EP1913164B1 - Agents de production de cuir - Google Patents

Agents de production de cuir Download PDF

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Publication number
EP1913164B1
EP1913164B1 EP06777879A EP06777879A EP1913164B1 EP 1913164 B1 EP1913164 B1 EP 1913164B1 EP 06777879 A EP06777879 A EP 06777879A EP 06777879 A EP06777879 A EP 06777879A EP 1913164 B1 EP1913164 B1 EP 1913164B1
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Prior art keywords
component
formaldehyde
weight
condensates
solution according
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Not-in-force
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EP06777879A
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German (de)
English (en)
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EP1913164A1 (fr
Inventor
Alain Lauton
Catherine Gabagnou
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.)
TFL Ledertechnik GmbH and Co KG
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TFL Ledertechnik GmbH and Co KG
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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
    • C14C3/18—Chemical tanning by organic agents using polycondensation products or precursors thereof
    • C14C3/20—Chemical tanning by organic agents using polycondensation products or precursors thereof sulfonated

Definitions

  • the present invention relates to an aqueous composition for the tanning of pelts or tanning, fatliquoring and dyeing of leather, a process for the tanning of pelts or tanning, fatliquoring and dyeing of leather and the leather treated by the process.
  • Chrome-free tanning has become more important in recent years, particularly for the area of automotive leather. However, it is particularly difficult to produce leather with an intense dyeing which was tanned exclusively by an anionic method, with either vegetable or synthetic tanning agents. The anionic character of the tanned leather then evidently does not enable the leather to fix the dye as desired in sufficient concentration. Frequently, the tanner is therefore forced to increase the amount of dyes, tanning agents and fatliquoring agents. This results in substantially poorer liquor exhaustion. Another disadvantage of chrome-free tanning is the substantially higher cost factor.
  • DE 28 56 628 describes a process for dyeing grain leather with anionic dyes for both anionically and cationically tanned leather, which is characterized in that the dyeing process is effected in the presence of two neutral surfactants in addition to the anionic dye.
  • These surfactants are oxyethylated aliphatic alcohols and oxyethylated primary amines, which are present in a weight ratio of 4:1 to 1:4.
  • the dye is first allowed to run for 5 to 90 minutes in the dye liquor separated from the tanning, and the surfactant mixture is then added which leads to a deepening of the colour. The subsequent fatliquoring of the leather can be effected in the presence of the surfactant mixture mentioned.
  • the invention firstly relates to an aqueous solution of
  • the tanning agents in the form of component B1) are known, cf. for example Ullmanns Enzyklopädie der ischen Chemie [Ullmann's Encyclopaedia of Industrial Chemistry], vol. 16, (4), 138 to 140 (1979 ), and can be prepared by processes as described in the references stated there.
  • aromatic compounds naphthalene, biphenyl, terphenyl, phenols, cresols, 4,4'-dihydroxydiphenyl sulphone, ⁇ -naphthol, dihydroxybenzenes, resorcinol, 2,2'-bis(hydroxyphenyl)propane and diaryl ethers, such as diphenyl ether and ditolyl ether, which are sulphonated in a known manner.
  • sulphonated aromatic compounds can be subjected, alone or in combination with a further aromatic, optionally likewise sulphonated compound, to a condensation with formaldehyde and/or urea.
  • the component B1) is preferably selected from the abovementioned tanning agents b), e), h) and k).
  • the oxyethylated aliphatic amines in the form of a component B2) are alkylamine ethoxylates of the following general formula (I). They are obtained by ethoxylation of aliphatic primary amines.
  • the data for the chain length n and degree of ethoxylation m in the following general formula (I) for alkylamine ethoxylates are mean values.
  • the component B2) is therefore a compound of the general formula (I): in which R denotes a linear or branched hydrocarbon radical having 8-20 C atoms and m denotes 5-80.
  • Alkylamine ethoxylates of linear aliphatic primary amines such as, for example, octyl-, nonyl-, tridecyl-, oleyl-, or stearylamine, whose hydrocarbon radical R has 12 to 18 C atoms, the degree of ethoxylation m being 5 to 12, are preferably used.
