EP0607554A1 - Agent tannant et procédé de tannage - Google Patents

Agent tannant et procédé de tannage Download PDF

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Publication number
EP0607554A1
EP0607554A1 EP93119884A EP93119884A EP0607554A1 EP 0607554 A1 EP0607554 A1 EP 0607554A1 EP 93119884 A EP93119884 A EP 93119884A EP 93119884 A EP93119884 A EP 93119884A EP 0607554 A1 EP0607554 A1 EP 0607554A1
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EP
European Patent Office
Prior art keywords
tanning
minutes
move
weight
formula
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
EP93119884A
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German (de)
English (en)
Other versions
EP0607554B1 (fr
Inventor
Harald Dr. Bauer
Christner Dr. Jürgen
Gertrud Wick
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.)
Roehm GmbH Darmstadt
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Roehm GmbH Darmstadt
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Publication of EP0607554A1 publication Critical patent/EP0607554A1/fr
Application granted granted Critical
Publication of EP0607554B1 publication Critical patent/EP0607554B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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 invention relates to tanning agents which contain an ⁇ , ⁇ '-dialdehyde in combination with a polymer P containing hydroxyl groups as well as a tanning process in which the tanning agents are used in combination.
  • chrome tanning which supplies excellent leather (chrome leather) but is ecologically unsafe (cf.Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd.Ed.Vol. 14 , pg. 200 - 231 , pg. 226ff, J. Wiley 1981; Ullmanns Encyclopedia of Industrial Chemistry, 5th Ed. Vol. A15, pg. 259-282, VCH 1990).
  • chrome tanning process previously used in practice, chromium salts are used in an amount of 1.5-2.5% chromium-III-oxide, based on the weight of the nakedness, to achieve a cookable leather.
  • Chromium-free or low-chromium tanning can also be carried out, for example, with aldehydes as the tanning agent (so-called aldehyde tanning, see Kirk-Othmer, loc.cit; F. Stather, tanning chemistry and tanning technology, Akademie-Verlag, Berlin 1967).
  • aliphatic dialdehydes in particular glutardialdehyde and succinic dialdehyde, have prevailed, but these are predominantly used in pretanning, ie followed by other tanning processes such as chrome tanning and retanning.
  • the amounts of pure glutaraldehyde required for pretanning - about 0.5 to 1% by weight, based on the weight of the nakedness - are comparatively small.
  • the crosslinking caused by glutaraldehyde is extremely stable to hydrolysis.
  • glutaraldehyde in pre-tanning, one often encounters difficulties because of the uneven penetration of the pimples pecked in cross-section; the peripheral zones were thus more networked than the middle class. In practice, therefore, lower shrinkage temperatures are observed in the middle layers than in the peripheral areas.
  • DE-C 38 11 267 proposes a process for the production of semi-finished leather products in which a reversibly inactivated C2-C8- ⁇ - ⁇ '-dialdehyde is used as the tanning agent with high penetration properties.
  • the inactivation is done by adding 0.2 to 4.0 mol of a hydroxy compound of the formula R - O - [- (C2H4O) x - (C3H6O) y - (C4H8O) z -] n H wherein n is from zero to 10, x + y + z is an integer from 1 to 20, R is hydrogen (if n ⁇ O) or C1-C12 alkyl optionally substituted with one or more hydroxyl groups.
  • the sum of components a) to d) in P is 100% by weight.
  • the proportion of the monomers of the formulas III and IV which contain hydroxyl groups or which can release them hydrolytically in a polymer-analogous reaction is in the range from 100 to 5% by weight, based on the polymers P.
  • the ratio between the tanning agent ⁇ , ⁇ '-dialdehyde of the formula I and the polymer P is usually in the range from 1: 4 to 4: 1 parts by weight.
  • the partial inactivation of the aldehydes of the formula I occurs on the one hand through the hydroxyl functions of the polymers P themselves, but it can advantageously be enhanced by adding one or more alcohols, preferably water-soluble alcohols.
  • Alcohols preferably water-soluble alcohols.
  • Polyhydric alcohols from the group consisting of glycol, glycerol, pentaerythritol, butyl glycol, 1,4-butanediol, polyethylene glycols, polyethylene propylene glycols and sugars and sugar alcohols such as glucose, fructose, sorbitol are particularly suitable for this purpose.
  • Hydroxycarboxylic acids such as glycolic acid are also suitable.
  • these alcohols are used in a molar ratio of 0 to 3.5, in particular 1 to 2 mol, based on the aldehydes of the formula I.
  • Glutardialdehyde is particularly preferred as the aldehyde of the formula I, as well as succinic dialdehyde.
  • the monomeric compounds of the formula II which may be mentioned are in particular (meth) acrylic acid, maleic acid, fumaric acid and itaconic acid, if appropriate also in a mixture, and also as the compound of the formula II-A Maleic anhydride and the itaconic anhydride called.
  • the hydroxy group-containing monomers of the formula III are the hydroxyethyl acrylate and the methacrylate, the 3-hydroxypropyl acrylate and the methacrylate, the 4-hydroxybutyl acrylate and the methacrylate, and also monoacrylates or methacrylates of polyols such as, for example, that Glycerol monoacrylate and methacrylate, neopentyl acrylate and methacrylate.
  • Particularly suitable compounds of the formula IV are vinyl acetate and vinyl propionate.
  • Monomers of the formula V which may be mentioned in particular are methyl methacrylate and methyl acrylate, ethyl acrylate, furthermore ethylhexyl acrylate and ethylhexyl methacrylate.
