EP2205768B1 - Verfahren zur herstellung von leder - Google Patents

Verfahren zur herstellung von leder Download PDF

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Publication number
EP2205768B1
EP2205768B1 EP08841840A EP08841840A EP2205768B1 EP 2205768 B1 EP2205768 B1 EP 2205768B1 EP 08841840 A EP08841840 A EP 08841840A EP 08841840 A EP08841840 A EP 08841840A EP 2205768 B1 EP2205768 B1 EP 2205768B1
Authority
EP
European Patent Office
Prior art keywords
formaldehyde
formulation
melamine
tanning
leather
Prior art date
Legal status (The legal status 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 status listed.)
Active
Application number
EP08841840A
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German (de)
English (en)
French (fr)
Other versions
EP2205768A1 (de
Inventor
Sebastien Garnier
Stephan Hüffer
Günter Scherr
Franz Glocknitzer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Publication date
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Priority to EP08841840A priority Critical patent/EP2205768B1/de
Publication of EP2205768A1 publication Critical patent/EP2205768A1/de
Application granted granted Critical
Publication of EP2205768B1 publication Critical patent/EP2205768B1/de
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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

Definitions

  • the present invention relates to a process for the production of leather, which comprises treating animal hides or semi-finished products with a formaldehyde-free formulation of melamine in a solvent or solvent mixture comprising at least one polyhydric alcohol.
  • soft leathers which are leathers that feel soft and full, but nevertheless have sufficient strength.
  • WO 01/09392 describes a process for tanning leather in the presence of melamine and tetrakis (hydroxymethyl) phosphonium salts to obtain refractory-finished leathers.
  • Such tanning agents can release formaldehyde long after their processing.
  • 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. It kick Furthermore, dimerization reactions, trimerization reactions and further oligomerization reactions, which are usually condensations, transacetalizations or Umaminalmaschineen.
  • the resin tanning agents described in this way are often polymer mixtures of indeterminate structure. Such Harzgerbstoffe can cleave formaldehyde, which is undesirable under certain conditions.
  • the cleaved formaldehyde or its semi-aminals is often blamed with melamine for the tanning or retanning action and softness desired of the leather. Also, in many cases, the high molecular weight is responsible for the abundance of leather.
  • 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, are preferably delimbed.
  • Semifinished products are animal hides which are pickled or pretanned or optionally tanned by any method, preferably semifinished 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 formaldehyde-free formulation of melamine. It is understood by formaldehyde-free that the formaldehyde content is less than 0.01 mol per mol 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.
  • Melamine is pure melamine, which has therefore not been reacted with formaldehyde or other aldehydes such as acetaldehyde or benzaldehyde.
  • melamine is used in a solvent or solvent mixture comprising at least one polyhydric alcohol.
  • polyhydric alcohols in the context of the present invention, those at room temperature understood liquid compounds which 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, particularly preferred are 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.
  • the formulations used according to the invention preferably contain no halogenated solvents, for example 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 melamine, preferably 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 11, preferably up to 4, it frequently being 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.
  • formaldehyde-free formulation of melamine 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, sheet silicates, 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 of melamine: conventional tanning agent or sum of conventional tanning agents is suitably from 0.01: 1 to 100: 1 (based on the solids contents).
  • only a few ppm of conventional tanning agent according to the invention are added to the formulation.
  • formaldehyde-free formulation of melamine is used together with one or more fatliquoring agents or oleophilic components.
  • formaldehyde-free formulation of melamine 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 conventional, ie, for example, with chrome tanning, phyllosilicates, mineral Tannins, polymer tanning, aldehydes or vegetable tannins tanned semi-finished or semi-finished products according to the invention as described above.
  • chrome tanning phyllosilicates, mineral Tannins, polymer tanning, aldehydes or vegetable tannins tanned semi-finished or semi-finished products according to the invention as described above.
  • at least one formaldehyde-free formulation of melamine is allowed to act on semifinished products, ie, at least one formaldehyde-free formulation of melamine is treated.
  • 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.
  • 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% by weight of formaldehyde-free formulation of melamine according to the invention is used, based on the content of melamine 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 coloring and further good use properties such as, for example, the embossability, the grain tightness and the uniformity of the mill break in 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.
  • Dynamic viscosities were always determined according to DIN ISO standard 3219 (former DIN standard 53018) at 23 ° C.
  • Table 1 Characterization of the formulations product Melamine [% by weight] Triethylene glycol [% by weight] Glycerol [% by weight] Temp. [° C] Viscosity [mPa ⁇ s] colour F.1 3.2 17.3 79.5 140 390 yellow F.2 3.2 17.3 79.5 80 385 colorless F.3 3.2 17.3 79.5 170 418 Amber F.4 7.6 41.5 50.9 170 589 brown F.5 7.0 46.0 47.0 140 426 brown
  • the leathers thus obtained were washed, dried, staked and evaluated according to the test criteria specified in Table 2.
  • the leathers L.1 to L.5 according to the invention were obtained.
  • the rating was based on a grading system from 1 (very good) to 5 (poor).
  • the comparative tanning agent V-F.6 used was an aqueous formulation which was prepared as follows:
  • aqueous sodium sulfite solution (20 wt .-%) was introduced and added dropwise with stirring within 20 minutes with 325 g of 30 wt .-% aqueous formaldehyde solution. Care was taken to ensure that the temperature did not rise above 60 ° C. After completion of the addition, the temperature was raised to 80 ° C and added to an aqueous suspension of 188.4 g of naphthalenesulfonic acid (mixture of isomers) and 45 g of melamine in 200 ml of water over a period of 15 minutes.
  • the mixture was stirred at 80 ° C. for 2 hours and then 170.7 g of a 50% by weight aqueous urea solution were added over a period of 20 minutes.
  • the mixture was stirred for a further hour at 80 ° C and then 6.9 g of aqueous sodium hydroxide solution (50 wt .-%) within 10 minutes, taking care that the temperature did not rise above 83 ° C.
  • the mixture was stirred for a further 90 minutes at 80 ° C and then allowed to cool to room temperature. With 2.7 g of 25 wt .-% aqueous sulfuric acid, a pH of about 8 was.
  • the leathers according to the invention had in particular outstanding fullness and softness with excellent scar resistance. Summing up, the experiments show that the leather according to the invention in comparison to native skin (about 2-5 ppm of formaldehyde) does not provide any negligible contribution to free formaldehyde and at the same time satisfies the requirement for excellent filling effect and softness with excellent scar resistance become. Another advantage is the finding that the so-called area selectivity could also be improved over the prior art (ratio of the abundance of the core area to the area).

