, fish, ostrich or game.
  • animal skins are usually depilated and, if they were depilated in the presence of lime, preferably decalcified.
  • Semifinished products are animal hides which are pickled or pre-tanned or optionally tanned by any processes, preferably semi-finished products produced by the action of chromium salts or in the presence of polymeric tanning agents.
  • Animal skins or semi-finished products are treated with a formulation of a compound of general formula I.
  • the formulation used in the process according to the invention is formaldehyde-free. It is characterized by formaldehyde freely understood that the formaldehyde content is less than 0.01 moles per mole of melamine.
  • the formaldehyde content of the formaldehyde used according to the invention is below 20 ppm, preferably below 15 ppm, determined, for example, according to DIN ISO / TN 17226 or according to DIN 53315 (old).
  • no formaldehyde is detectable in the formaldehyde-free formulations used according to the invention.
  • Formulations used according to the invention contain at least one compound of general formula I.
  • n is an integer in the range of zero to 5, preferably zero or 1 and in particular zero,
  • t is an integer in the range of 1 to 4, preferably 1 or 2,
  • n is different or the same and selected from 1 to 20, preferably 1 to 5.
  • compound of the general formula I is generally not present as pure substance, but as a mixture of compounds with different degrees of alkoxylation, so that the values each m is averages (number average).
  • AO is different or the same alkylene oxide, selected from propylene oxide, 1, 2-butylene oxide, 1, 4-butylene oxide, 2,3-butylene oxide, 1, 2-pentenoxide and 1, 2-hexene oxide, preferably 1, 2-butylene oxide and in particular propylene oxide .
  • a total of up to 20 mol% of AO may be ethylene oxide, preferably up to a total of 10 mol%.
  • compound of the general formula I is employed in a solvent or in a solvent mixture which comprises at least one polyhydric alcohol.
  • polyhydric alcohols are understood to mean compounds which are liquid at room temperature and carry at least two alcoholic hydroxyl groups per mole. Such hydroxy groups may be secondary or primary hydroxy groups.
  • Preferred polyhydric alcohols are ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, glycerol and diglycerol.
  • formulations used according to the invention comprise at least two polyhydric alcohols.
  • formulations used according to the invention comprise at least one dihydric and at least one trihydric alcohol.
  • the solvent mixture used is a combination comprising glycerol as the trihydric alcohol and ethylene glycol, diethylene glycol or triethylene glycol as the dihydric alcohol, more preferably combinations of glycerol and triethylene glycol.
  • formulations used in the invention comprise from 10 to 50% by weight of dihydric alcohol and from 50 to 90% by weight of trivalent alcohol, based in each case on the entire solvent mixture.
  • formulations used according to the invention have a pH in the range from 8 to 13, preferably 8 to 10.
  • formulations used according to the invention have at least one base, for example at least one basic alkali metal compound.
  • bases for example at least one basic alkali metal compound.
  • alkali metal carbonates and alkali metal hydroxides in particular potassium hydroxide and sodium hydroxide.
  • Formulations used according to the invention preferably contain no halogenated solvents such as chlorobenzene, chloroform or carbon tetrachloride. It is understood by “contain no halogenated solvents” that can be detected by known measures such as elemental analyzes less than 100 ppm, preferably no halogenated solvent.
  • the formulation used according to the invention contains one or more polyhydric alcohols as sole organic solvent (s).
  • Formulation used according to the invention may further comprise water.
  • the formulation used according to the invention contains from 0.1 to 20% by weight of compound of the general formula I, preference being given to from 1 to 10% by weight.
  • the process according to the invention for the production of leather is carried out as a tanning process, hereinafter also referred to as tanning process according to the invention, preferably as a retanning process, hereinafter also referred to as retanning process according to the invention.
  • the tanning process according to the invention is generally carried out by adding at least one formulation according to the invention in one portion or in several portions immediately before or else during the tanning step.
  • the tanning process according to the invention is preferably carried out at a pH of from 2.5 to 1 l, preferably to 4, it being frequently observed that the pH increases by about 0.3 to three units during the performance of the tanning process according to the invention.
  • the novel tanning process is generally carried out at temperatures of 10 to 45 ° C, preferably at 20 to 30 0 C. Has proven useful a duration of 10 minutes to 12 hours, preferably one to three hours.
