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WO2011158168A1 - Procédé de fabrication de cuir - Google Patents

Procédé de fabrication de cuir Download PDF

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Publication number
WO2011158168A1
WO2011158168A1 PCT/IB2011/052561 IB2011052561W WO2011158168A1 WO 2011158168 A1 WO2011158168 A1 WO 2011158168A1 IB 2011052561 W IB2011052561 W IB 2011052561W WO 2011158168 A1 WO2011158168 A1 WO 2011158168A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkoxylate
mixture
leather
alkoxylates
primary
Prior art date
Application number
PCT/IB2011/052561
Other languages
German (de)
English (en)
Inventor
Andreas Kunst
Jochen Ammenn
Original Assignee
Basf Se
Basf (China) Company Limited
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, Basf (China) Company Limited filed Critical Basf Se
Priority to CN2011800290776A priority Critical patent/CN102939393A/zh
Priority to EP20110795273 priority patent/EP2580356A4/fr
Publication of WO2011158168A1 publication Critical patent/WO2011158168A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents

Definitions

  • the present invention relates to a process for the production of leather, which comprises treating semi-finished products or pelts in an aqueous liquor with a mixture of
  • tanning and retanning agents have been developed which allow the production of low-formaldehyde leather, for example glutaraldialdehyde.
  • the requirements include, for example, the mechanical and haptic properties of the leather, the coloration, levelness and brilliance of the color, the heat yellowing resistance and the yellowing resistance.
  • WO 2008/1 10532 discloses alkoxylated melamines which can be used as tannin and in particular as retanning agent.
  • the method defined at the outset was found, also briefly referred to as the method according to the invention.
  • the inventive method is based on semi-finished products or pelts.
  • pelts are termed depilated hides of dead animals, for example dead cattle, pigs, goats or deer, which may have been freed from horns. It is not essential for the method according to the invention whether the animals were killed, for example, by slaughtering or have died of natural causes.
  • the skins of dead animals can be pretreated by conventional methods.
  • conventional methods of pre-treatment include liming, deliming, pickling and pimpling, as well as mechanical operations such as skinning the skins.
  • Aqueous liquors are understood to mean aqueous formulations whose essential liquid constituent is water.
  • Aqueous liquors may contain one or more organic solvents, for example, ethanol, isopropanol or ethylene glycol.
  • organic solvents for example, ethanol, isopropanol or ethylene glycol.
  • aqueous liquors contain less than 5% by weight of organic solvent, based on water, more preferably less than 0.5% by weight.
  • aqueous liquors in the present invention contain no organic solvent.
  • alkoxylate At least one alkoxylate of at least one triazine having at least two functional groups per molecule, also called alkoxylate (A) for short, and (B) at least one alkoxylate of ammonia or at least one compound having at least two functional groups, in short also alkoxylate (B ), wherein functional groups selected from primary or secondary amino groups and hydroxyl groups.
  • alkoxylates (A) are understood as meaning reaction products of triazine having at least two functional groups per molecule, abbreviated triazine (a), with one or more equivalents of alkylene oxide, preferably C 2 -C 5 -alkylene oxide, for example with ethylene oxide, 1, 2-propylene oxide, 1, 2-butylene oxide or 1, 2-pentenoxide or mixtures of one or more of the aforementioned C2-Cs-alkylene oxides, preferably with one or more equivalents of ethylene oxide per functional group of triazine (a).
  • the preparation of alkoxylate (A) is carried out using a triazine (a) and a mixture of 80 to 99.9% by weight of ethylene oxide and 0.1 to 50% by weight of propylene oxide, preferably up to 20 Wt .-% of propylene oxide, based on the total amount of alkoxylate (A).
  • Examples of functional groups on triazine (a) are S-H groups, hydroxyl groups and amino groups, which may be primary or secondary, preferably primary amino groups.
  • the functional groups on triazine (a) may be different or the same, for example, it may be an NH 2 group and an OH group, they are preferably the same.
  • the functional groups can be bonded to the triazine ring via a spacer or can be bonded directly to the triazine ring, preferably they are directly linked to the triazine ring.
  • Triazine (a) may carry two or more functional groups, preferably two or three.
  • alkoxylate (A) alkoxylates of at least one compound of the general formula (I) are selected.
  • R 1 is selected from NH 2 ,
  • C 1 -C 10 -alkyl branched or preferably unbranched, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, especially methyl, n-butyl or n-nonyl; and C 6 -C 14 aryl, for example 1-naphthyl, 2-naphthyl, 1-antracenyl, 2-antracenyl, 9-antracenyl, preferably phenyl,
  • triazine (a) are benzoguanamine, acetoguanamine, caprinoguanamine and especially melamine.
  • triazine (a) carries one or more Nh groups, then of these Nh groups in alkoxylate (A) one or both protons may be substituted by alkoxide radicals, preferably both are substituted by alkoxide radicals.
  • triazine (a) is alkoxylated with 1 to 50 molecules, preferably 1 to 20, particularly preferably 1 to 10 molecules of alkylene oxide per functional group.