  • the oxyethylated aliphatic alcohols in the form of a component B3) are alkyl alcohol ethoxylates of the following general formula (II). These are prepared by ethoxylation of industrial fatty alcohols from fat hydrogenation or from alkanols of petrochemical (oxo alcohols) origin. Several moles of ethylene oxide are subjected to an addition reaction with one mole of fatty alcohol or oxo alcohol by preferably alkaline catalysis. Adducts having more than 80 ethylene oxide units are possible. This leads to a distribution between polyethylene glycol ethers of different degrees of ethoxylation (EO degree).
  • EO degree polyethylene glycol ethers of different degrees of ethoxylation
  • Homologues are defined as those AEOs which differ in the length of the alkyl radical and ethoxymers are defined as those AEOs which differ in the number of ethoxy units.
  • the data for the chain length n and EO degree m in the following general formula for alkyl alcohol ethoxylates are therefore mean values.
  • the component B3) is therefore a compound of the general formula (II): in which R denotes a linear or branched hydrocarbon radical having 8-20 C atoms and m denotes 5-80.
  • Alkyl alcohol ethoxylates of linear aliphatic fatty alcohols, whose hydrocarbon radical R has 12 to 18 C atoms and in which the EO degree m is 5 to 12 are preferably used.
  • composition according to the invention contains, as a proportion of B), a component B1) in an amount of 5-95% by weight, preferably 20-90% by weight, particularly preferably 40-90% by weight, especially preferably 55-90% by weight.
  • composition according to the invention thus furthermore contains, as a proportion of B) and summing to 100% by weight, the component B2) in an amount of 95-5% by weight, preferably 80-10% by weight, particularly preferably 60-10% by weight, especially preferably 10-45% by weight.
  • the component B2) can be partially replaced by the optional component B3).
  • Use of the component B3) is not decisive for the improved dyeing according to the invention and regular distribution of tanning agents and fatliquoring agents and improved liquor exhaustion. However, it was found that an emphatically brilliant dyeing can be achieved with the use of component B3).
  • An aqueous solution according to the invention consists of
  • a composition according to the invention can be prepared by simply combining the components described above.
  • the initially prepared component B1) is initially introduced into a vessel as an aqueous solution which is optionally adjusted with a base to a slightly basic pH of about 7.0 to 8.0, and subsequently aqueous solutions of the component B2) and optionally B3) are stirred in, clear, pale or brown solutions being obtained.
  • the solutions are, if required, adjusted to an approximately neutral to moderately basic pH with the aid of bases, such as ammonia or alkali.
  • the pH of the solution which is established in this manner should be above 6.0 and should not exceed 9.0.
  • Preferred pH values are above 6.5, in particular above 6.8, and should not exceed a value of 8.5.
  • the particularly preferred pH range extends from 7.0 to 8.0.
  • the tanning agents in the form of the component B1) are therefore always used predominantly, as a rule completely, in the form of their salts, especially lithium, potassium or ammonium salts or in particular their sodium salts.
  • Ammonium salts are understood as meaning salts which are derived from ammonia or primary, secondary and tertiary amines.
  • a feature essential to the invention is therefore the circumstance that the naturally acidic compounds (free sulphonic acids) in the form of the component B1) are adjusted to an approximately neutral to moderately basic pH, and that furthermore a component B1) neutralized in this manner, together with a fatty amine in the form of the component B2), gives a clear and surprisingly storage-stable solution.
  • the addition of an optional component B3) changes nothing about this.
  • compositions according to the invention in the form of the solutions described above can advantageously be used in principle with all substrates for leather production.
  • the following may be mentioned:
  • the following amounts of the solutions according to the invention are suitable for use, for example for a 40-50% strength solution of composition as described above, and based on the shaved weight of the hide or of the leather:
  • a wet-white leather pre-tanned in this manner is very suitable for further processing with tanning agents, for example with a solution according to the invention or other tanning agents, for the production of leathers free of heavy metals.
  • a solution according to the invention are expedient for the main tanning, dyeing and fatliquoring on already pre-tanned leather in the presence of aldehydes or vegetable tanning agents.
