EP1831405A1 - Composition pour le traitement du cuir - Google Patents

Composition pour le traitement du cuir

Info

Publication number
EP1831405A1
EP1831405A1 EP05850465A EP05850465A EP1831405A1 EP 1831405 A1 EP1831405 A1 EP 1831405A1 EP 05850465 A EP05850465 A EP 05850465A EP 05850465 A EP05850465 A EP 05850465A EP 1831405 A1 EP1831405 A1 EP 1831405A1
Authority
EP
European Patent Office
Prior art keywords
weight
leather
component
acid
phenol
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
EP05850465A
Other languages
German (de)
English (en)
Other versions
EP1831405B1 (fr
Inventor
Alain Lauton
Aykut Direk
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
Original Assignee
TFL Ledertechnik GmbH and Co KG
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 TFL Ledertechnik GmbH and Co KG filed Critical TFL Ledertechnik GmbH and Co KG
Publication of EP1831405A1 publication Critical patent/EP1831405A1/fr
Application granted granted Critical
Publication of EP1831405B1 publication Critical patent/EP1831405B1/fr
Not-in-force 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
    • C14C3/28—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 a composition comprising various synthetic retanning agents, a process for the treatment of pretanned leathers using this composition, and a material obtained by this process.
  • the customary process steps of a leather tanned with metal salts comprise first washing and neutralization of a leather tanned with metal salts, which has a pH of about 4.5 to 6.5 in water.
  • the leather is then treated in turn with retanning agents in a weakly alkaline, aqueous medium in order to achieve certain properties, such as, for example, tensile strength, fullness, hardness or softness.
  • a leather pretreated in this manner is treated with anionic dyes in a fresh bath, preferably above the isoelectric point and often in the presence of penetration auxiliaries, in order thus to achieve complete dyeing of the leather and a good colour strength.
  • the leather is then treated with fatliquoring agents which impart the desired softness, flexibility and strength to the leather.
  • the dyeing process in the aqueous alkaline medium is complex owing to the different process steps and concomitantly used chemicals and gives rise to a large amount of wastewaters which make disposal expensive.
  • Vegetable tanning agents, aromatic syntans, resin tanning agents, reactive tanning agents and mineral and polymeric tanning agents are mentioned as retanning agents which may be used.
  • the combination of retanning agents according to the present invention is not mentioned.
  • the compositions according to DE 197 46 445 A1 may also contain further additives, including neutralizing agents, dye formulations or finishing agents. If the composition contains only retanning agents and fatliquoring agents, the steps of neutralization, dyeing and finishing are carried out in separate steps.
  • the invention firstly relates to a composition containing a) 1 - 95% by weight of a product of the reaction of a phenol and a sulphonating agent, the molar ratio (phenol):(SO 3 ) being (1):(1.1-2.2), b) 1 - 95% by weight of a condensate of the reaction of a naphthalenesulphonic acid and formaldehyde, and c) 5 - 50% by weight c1) of a formaldehyde condensate of a dihydroxydiarylsulphonic acid with aryl- or (hydroxy)arylsulphonic acid and/or c2) of a urea/formaldehyde condensate of a phenol and phenolsulphonic acid, the sum of the components a), b), c1) and c2) being 100% by weight.
  • the component a) of the composition is the product of the reaction of a phenol and a sulphonating agent, the molar ratio (phenol):(SO 3 ) being (1):(1.1-2.2).
  • the component a) is already known, for example from EP 0 554 218 A1, which describes the advantageous use of the component a) for pickling pelts.
  • a preferably used sulphonating agent for the preparation of component a) is SO 3 or especially oleum. Oleum is a solution of SO 3 in concentrated sulphuric acid.
  • reaction products of phenol and oleum are particularly suitable, the molar ratio (phenol):(SO 3 ) being especially (1):(1.4-1.8).
  • the reaction products are usually present in the form of mixtures, substantially sulphonated diphenoldisulphonic acid being obtained in the abovementioned reaction, corresponding to the following formula (I):
  • n and m are each O, 1 or 2, provided that the sum of n and m is 1 or 2.