  • Alkoxylates (B) in the context of the present invention are reaction products of ammonia or at least one compound having at least two functional groups, abbreviated to compound (b), with one or more equivalents of alkylene oxide, in particular C 2 -C 5 -alkylene oxide, for example with Ethylene oxide, 1, 2-propylene oxide, 1, 2-butylene oxide or 1, 2-pentenoxide or mixtures of one or more of the aforementioned C2-Cs-alkylene oxides, preferably with one or more equivalents of ethylene oxide per functional group of compound (b).
  • compound (b) is different from triazine (a).
  • compound (b) is used to prepare alkoxylate (B) and a mixture of from 80 to 99.9% by weight of ethylene oxide and from 0.1 to 20% by weight of propylene oxide, based on total Amount of alkoxylate (B).
  • compound (b) is alkoxylated with 1 to 50 molecules, preferably 1 to 20, particularly preferably 1 to 10 molecules of alkylene oxide per functional group.
  • Examples of compounds (b) are diols, triols, tetraols, amino alcohols having at least one primary or secondary amino group, mercaptoalcohols, primary or secondary diamines, triamines having a total of 3 primary or secondary amino groups, furthermore higher alcohols such as, for example, pentoles and hexols ,
  • amino alcohols examples include ethanolamine, isopropanolamine, the isomeric aminophenols, ⁇ , ⁇ -diethanolamine, N-methylmonoethanolamine, N-methyldiethanolamine, N-methylaminophenol, triethanolamine, tris (hydroxymethyl) aminomethane, triisopropanolamine and N, N-dimethylethanolamine.
  • diols, triols and higher alcohols such as tetrols, pentols and hexols
  • suitable diols, triols and higher alcohols are ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1, 3-propanediol, 1, 4-butanediol, neopentyl glycol, 1, 5-pentanediol, 3-methyl -1, 5-pentanediol, 1, 6-hexanediol, 1, 9-nonanediol, 2-methyl-1, 8-octanediol, cyclohexanediol and 1, 4-dicyclohexanedimethanol, glycerol, 1,1,1-trimethylolpropane, 1, 1 , 1-trimethylolbutane, trimethylolethane, pentaerythritol, sucrose, sucrose, glucose, fructose, mannose,
  • alkoxylate (B) is selected from alkoxylates of at least one triol or triamine.
  • alkoxylate (B) is selected from alkoxylates of at least one sugar alcohol, for example mannitol, xylitol and preferably sorbitol, in particular as D - (-) sorbitol.
  • Particularly preferred compounds (b) are ammonia, 2,3-toluenediamine, ethylenediamine, triisopropanolamine, triethanolamine, ethylene glycol, propylene glycol, glycerol, 1,1,1-trimethylolpropane and sorbitol, in particular as D - (-) - sorbitol.
  • alkoxylate (A) and alkoxylate (B) are known per se.
  • alkoxylate (A) and alkoxylate (B) can be prepared separately and mixed together. It is preferred to prepare alkoxylate (A) and alkoxylate (B) by alkoxylation of a mixture of triazine (a) and compound (b) in one step, as described, for example, in DE 34 12 082 A1.
  • alkoxylate (A) and alkoxylate (B) are selected in a weight ratio ranging from 95: 5 to 5:95, preferably from 3: 7 to 7: 3, more preferably from 2: 3 to 3: second
  • mixtures of alkoxylate (A) and alkoxylate (B) are selected from those prepared by alkoxylating a mixture of triazine (a) and compound (b), wherein triazine (a) and compound (b ) in a weight ratio ranging from 95: 5 to 5:95, preferably from 3: 7 to 7: 3, more preferably from 2: 3 to 3: 2 have been used.
  • a mixture of alkoxylate (A) and alkoxylate (B) which has a hydroxyl number in the range of 20 to 1000 mg KOH / g, preferably in the range of 50 to 400 mg KOH / g , particularly preferably in the range of 100 to 300 mg KOH / g, measured in each case according to DIN 53240.
  • M n number average molecular weight
  • a mixture of alkoxylate (A) and alkoxylate (B) is used, which at 25 ° C. has a dynamic viscosity in the range from 100 to 100,000 mPa.s, preferably 100 to 10,000 mPa.s, particularly preferred 500 to 5,000 mPa-s, determined according to DIN 51550.
  • at least one alkoxylate, abbreviated to alkoxylate (C) is additionally treated with (C) by at least one primary C 1 -C 30 -alkanol, abbreviated to alkanol (c), preferably by at least one primary cyan. C2o-alkanol.
  • Suitable primary alkanols (c) are, in particular, methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-octanol, n-decanol, n-dodecanol, n-tetradecanol, stearyl alcohol and n-eicosanol.
  • Suitable secondary alkanols (c) are, for example, isopropanol and sec-butanol.
  • alkanol (c) is alkoxylated with 1 to 50 molecules, preferably 1 to 20, particularly preferably 1 to 10 molecules of alkylene oxide per functional group.
  • Alkylene oxide is as defined above. Particularly preferred alkylene oxide is ethylene oxide.
  • compound (b) is alkoxylated with 1 to 50 molecules, preferably 1 to 20, particularly preferably 1 to 10 molecules of alkylene oxide per functional group.
  • alkoxylate (C) up to 50% by weight of alkoxylate (C), preferably at most 20% by weight of alkoxylate (C), based on the total amount of alkoxylate (A), alkoxylate (B), are used. and alkoxylate (C).
  • no alkoxylate (C) is used.
  • a mixture of alkoxylate (A), alkoxylate (B) and alkoxylate (C) which has a hydroxyl number in the range of 20 to 1000 mg KOH / g, preferably in the range of 50 to 400 mg KOH / g, particularly preferably in the range of 100 to 300 mg KOH / g, measured in each case according to DIN 53240.