  • a substantial effect according to the invention is based on the possibility firstly of carrying out the steps of tanning, dyeing and fatliquoring without changing the liquor, and on the fact that secondly a very good liquor exhaustion is achieved and optimal dyeing can be achieved.
  • ком ⁇ онент 4-10% by weight of a composition according to the invention are sufficient for retanning and for deepening the colour in dyeing with dyes.
  • the invention therefore furthermore relates to a process for the pretanning of pelts or retanning of wet-white, wet-blue or vegetable-pretanned leather as a substrate, characterized in that a solution according to the invention is added to the aqueous liquor and said liquor is allowed to act on the substrate. Depending on the substrate, the solution according to the invention penetrates completely into the leather within 1 to 3 hours.
  • the solution according to the invention is added during the pretanning but after the treatment with aldehyde. If the solution according to the invention is used during the retanning, it should be used firstly before the dyes and secondly together with the fatliquoring agents in order to achieve a deepening of colour and an improvement in the bath exhaustion.
  • the present invention furthermore relates to the leathers produced by the process according to the invention or tanned using a composition according to the invention.
  • Example 1 Agents consisting of the components B1), B2) and B3)
  • Example 2 Agent consisting of the components B1) and B2)
  • Example 3 Agent consisting of the components B1), B2) and B3):
  • Example 4 Agent consisting of the components B1) and B2):
  • Example 5 Agent consisting of the components B1), B2) and B3):
  • the stated percentages relate to the salted weight of the leather hides or skins.
  • Example B1 Use for the pretanning of pelts
  • 100 parts of a pickled calf pelt are first treated with 2.5% of a 25% strength glutardialdehyde solution for 6 hours at 25°C in a rotating drum and then stirred for a further 2 hours with 5% of the composition according to preparation example A1.
  • the pH is then adjusted to 4.0 with pulverized sodium bicarbonate or sodium formate.
  • the leather thus treated (wet-white leather) is dewatered and is shaved to the desired thickness.
  • This pre-tanned leather is outstandingly suitable for further processing with mineral, vegetable or synthetic tanning agents for the production of leather free of heavy metals.
  • the dyeing is carried out with 2.2% of commercially available dye, such as C.I. Acid Black 210 and mixtures of this dye with other C.I. Acid Black dyes as secondary components.
  • the dyes are allowed to act for 240 minutes.
  • the mixture is acidified with 0.8% of formic acid after 60 minutes until complete exhaustion of the liquor.
  • the bath is discharged and the leather is washed for 10 minutes with water at 50°C.
  • 3% of product, according to example A5 is added for 20 minutes.
  • 200% of water at 50°C and 3% of product according to example A5 are introduced into the drum, and the run time is 20 minutes.
  • 12% of the fatliquoring agent are added and, after 60 minutes, the mixture is acidified with 1 % of formic acid for 45 minutes until complete exhaustion of the liquor.
  • the leather thus obtained has good fullness and has a deep black brilliant hue.
  • the wet-blue leather (cut to 1.0-1.2 mm) is rinsed, washed and neutralized to pH 5.5 in 150% of water containing a sodium bicarbonate/sodium formate mixture, in the usual manner.
  • the preparatory fatliquoring (an about 50% strength aqueous solution of a fatliquoring agent based on sulphited natural and synthetic fats) is applied, the fatliquoring agent is discharged and the leather is washed for 10 minutes with 200% of water at 30°C.
  • 100% of water at 30°C and 10% of commercially available phenol sulphonic acids as a tanning agent together with 4% of vegetable extract (tara extract) and 3% of fatliquoring agent (an about 50% aqueous solution of a fatliquoring agent based on sulphited natural and synthetic fats) are introduced into the drum, and the run time is 30 minutes.
  • Retanning is effected with 6% of product according to example A2 for 20 minutes. Thereafter, 2.5% of C.I. Acid Black 210 is added and dyeing is effected; the process may take up to 60 minutes before the desired dyeing is achieved. After the fatliquoring, discharge is effected in the usual manner and 6% of commercially available phenol sulphonic acids as a tanning agent together with 2% of a vegetable extract are added for 45 minutes.
  • the leather thus obtained has a level black dyeing in an optimal hue and fastness.