  • the polymers P to be used according to the invention preferably have a molar mass in the range from 1,000 to 50,000, in particular less than 5,000 g / mol. Molecular weight is determined using size exclusion chromatography (SEC) (cf. HF Mark et al. Encyclopedia of Polymer Science & Engineering, 2nd. Ed. Vol. 10 , pg. 1 - 18, J. Wiley 1987; Ullmann's Encyclopedia of Industrial Chemistry 5th Ed. Vol. 20A, pg. 563-568, VCI (1992)).
  • SEC size exclusion chromatography
  • the tanning agents GM usually have a polymer content P (dry weight) of 10-60% by weight, preferably 20-40% by weight.
  • the tanning agents GM according to the invention have, as aqueous formulations, a pH in the range from 0.5 to 5, preferably from 2 to 4.
  • the polymers P can be prepared in a manner known per se by radical polymerization of the monomers of the formulas I-V in accordance with the desired proportions (cf. H. Rauch Puntigam, Th. Völker, Acryl- und Methacrylitatien, Springer Verlag 1968).
  • the polymers P in hydrophilic monomers it is advisable to carry out the polymerization in the form of solution polymerization. This is carried out in an aqueous phase with the addition of water-soluble accelerators, the concentration of the monomers generally being kept below 25% by weight, since the reaction is exothermic.
  • water-soluble accelerators the concentration of the monomers generally being kept below 25% by weight, since the reaction is exothermic.
  • molecular weight regulators in particular sulfur regulators, especially water-soluble regulators such as mercaptoethanol or thioglycolic acid or, if necessary.
  • the initiator content is generally in the range from 0.01 to 1% by weight, based on the monomers.
  • Redox systems known per se are particularly preferred as initiators, for example those which contain heavy metal ions, for example iron ions, in combination with water-soluble per compounds such as hydrogen peroxide or persulfate.
  • the polymerization can advantageously be carried out as a two-stage redox batch polymerization in a suitable reaction vessel. For example, half of the monomers are placed in the aqueous phase if necessary. together with the reducing component of the initiator at room temperature before, as a guide, about 3 to 3.5 times the amount of water can be used.
  • the polymerization is then started by adding the per compound, for example 30% aqueous perhydrol solution. The temperature then rises, for example to approximately 80 degrees C.
  • the mixture is cooled, for example to about 35 ° C., and the complete batch of the second stage, usually consisting of the second half of the monomers and the regulator or the reducing agent, is added and the is added by adding about the same amount of per compound Reaction started, the temperature rising again, for example to 85 degrees C.
  • the mixture is advantageously stirred for another hour and then cooled.
  • the process products can advantageously be used in the liquid phase, ie without isolating the polymers P.
  • the advantage of the process according to the invention is, inter alia, that the di-aldehydes of the formula I, in particular the glutardialdehyde, are inactivated to the desired extent by the organically bound hydroxyl groups present, and thus the self-condensation is prevented. It is of particular importance that the polymer penetrates deeper in the skin cross-section due to the modification that occurs with the dialdehyde and this results in a better filling effect. Furthermore, with a subsequent low-chrome retanning, a more even chrome distribution is obtained. When using the polymer P there is also a better leveling of the coloring and better foldability.
  • Polymer P-1 polymer based on acrylic acid and 2-hydroxyethyl acrylate in a weight ratio of 9/1.
  • Polymer P-2 polymer based on acrylic acid and 2-hydroxyethyl acrylate in a weight ratio of 8/2
  • the polymer P-1 with a molecular weight of approx. 1200 is produced in a 2-stage redox batch.
  • the entire 1st stage (7.49 kg water, 2.097 kg acrylic acid, 0.233 kg 2-hydroxyethyl acrylate, 466 g mercaptoethanol and 23 g FeSO4 solution 1%) is placed in the reaction vessel and at room temperature by adding 585 g perhydrol (30 % H2O2) started. The temperature rises to 80 degrees C. After the maximum temperature has been exceeded, the mixture is cooled to 35 ° C. and the complete second stage (2.097 kg of acrylic acid and 0.233 kg of 2-hydroxyethyl acrylate and 466 g of mercaptoethanol) is used and started again by adding 585 g of perhydrol. The temperature rises to 85 degrees C. After the maximum temperature has been reached, stirring is continued for 1 hour and then cooling. The polymer P is obtained in an aqueous phase which can be used as such.
  • Polymer P-2 is prepared analogously. TABLE 1 Properties of the polymers P polymer Dryness (%) viscosity pH P-1 40 ⁇ 50 mPas 4.0 P-2 40 ⁇ 50 mPas 3.8
  • the tanning agents GM according to the invention are obtained by mixing the components, the polymer (s) P, the aldehyde of the formula I and if necessary. alcohol at room temperature or by briefly heating to 50 degrees C (pH 3-4).
  • the polymers P are preferably used, as are directly obtained in the polymerization.
  • a list of tested GM tanning agents is given in Table 2 below: TABLE 2 Tanning agent GM No. Glutardialdehyde + polymer P + alcohol Molar ratio glutar.
  • the percentages relate to the weight of the nakedness.
  • Example C-1a Chromium-free pre-tanning
  • the percentages relate to the weight of the nakedness
  • Example C-2 Chrome Tanning
  • Example C-2a Chrome retanning of the chrome-free pretanned leather from Example C-1
  • Example C-3a Vegetable retanning of the chrome-free pretanned leather from Example C-1
  • fatliquor e.g. sulfited oils 10.0% fatliquor, e.g. sulfosuccinic acid ester Move 60 minutes
  • Example C-4a Synthetic retanning of the chrome-free pretanned leather from Example C-1
  • fatliquor e.g. sulfited oils 10.0% fatliquor, eg sulfosuccinic acid ester Move 60 minutes