  • the tanning process according to the invention can be carried out in any conventional tanning vessel, for example by walking in barrels or in rotated drums.
  • a total of 0.01 to 10 wt .-% formulation of compound of general formula I, based on the content of compound of general formula I in the invention used formulation on the one hand and the shaved weight on the other hand, are preferred 0.5 to 3 wt .-%.
  • formulation of compound of general formula I is used together with one or more conventional tanning agents, in particular with at least one formaldehyde-free tanning or retanning agent, for example with chrome tanning agents, mineral tannins, layered silicates, polymer tanning agents or vegetable tanning agents, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Volume A15, pages 259 to 282 and especially page 268 ff., 5th edition, (1990), Verlag Chemie Weinheim.
  • the weight ratio of compound of the general formula I: conventional tanning agent or sum of the conventional tanning agents is suitably from 0.01: 1 to 100: 1 (based in each case on the solids contents).
  • an advantageous Variant of the tanning process according to the invention is added to only a few ppm conventional tanning agent inventive formulation.
  • formulation of compound of general formula I is used together with one or more fatliquoring agents or oleophilic components.
  • formulation of compound of general formula I is started in one portion or in several portions before or during pre-tanning.
  • An addition in the pimple is conceivable.
  • the Nachgerbvons invention is based on conventional, i. for example with chrome tanning agents, phyllosilicates, mineral tannins, polymer tanning agents, aldehydes or vegetable tanning agents tanned semi-finished products or semifinished products produced according to the invention as described above.
  • chrome tanning agents, phyllosilicates, mineral tannins, polymer tanning agents, aldehydes or vegetable tanning agents tanned semi-finished products or semifinished products produced according to the invention as described above.
  • at least one formulation of compound of general formula I is allowed to act on semifinished products, that is to say treated with at least one formaldehyde-free formulation of compound of general formula I.
  • the retanning process according to the invention can be carried out under otherwise customary conditions. It is expedient to choose one or more, ie 2 to 6, action steps and to be able to rinse with water between the interaction steps.
  • the temperature during the individual treatment steps is in each case from 5 to 60 0 C, preferably 20 to 45 ° C. It is expedient to use one or more further agents customarily used during the retanning, for example fatliquors, polymer tanning agents and acrylate- and / or methacrylate-based fatliquoring agents, tanning agents based on vegetable tanning agents, fillers, leather dyes or emulsifiers.
  • fatliquors for example fatliquors, polymer tanning agents and acrylate- and / or methacrylate-based fatliquoring agents, tanning agents based on vegetable tanning agents, fillers, leather dyes or emulsifiers.
  • Has proven useful for the Nachgerb compiler invention a duration of 10 minutes to 12 hours, preferably one to three hours.
  • the retanning process according to the invention can be carried out in any conventional tanning vessel, for example by walking in barrels or in rotated drums.
  • a total of 0.01 to 10 wt .-% formulation of compound of general formula I based on the content of compound of general formula I on the one hand and on the shaved weight on the other hand, preferably 0.5 to 5% by weight.
  • Another object of the present invention is leather, prepared by the method according to the invention.
  • leather according to the invention is characterized by good fullness, softness and intensity of the dyeing and further good use properties such as the embossability, the grain tightness and the uniformity of the millbase on furniture and clothing leather.
  • leather according to the invention is suitable, for example, for producing shoe upper leather, items of clothing such as, for example, jackets, coats or trousers, and furthermore furniture.
  • Formulations according to the invention contain at least one compound of general formula I.
  • n is an integer in the range of zero to 5, preferably zero or 1 and in particular zero,
  • t is an integer in the range of 1 to 4, preferably 1 or 2,
  • n is different or the same and selected from 1 to 20, preferably 1 to 5.
  • compound of the general formula I is generally not present as pure substance, but as a mixture of compounds with different degrees of alkoxylation, so that the values each m is averages (number average).
  • AO is different or the same alkylene oxide, selected from propylene oxide, 1, 2-butylene oxide, 1, 4-butylene oxide, 2,3-butylene oxide, 1, 2-pentenoxide and 1, 2-hexene oxide, preferably 1, 2-butylene oxide and in particular propylene oxide .
  • a total of up to 20 mol% of AO may be ethylene oxide, preferably up to a total of 10 mol%.