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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)

Claims (10)

  1. Solution aqueuse de
    A) de 20 à 90 % en poids d'eau et, dissous dans celle-ci,
    B) de 10 à 80 % en poids d'une composition contenant
    B1) un composé aromatique de tannage renfermant au moins un groupe sulfo ou un sel de celui-ci, choisi parmi :
    a) des produits de condensation de l'acide naphtalènesulfonique et du formaldéhyde ;
    b) des produits de condensation au formaldéhyde de 4,4'-dihydroxydiphénylsulfones avec des acides (hydroxy)arylsulfoniques ;
    c) des produits de condensation au formaldéhyde de composés hydroxyle aromatiques renfermant des groupes sulfo avec des halogénures d'aralkyle ;
    d) des produits de condensation urée-formaldéhyde de phénols et d'acides phénolsulfoniques ;
    e) des produits de réaction du phénol et d'un agent de sulfonation, tel que l'oléum, le rapport molaire (phénol):(SO3) étant de (1):(0,8-2,2) ;
    f) des produits de condensation d'éthers diaryliques sulfonés et du formaldéhyde ;
    g) des produits de condensation de di- ou de terphényles sulfonés et du formaldéhyde ;
    h) des produits de condensation de la 4,4'-dihydroxydiphénylsulfone et de la 4,4'-dihydroxydiphénylsulfone sulfonée avec le formaldéhyde ;
    i) des produits de condensation au formaldéhyde d'un acide diaryléthersulfonique et de la 4,4'-dihydroxydiphénylsulfone ;
    j) des produits de condensation au formaldéhyde du phénol avec des acides arylsulfoniques ou des acides hydroxyarylsulfoniques ; et
    k) des produits de condensation au formaldéhyde de dioxydiarylsulfones avec des sulfites,
    B2) un composé de formule générale (I) :
    Figure imgb0007
     dans laquelle R désigne un radical hydrocarboné linéaire ou ramifié renfermant de 8 à 20 atomes de carbone, et m vaut de 5 à 80,
    et éventuellement
    B3) un composé de formule générale (II) :
    Figure imgb0008
     dans laquelle R désigne un radical hydrocarboné linéaire ou ramifié renfermant de 8 à 20 atomes de carbone, et m vaut de 5 à 80,
    la solution présentant un pH supérieur à 6,0.
  2. Solution selon la revendication 1, caractérisée en ce que le composant B1) est choisi parmi b), e), h) et k).
  3. Solution selon la revendication 1, caractérisée en ce que le composant B2) est présent sous la forme d'un sel de lithium, de potassium ou d'ammonium, ou en particulier sous la forme d'un sel de sodium.
  4. Solution selon la revendication 1, caractérisée en ce que des alkylamines-éthoxylates d'amines primaires aliphatiques linéaires, dont le radical hydrocarboné R renferme de 12 à 18 atomes de carbone, le degré d'éthoxylation m étant de 5 à 12, sont utilisés en tant que composant B2).
  5. Solution selon la revendication 1, caractérisée en ce que des éthoxylates d'alcool alkyliques d'alcools primaires aliphatiques linéaires, dont le radical hydrocarboné R renferme de 12 à 18 atomes de carbone, le degré d'éthoxylation m étant de 5 à 12, sont utilisés en tant que composant B3).
  6. Solution selon la revendication 1, caractérisée en ce que la composition contient
    un composant B1) en une quantité de 5 à 95, de préférence de 20 à 90 % en poids et
    un composant B2) en une quantité de 95 à 5, de préférence de 10 à 80 % en poids.
  7. Solution selon la revendication 6, caractérisée en ce que, dans la composition, de 1 à 30, de préférence de 5 à 20, particulièrement préférablement de 5 à 15 % en poids du composant B2) sont remplacés par un composant B3).
  8. Solution selon la revendication 1, caractérisée en ce que le pH de la solution est supérieur à 6,5 et ne dépasse pas 9,0, de préférence est supérieur à 6,8 et ne dépasse pas 8,5, en particulier s'échelonne de 7,0 à 8,0.
  9. Solution selon la revendication 1, qui est constituée de
    A) de 35 à 65, de préférence de 45 à 60 % en poids d'eau et, dissous dans celle-ci,
    B) de 35 à 65, de préférence de 40 à 55 % en poids de la composition.
  10. Procédé de pré-tannage de peaux ou de retannage de cuir blanc humide, bleu humide ou à prétannage végétal en tant que substrat, caractérisé en ce qu'une solution selon l'une quelconque des revendications 1 à 9 est ajoutée à la liqueur aqueuse et on laisse ladite liqueur agir sur le substrat.
EP06777879A 2005-07-25 2006-07-21 Agents de production de cuir Not-in-force EP1913164B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH12352005 2005-07-25
PCT/EP2006/064487 WO2007012606A1 (fr) 2005-07-25 2006-07-21 Agents de production de cuir