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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP93119884A 1992-12-14 1993-12-09 Agent tannant et procédé de tannage Expired - Lifetime EP0607554B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4242076A DE4242076A1 (de) 1992-12-14 1992-12-14 Gerbmittel und Gerbverfahren
DE4242076 1992-12-14

Publications (2)

Publication Number Publication Date
EP0607554A1 true EP0607554A1 (fr) 1994-07-27
EP0607554B1 EP0607554B1 (fr) 1997-03-05

Family

ID=6475182

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93119884A Expired - Lifetime EP0607554B1 (fr) 1992-12-14 1993-12-09 Agent tannant et procédé de tannage

Country Status (9)

Country Link
US (2) US5505864A (fr)
EP (1) EP0607554B1 (fr)
JP (1) JPH06212200A (fr)
KR (1) KR940014813A (fr)
AT (1) ATE149573T1 (fr)
BR (1) BR9305035A (fr)
DE (2) DE4242076A1 (fr)
ES (1) ES2099357T3 (fr)
TW (1) TW229232B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996015276A1 (fr) * 1994-11-15 1996-05-23 Basf Aktiengesellschaft Procede de preparation de cuir et de fourrures au moyen de matieres tannantes polymeres
EP1029930A1 (fr) * 1999-02-15 2000-08-23 Dr. Th. Böhme KG Chem. Fabrik GmbH & Co. Procédé de tannage