  • polyhydric alcohol and compound of general formula I are defined above.
  • Preferred polyhydric alcohols are ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols having an average molecular weight M w in the range from 250 to 5,000 g / mol, glycerol and diglycerol.
  • formulations according to the invention comprise at least two polyhydric alcohols.
  • Preferred formulations according to the invention comprise at least one dihydric and at least one trihydric alcohol.
  • the solvent mixture used is a combination comprising glycerol as the trihydric alcohol and ethylene glycol, diethylene glycol or triethylene glycol as the dihydric alcohol, particularly preferred are combinations of glycerol and triethylene glycol.
  • formulations according to the invention comprise in the range from 50 to 90% by weight of dihydric alcohol and 10 to 50% by weight of trivalent alcohol, based in each case on the entire solvent mixture.
  • formulations according to the invention are formaldehyde-free.
  • formaldehyde-free is defined above.
  • Formulations according to the invention preferably contain no halogenated solvents such as chlorobenzene, chloroform or carbon tetrachloride.
  • containing no halogenated solvents means that less than 100 ppm, preferably no halogenated, solvent can be detected by conventional measures.
  • Formulations of the invention preferably contain no acids such as sulfuric acid, hydrochloric acid or phosphoric acid.
  • formulations according to the invention comprise at least one base, preferably at least one alkali metal hydroxide or alkali metal carbonate. Particularly preferred are potassium hydroxide and especially sodium hydroxide. Suitable amounts of alkali metal hydroxide are, for example, from 0.1 to 10% by weight, based on the compound of the general formula I.
  • formulations according to the invention have a pH in the range from 7 to 12, preferably 8 to 11.
  • formulation according to the invention contains one or more polyhydric alcohols as sole organic solvent (s).
  • Formulation according to the invention may further contain water.
  • formulation according to the invention contains from 0.1 to 20% by weight of compound of general formula I, preference being given to from 1 to 10% by weight.
  • Formulations according to the invention in many cases have the appearance of solutions. Formulations according to the invention generally look completely clear at the starting temperature in the process according to the invention, that is to say they are visible to the naked eye without haze.
  • the formulations according to the invention are solutions of compound of the general formula I.
  • formulations according to the invention are colorless. In another embodiment of the present invention, formulations according to the invention may have a yellowish, amber or brownish color.
  • Another object of the present invention is a process for the preparation of formulations according to the invention.
  • Formulations can be carried out by mixing compound of general formula I with a polyhydric alcohol or a solvent mixture comprising at least one polyhydric alcohol.
  • For mixing can proceed according to known procedures. It is preferable to stir for mixing.
  • the mixing can be carried out for example at room temperature or under heating, for example to temperatures in the range of 40 to 190 0 C, in particular 50 to 170 0 C.
  • the mixing can be carried out preferably at atmospheric pressure, but also pressures such as 1, 5 to 15 bar are conceivable.
  • Formulations of the invention are very suitable for the production of leather, for example by the method described above.
  • a further subject of the present invention is thus the use of formulations according to the invention for the production of leather.
  • the invention will be explained by working examples.
  • Dynamic viscosities were always determined according to DIN ISO standard 3219 (former DIN standard 53018) at 23 ° C.
  • the Walk drums 1 to 3 at 25 to 35 ° C with 2% each of a 40% aqueous formulation of polyacrylic acid (M n 70,000 g / mol, pH 5.5).
  • page 3 line 12 et seq were successively in each case 2% Kaolin, average particle diameter (weight average) of 1, 3 microns (determined after 30 minutes of vigorous stirring in water at 50 0 C in accordance with ISO 13320-1, s. and Example B1.1 from WO 2004/22790), furthermore 3% vegetable tanning mimosa and 5% of the formulation according to the invention according to Table 1.
  • the leathers thus obtained were washed, dried, staked and evaluated according to the test criteria specified in Table 2.
  • the leathers of the invention were obtained L.1 and L.2.
  • the rating was based on a grading system from 1 (very good) to 5 (poor).
  • the leathers according to the invention had in particular good body and softness with excellent scar resistance.
  • the experiments show that the leather according to the invention in comparison to native skin (about 2-5 ppm formaldehyde) have no proportion of free formaldehyde and at the same time meet the demand for good filling effect and softness with good grain firmness.

