EP2205768A1 - Procédé de production de cuir - Google Patents

Procédé de production de cuir

Info

Publication number
EP2205768A1
EP2205768A1 EP08841840A EP08841840A EP2205768A1 EP 2205768 A1 EP2205768 A1 EP 2205768A1 EP 08841840 A EP08841840 A EP 08841840A EP 08841840 A EP08841840 A EP 08841840A EP 2205768 A1 EP2205768 A1 EP 2205768A1
Authority
EP
European Patent Office
Prior art keywords
glycol
formaldehyde
melamine
formulation
free
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.)
Granted
Application number
EP08841840A
Other languages
German (de)
English (en)
Other versions
EP2205768B1 (fr
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
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
Priority to EP08841840A priority Critical patent/EP2205768B1/fr
Publication of EP2205768A1 publication Critical patent/EP2205768A1/fr
Application granted granted Critical
Publication of EP2205768B1 publication Critical patent/EP2205768B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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 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.
  • the present invention relates to formaldehyde-free formulations 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.
  • 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.
  • dimerization reactions, trimerization reactions and further oligomerization reactions occur, which are usually condensations, transacetalizations or umaminalizations.
  • the resin tanning agents described in this way are often polymer mixtures of indeterminate structure. Such resin tanning agents can cleave formaldehyde, which is undesirable under certain conditions.
  • the cleaved formaldehyde or its hemiaminal 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, preferably decalcified.
  • 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 hides 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 are used at room temperature. for 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.
  • containing no halogenated solvents means that less than 100 ppm, preferably no halogenated solvent, can be detected by means of measures known per se, such as elemental analyzes.
  • 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 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% by weight of formaldehyde-free formulation of melamine is used, based on the melamine content of the formulation used according to the invention on the one hand and on the shaved weight on the other hand, preferably 0.5 to 3 wt .-%.
  • 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 neutralizing agent, for example with chrome tanning agents, mineral tannins, sheet 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 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 agents, phyllosilicates, mineral see tannins, polymer tanning agents, aldehydes or vegetable tannins tanned semi-finished or semi-finished products according to the invention as described above.
  • chrome tanning agents, phyllosilicates, mineral see tannins, polymer tanning agents, 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 expedient to select one or more, ie 2 to 6, action steps and 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% 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 dyeing and further good use properties such as, for example, the embossability, the grain tightness and the uniformity of the 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.
  • Another object of the present invention are formaldehyde-free formulations of melamine, comprising at least one polyhydric alcohol.
  • formaldehyde-free, polyhydric alcohol and melamine 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, more preferably 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 of 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, in particular at least one alkali metal hydroxide or alkali metal carbonate. Preference is given to potassium hydroxide and in particular sodium hydroxide. Suitable amounts of alkali metal hydroxide are, for example, from 0.1 to 10% by weight, based on melamine.
  • 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 as sole organic solvent (s) one or more polyhydric alcohols.
  • Formulation according to the invention may further contain water.
  • formulation according to the invention contains 0.1 to 20 wt .-% melamine, preferably 1 to 10 wt .-%.
  • 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.
  • Formulations according to the invention may be reaction mixtures with reaction products of melamine or solutions of melamine.
  • the formulations according to the invention are solutions of melamine.
  • 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.
  • dyeings are not in any case attributable to reaction products of melamine with polyhydric alcohol, but are not intended to give preference to any particular theory, but are believed to be due to interactions between two or more melamine molecules.
  • Another object of the present invention is a process for the preparation of formulations according to the invention.
  • 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 120 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 Walk drums 1 to 7 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).
  • 2% by weight of a 50% by weight (solids content) aqueous formulation of dyes whose solids were composed as follows were metered in:
  • 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:
  • 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 flame).
EP08841840A 2007-10-24 2008-10-20 Procédé de production de cuir Active EP2205768B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08841840A EP2205768B1 (fr) 2007-10-24 2008-10-20 Procédé de production de cuir

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07119191 2007-10-24
EP08841840A EP2205768B1 (fr) 2007-10-24 2008-10-20 Procédé de production de cuir
PCT/EP2008/064118 WO2009053328A1 (fr) 2007-10-24 2008-10-20 Procédé de production de cuir

Publications (2)

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

Family

ID=40266126

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08841840A Active EP2205768B1 (fr) 2007-10-24 2008-10-20 Procédé de production de cuir

Country Status (8)

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

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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009053328A1 *

Also Published As

Publication number Publication date
KR20100080840A (ko) 2010-07-12
EP2205768B1 (fr) 2011-08-24
ATE521720T1 (de) 2011-09-15
WO2009053328A1 (fr) 2009-04-30
ES2368671T3 (es) 2011-11-21
BRPI0817963B1 (pt) 2018-12-26
BRPI0817963A2 (pt) 2015-05-05
CN101835909A (zh) 2010-09-15
CN101835909B (zh) 2013-09-18
PT2205768E (pt) 2011-09-06
KR101540134B1 (ko) 2015-07-28

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