  • a mixture of alkoxylate (A), alkoxylate (B) and alkoxylate (C) having a number average molecular weight (M n ) in the range of 300 to 5,000 g / mol, preferably in the range of 500 to 3000 g / mol, measured for example by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • a mixture of alkoxylate (A), alkoxylate (B) and alkoxylate (C) is used which at 25 ° C. has a dynamic viscosity in the range from 100 to 100,000 mPas, preferably 100 to 10,000 mPas -s, more preferably 500 to 5,000 mPa-s, determined according to DIN 51550.
  • the process according to the invention is carried out as a tanning process, hereinafter also referred to as a tanning process according to the invention, preferably as a retanning process, hereinafter also referred to as a retanning process according to the invention.
  • the tanning process according to the invention is generally carried out by adding a mixture of alkoxylate (A) and alkoxylate (B) and optionally alkoxylate (C) 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 2.5 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 tanning process according to the invention is generally carried out at temperatures of from 10 to 45.degree. C., preferably at from 20 to 30.degree. 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 mixture of alkoxylate (A) and alkoxylate (B) and optionally alkoxylate (C) is used together with one or more conventional tanning agents, for example with chrome tanning agents, mineral tannins, syntans, polymer tanning agents or vegetable tanning agents, such as they are 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 mixture of alkoxylate (A) and alkoxylate (B) and optionally alkoxylate (C): conventional tanning agent or sum of conventional tanning agents is suitably from 0.01: 1 to 100: 1.
  • a mixture of alkoxylate (A) and alkoxylate (B) and optionally alkoxylate (C) is used together with one or more fatliquoring agents or olephilic components.
  • a mixture of alkoxylate (A) and alkoxylate (B) and optionally alkoxylate (C) is added 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 conventionally, ie, for example, with chrome tanning agents, mineral tannins, polymer tanning agents, aldehydes, syntans or resin tanning tanned semi-finished or inventively prepared as described above semifinished products.
  • at least one mixture of alkoxylate (A) and alkoxylate (B) and optionally alkoxylate (C) act on semi-finished products, ie, treated with at least one mixture of alkoxylate (A) and alkoxylate (B) and optionally Alkoxylate (C).
  • the retanning process according to the invention can be carried out under otherwise customary conditions. It is convenient to choose one or more, i. 2 to 6 action steps and can rinse with water between the interaction steps.
  • the temperature in the individual reaction steps is in each case from 5 to 60.degree. C., preferably from 20 to 45.degree.
  • 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.
  • Another object of the present invention are leather, obtainable by the novel process, also referred to as leather according to the invention.
  • leathers of the invention are characterized by the fact that they are particularly soft and have a very pleasant feel.
  • leathers according to the invention generally contain from about 10 ppm up to 4% by weight, based in each case on the shaved weight, of a mixture of alkoxylate (A) and alkoxylate (B) and optionally alkoxylate (C).
  • leathers according to the invention are particularly suitable for the production of garments, for example jackets, trousers, belts or shoes.
  • leathers according to the invention are also well suited for the production of furniture or furniture parts, such as sofas, armchairs, chairs, and for the production of automotive interior parts, such as car seats, center consoles, door panels and dashboards.
  • Another object of the present invention is therefore the use of inventive leather for the production of clothing, furniture, furniture parts and / or automotive interior parts.
  • Another object of the present invention are clothing, furniture, furniture parts and automotive interior parts, containing or manufactured from leather according to the invention.
  • Viscosity 935 mPa-s I.2 Preparation of Mixture 2 of Alkoxylate (A.2) and Alkoxylate (B.2)
  • Viscosity 1591 mPa-s I.3 Preparation of Mixture 3 of Alkoxylate (A.3) and Alkoxylate (B.3)
  • V-NGM.3 As a comparative retanning agent V-NGM.3 a melamine-formaldehyde condensate was used.
  • a commercially available bovine wet blue (Packer, USA) was folded to a thickness of 1, 5 to 1, 8 mm. The core area was cut into three strips of 1700 g each. The strips were then mixed in a drum (50 l) and a liquor length of 200% (based on shaved weight) at intervals of 10 minutes with 1.5% by weight of sodium formate and 0.5% of sodium bicarbonate and 1% of a naphthalenesulfonic acid Formaldehyde condensation product, prepared according to US 5,186,846, example "Dispersant 1.” After 70 minutes, the liquor was drained off and the strips were then distributed to separate walk-drums 1 to 3. Together with 100% water, the walking barrels became 1 to 3 at 25 ° to 35 ° C.
  • Example A Thereafter, in 100% water (50 ° C.), 4% of a fatliquor according to WO 2003/023069, Example A was metered. After 20 minutes, the mixture was acidified to pH 3.8 with 1% formic acid. The leathers thus obtained were washed, dried, staked, treated in a vacuum dryer at 60 ° C. for 30 seconds and evaluated according to the test criteria specified in Table 1. The leathers L.1 and L.2 according to the invention and the comparison leather V-L.3 were obtained. The rating was based on a grading system from 1 (very good) to 5 (poor).