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0717114A3 (fr) * 1994-12-15 1996-08-21 Ciba Geigy Ag Composition aqueuse pour le prétannage de peaux ou le retannage de cuir
DE19546254A1 (de) * 1995-12-12 1997-06-19 Basf Ag Verwendung von wäßrigen Lösungen oder Dispersionen von Copolymerisaten aus carboxylgruppenhaltigen Monomeren, ethylenisch ungesättigten Acetalen, Ketalen oder Orthocarbonsäureestern und gegebenenfalls weiteren copolymerisierbaren Monomeren als Ledergerbstoffe
DE102005032585A1 (de) * 2005-07-11 2007-01-25 Basf Ag Verfahren zur Herstellung von Leder
JP5172228B2 (ja) * 2007-06-28 2013-03-27 ミドリホクヨー株式会社 革
ITUB20152180A1 (it) * 2015-07-14 2017-01-14 Db Patents Ltd Metodo migliorato per conciare una pelle animale.
IT201700095318A1 (it) * 2017-08-23 2019-02-23 Db Patents Ltd Metodo per conciare una pelle animale.
CN111747593A (zh) * 2020-07-01 2020-10-09 河北东明皮革有限公司 制革准备与鞣制工段废液分段循环系统及其使用方法
CN117187447B (zh) * 2023-09-06 2025-07-11 天津美科信生物科技有限公司 一种醛-树脂结合鞣制备菌丝纤维皮的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2423118C3 (de) * 1974-05-13 1979-04-26 Schill & Seilacher Gmbh & Co, 7030 Boeblingen Verfahren zur Herstellung von Leder
EP0118213A1 (fr) * 1983-02-07 1984-09-12 Rohm And Haas Company Procédé de tannage du cuir
DE3811267C1 (fr) * 1988-04-02 1989-05-18 Schill & Seilacher Gmbh & Co, 7030 Boeblingen, De

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2205883A (en) * 1938-06-16 1940-06-25 Du Pont Tanning
US2941859A (en) * 1959-04-08 1960-06-21 Martin L Fein Tanning with glutaraldehyde
GB952557A (en) * 1961-08-29 1964-03-18 Degussa Process for the treatment of leather
US3945792A (en) * 1969-07-09 1976-03-23 Ciba-Geigy Corporation Process for the filling of leather and compositions therefor
ES421535A1 (es) * 1973-01-13 1976-06-16 Roehm Gmbh Procedimiento para la preparacion de pellejos dispuestos para curtir a partir de cuero y pieles de origen animal.
DE2404789C3 (de) * 1974-02-01 1979-02-15 Roehm Gmbh, 6100 Darmstadt Verfahren zur Herstellung gerbfertiger Blößen aus tierischen Häuten und Fellen
DE2930342A1 (de) * 1979-07-26 1981-02-19 Roehm Gmbh Verbessertes verfahren zur herstellung von leder
DE3267088D1 (en) * 1981-03-06 1985-12-05 Ciba Geigy Ag Method of retanning leather with acrylic oligomers
SU1520068A1 (ru) * 1987-11-12 1989-11-07 Ереванский государственный университет Тройной сополимер N, N-диметиламиноэтилметакрилата, винилацетата и винилового спирта в качестве стабилизатора дубител дл обработки голь
DE3926168A1 (de) * 1989-08-08 1991-02-14 Basf Ag Verwendung von copolymerisaten auf basis von langkettigen alkylvinylethern und ethylenisch ungesaettigten dicarbonsaeureanhydriden zum hydrophobieren von leder und pelzfellen

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2423118C3 (de) * 1974-05-13 1979-04-26 Schill & Seilacher Gmbh & Co, 7030 Boeblingen Verfahren zur Herstellung von Leder
EP0118213A1 (fr) * 1983-02-07 1984-09-12 Rohm And Haas Company Procédé de tannage du cuir
DE3811267C1 (fr) * 1988-04-02 1989-05-18 Schill & Seilacher Gmbh & Co, 7030 Boeblingen, De

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996015276A1 (fr) * 1994-11-15 1996-05-23 Basf Aktiengesellschaft Procede de preparation de cuir et de fourrures au moyen de matieres tannantes polymeres
EP1029930A1 (fr) * 1999-02-15 2000-08-23 Dr. Th. Böhme KG Chem. Fabrik GmbH & Co. Procédé de tannage

Also Published As

Publication number Publication date
US5505864A (en) 1996-04-09
US5492539A (en) 1996-02-20
JPH06212200A (ja) 1994-08-02
ATE149573T1 (de) 1997-03-15
TW229232B (fr) 1994-09-01
EP0607554B1 (fr) 1997-03-05
BR9305035A (pt) 1994-06-21
DE4242076A1 (de) 1994-06-16
KR940014813A (ko) 1994-07-19
DE59305626D1 (de) 1997-04-10
ES2099357T3 (es) 1997-05-16

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