Landscapes

  • 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)
EP08841840A 2007-10-24 2008-10-20 Verfahren zur herstellung von leder Active EP2205768B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08841840A EP2205768B1 (de) 2007-10-24 2008-10-20 Verfahren zur herstellung von leder

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07119191 2007-10-24
EP08841840A EP2205768B1 (de) 2007-10-24 2008-10-20 Verfahren zur herstellung von leder
PCT/EP2008/064118 WO2009053328A1 (de) 2007-10-24 2008-10-20 Verfahren zur herstellung von leder

Publications (2)

Publication Number Publication Date
EP2205768A1 EP2205768A1 (de) 2010-07-14
EP2205768B1 true EP2205768B1 (de) 2011-08-24

Family

ID=40266126

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08841840A Active EP2205768B1 (de) 2007-10-24 2008-10-20 Verfahren zur herstellung von leder

Country Status (8)

Country Link
EP (1) EP2205768B1 (ko)
KR (1) KR101540134B1 (ko)
CN (1) CN101835909B (ko)
AT (1) ATE521720T1 (ko)
BR (1) BRPI0817963B1 (ko)
ES (1) ES2368671T3 (ko)
PT (1) PT2205768E (ko)
WO (1) WO2009053328A1 (ko)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101613769B (zh) * 2009-07-15 2013-11-20 天津市雄冠科技发展有限公司 白色合成鞣剂及其制备方法
CN102939393A (zh) * 2010-06-14 2013-02-20 巴斯夫欧洲公司 生产皮革的方法
KR20220057975A (ko) 2020-10-30 2022-05-09 주식회사 마젠 유연한 향기 나는 말가죽 제조 방법
KR102506705B1 (ko) 2020-12-23 2023-03-09 화이트산업 주식회사 피혁 도장용 탑 코팅제 및 이를 이용한 피혁 탑 도장방법

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2470450A (en) * 1945-09-07 1949-05-17 John R Evans & Company Tanning with free formaldehyde and melamine simultaneously
DE3632587A1 (de) * 1986-09-25 1988-04-07 Cassella Ag Verfahren zur gerbung von leder
GB9917704D0 (en) * 1999-07-29 1999-09-29 Albright & Wilson Uk Ltd Tanning leather
DE10047024A1 (de) * 2000-09-22 2002-04-11 Basf Ag Verfahren zur Herstellung von flammgeschützten Polyurethanweichschaumstoffen
DE102005008034A1 (de) * 2005-02-22 2006-08-31 Lanxess Deutschland Gmbh Säuregruppenhaltige Kondensationsprodukte
US7153962B1 (en) * 2005-07-12 2006-12-26 Casale Chemicals S.A. Process for gently cooling and crystallizing melamine from a melamine melt or from the gaseous phase

Also Published As

Publication number Publication date
KR20100080840A (ko) 2010-07-12
BRPI0817963B1 (pt) 2018-12-26
CN101835909B (zh) 2013-09-18
PT2205768E (pt) 2011-09-06
EP2205768A1 (de) 2010-07-14
WO2009053328A1 (de) 2009-04-30
KR101540134B1 (ko) 2015-07-28
ES2368671T3 (es) 2011-11-21
CN101835909A (zh) 2010-09-15
ATE521720T1 (de) 2011-09-15
BRPI0817963A2 (pt) 2015-05-05

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