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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 fabrication de cuir caractérisé en ce qu'on traite des semi-produits ou des peaux brutes dans un liquide aqueux avec un mélange de (A) au moins un alcoxylate d'au moins une triazine comprenant au moins deux groupes fonctionnels par molécule et (B) au moins un alcoxylate d'ammoniac ou d'au moins un composé comprenant au moins deux groupes fonctionnels, sélectionnés parmi des groupes amine primaire ou secondaire et des groupes hydroxyle.
PCT/IB2011/052561 2010-06-14 2011-06-14 Procédé de fabrication de cuir WO2011158168A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN2011800290776A CN102939393A (zh) 2010-06-14 2011-06-14 生产皮革的方法
EP20110795273 EP2580356A4 (fr) 2010-06-14 2011-06-14 Procédé de fabrication de cuir

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP10165846 2010-06-14
EP10165846.6 2010-06-14

Publications (1)

Publication Number Publication Date
WO2011158168A1 true WO2011158168A1 (fr) 2011-12-22

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PCT/IB2011/052561 WO2011158168A1 (fr) 2010-06-14 2011-06-14 Procédé de fabrication de cuir

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EP (1) EP2580356A4 (fr)
CN (1) CN102939393A (fr)
WO (1) WO2011158168A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108998600B (zh) * 2018-08-13 2020-12-22 四川大学 一种透明皮革及其制造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008022918A2 (fr) * 2006-08-23 2008-02-28 Basf Se Composés et leur utilisation pour la fabrication de cuir et en tant qu'agents de dispersion
US20080248322A1 (en) * 2005-10-18 2008-10-09 Basf Se Leather Production Method and Products Suited Thereof
WO2009053328A1 (fr) * 2007-10-24 2009-04-30 Basf Se Procédé de production de cuir

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB790933A (en) * 1954-08-13 1958-02-19 Boehme Fettchemie Gmbh Tanning, retanning and filling processes
DE10143949A1 (de) * 2001-09-07 2003-03-27 Basf Ag Emulgatorzusammensetzung und fogging-arme, hochauszehrende Fettungsmittel, ihre Herstellung und Verwendung

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080248322A1 (en) * 2005-10-18 2008-10-09 Basf Se Leather Production Method and Products Suited Thereof
WO2008022918A2 (fr) * 2006-08-23 2008-02-28 Basf Se Composés et leur utilisation pour la fabrication de cuir et en tant qu'agents de dispersion
WO2009053328A1 (fr) * 2007-10-24 2009-04-30 Basf Se Procédé de production de cuir

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2580356A4 *

Also Published As

Publication number Publication date
CN102939393A (zh) 2013-02-20
EP2580356A4 (fr) 2014-01-01
EP2580356A1 (fr) 2013-04-17

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