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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)

Abstract

L'invention concerne un procédé de production de cuir caractérisé en ce qu'on traite des peaux d'animaux ou des demi-produits avec une formulation, exempte de formaldéhyde, d'au moins un composé de formule générale (I) dans un solvant ou un mélange de solvants comprenant au moins un alcool polyvalent. Dans la formule (I), les variables sont définies comme suit : n est un entier compris entre 0 et 5, t est un entier compris entre 1 et 4, m est différent ou identique et est sélectionné parmi 1 à 20, AO est un oxyde d'alkylène différent ou identique sélectionné parmi oxyde de propylène, oxyde de butylène-1,2, oxyde de butylène-1,4, oxyde de butylène-2,3, oxyde de pentène-1,2 et oxyde d'hexène-1,2, jusqu'à 20 % en moles de AO en tout pouvant être de l'oxyde d'éthylène.
PCT/EP2009/063499 2008-10-17 2009-10-15 Procédé de production de cuir WO2010043680A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP08166954.1 2008-10-17
EP08166954 2008-10-17

Publications (1)

Publication Number Publication Date
WO2010043680A1 true WO2010043680A1 (fr) 2010-04-22

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PCT/EP2009/063499 WO2010043680A1 (fr) 2008-10-17 2009-10-15 Procédé de production de cuir

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102051419A (zh) * 2010-11-09 2011-05-11 赵志明 一种染色复鞣制革工艺
CN106222327A (zh) * 2016-08-23 2016-12-14 焦作隆丰皮草企业有限公司 一种全粒面无涂环保鞋面革的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0023978A2 (fr) * 1979-08-09 1981-02-18 Basf Wyandotte Corporation Produits cosmétiques et de toilette inoffensifs et procédé pour leur préparation
EP0251464A2 (fr) * 1986-05-27 1988-01-07 The Boots Company PLC Composition insecticide
EP0265657A1 (fr) * 1986-09-25 1988-05-04 Hoechst Aktiengesellschaft Procédé de tannage du cuir
DE4108139A1 (de) * 1991-03-13 1992-09-17 Boehme Chem Fab Kg Verfahren zum gerben von leder und pelzen
US20070191236A1 (en) * 2006-02-14 2007-08-16 Putzig Donald E Permeable zone and leak plugging using cross-linking composition comprising zirconium triethanolamine complex

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0023978A2 (fr) * 1979-08-09 1981-02-18 Basf Wyandotte Corporation Produits cosmétiques et de toilette inoffensifs et procédé pour leur préparation
EP0251464A2 (fr) * 1986-05-27 1988-01-07 The Boots Company PLC Composition insecticide
EP0265657A1 (fr) * 1986-09-25 1988-05-04 Hoechst Aktiengesellschaft Procédé de tannage du cuir
DE4108139A1 (de) * 1991-03-13 1992-09-17 Boehme Chem Fab Kg Verfahren zum gerben von leder und pelzen
US20070191236A1 (en) * 2006-02-14 2007-08-16 Putzig Donald E Permeable zone and leak plugging using cross-linking composition comprising zirconium triethanolamine complex

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102051419A (zh) * 2010-11-09 2011-05-11 赵志明 一种染色复鞣制革工艺
CN102051419B (zh) * 2010-11-09 2013-07-17 赵志明 一种染色复鞣制革工艺
CN106222327A (zh) * 2016-08-23 2016-12-14 焦作隆丰皮草企业有限公司 一种全粒面无涂环保鞋面革的制备方法

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