Publications (2)

Publication Number Publication Date
EP1913164A1 EP1913164A1 (fr) 2008-04-23
EP1913164B1 true EP1913164B1 (fr) 2008-11-19

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EP (1) EP1913164B1 (fr)
AR (1) AR057081A1 (fr)
AT (1) ATE414796T1 (fr)
DE (1) DE602006003772D1 (fr)
WO (1) WO2007012606A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104450993A (zh) * 2014-12-24 2015-03-25 上海金狮化工有限公司 一种复鞣剂及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011131542A1 (fr) * 2010-04-21 2011-10-27 Basf Se Produits, procédés pour leur préparation et leur utilisation
EP2579751A4 (fr) 2010-06-08 2013-10-23 Dixie Consumer Products Llc Système et procédé pour solidariser des articles de coutellerie
MX2013001224A (es) 2010-08-12 2013-04-24 Dixie Consumer Products Llc Cubiertos acoplados y metodos relacionados.
CA2805734C (fr) 2010-08-24 2018-09-18 Dixie Consumer Products Llc Bande amovible pour le rangement de couverts de table et procedes associes
WO2012078938A1 (fr) 2010-12-10 2012-06-14 Dixie Consumer Products Llc Mécanisme de distribution pour distributeur d'ustensiles et procédés associés
MX2013005936A (es) 2010-12-10 2013-09-26 Dixie Consumer Products Llc Impulsion de tuercas para dispensar cuberteria y metodos relacionados.
CA2819646C (fr) 2010-12-14 2019-10-01 Dixie Consumer Products Llc Entrainement par courroie pour distribuer de la coutellerie et procedes associes
US9439518B2 (en) 2011-08-19 2016-09-13 Dixie Consumer Products Llc Cutlery dispenser

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Publication number Priority date Publication date Assignee Title
DE2856628C2 (de) * 1978-12-29 1980-04-24 Basf Ag, 6700 Ludwigshafen Verfahren zum Färben von Narbenleder
CH671052A5 (fr) * 1985-01-30 1989-07-31 Sandoz Ag
US5300121A (en) * 1987-04-28 1994-04-05 Commonwealth Scientific And Industrial Research Organisation Process for the treatment of wool skins

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104450993A (zh) * 2014-12-24 2015-03-25 上海金狮化工有限公司 一种复鞣剂及其制备方法

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Publication number Publication date
EP1913164A1 (fr) 2008-04-23
WO2007012606A1 (fr) 2007-02-01
AR057081A1 (es) 2007-11-14
ATE414796T1 (de) 2008-12-15
DE602006003772D1 (de) 2009-01-02

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