  • Phenolsulphonic acid is also formed as a byproduct.
  • composition according to the invention contains 1 - 95% by weight, preferably 10 - 60% by weight, particularly preferably 15 - 55% by weight, particularly preferably 20 - 50% by weight, of component a).
  • naphthalene is sulphonated according to the known prior art and the sulphonated product is condensed with formaldehyde at elevated temperature with elimination of water to give the desired product.
  • the sulphonation is preferably effected analogously to component a) with the aid of oleum according to the following reaction scheme for naphthalenesulphonic acid by way of example:
  • composition according to the invention contains 1 - 95% by weight, preferably 20 - 80% by weight, particularly preferably 30 - 70% by weight, particularly preferably 40 - 60% by weight, of component b).
  • component c1 For the preparation of component c1 ) known from the prior art, an aryl- or (hydroxy)arylsulphonic acid is condensed with dihydroxydiphenyl sulphone in the presence of formaldehyde with elimination of water, and the product obtained is neutralized, for example - A -
  • the dihydroxydiphenyl sulphone used is preferably 4,4'-dihydroxydiphenyl sulphone.
  • Naphthalenesulphonic acid is particularly preferably used.
  • component c2 For the preparation of component c2) known from the prior art, phenol and sulphonated phenol are condensed with urea and/or formaldehyde.
  • composition according to the invention contains 5 - 50% by weight, preferably 5 - 40% by weight, particularly preferably 5 - 30% by weight, particularly preferably 10 - 25% by weight of component c1) and/or c2).
  • Mixtures of different c1) and/or c2) components can also be used as component c), the abovementioned weight data being applicable for the mixtures.
  • a component c1) is preferably used as component c), particularly preferably the formaldehyde condensate of 4,4'-dihydroxydiphenyl sulphone and naphthalenesulphonic acid.
  • the abovementioned condensates are present in the form of the free acids and can be partly or completely neutralized by suitable alkalis and/or ammonia in aqueous solution.
  • composition according to the invention can be prepared by simply combining the components described above.
  • water is initially introduced into a vessel, for example into a sulphonation flask, and components a), b) and c) are stirred in at room temperature in succession, clear, generally brown solutions being obtained.
  • compositions according to the invention i.e. there are 50 parts by weight of the composition according to the invention per 50 parts by weight of water.
  • a composition i.e. for example adjusted to a concentration of 50%, is added to the liquor in an amount of 1 - 20, preferably 3 - 12, particularly preferably 5 - 10, % by weight, based on the shaved weight of the leather. If the composition according to the invention is adjusted to a different concentration, the amounts used should be appropriately adapted.
  • the composition according to the invention is used in leather production after the pickling and the pretanning but before the retanning, dyeing and fatliquoring.
  • the composition according to the invention it is possible to dispense with the step of neutralization of the tanned leather, and the customary agents for retanning, fatliquoring and dyeing can be added as usual, but without a liquor change being necessary for this purpose.
  • the quality of the leathers obtained is particularly convincing, and said leathers are substantially fuller and stronger than leathers produced by conventional processes.
  • the invention furthermore relates to a process for the treatment of wetwhite, wetblue or vegetable pretanned leather as a substrate, characterized in that - for the purpose of said treatment - a composition according to the invention in the form of an aqueous solution is added to the aqueous liquor and said composition is allowed to act on the pretanned leather.
  • the leather can be produced in all machines suitable for wet finishing, i.e. drum, dosamat, tanning machine or mixer.
  • the invention furthermore relates to a process for the pretreatment and wet finishing of pretanned leather, comprising the steps a) treatment of the leather with the composition according to the invention, b) aftertreatment of the leather which comprises one or more of the steps retanning, dyeing and fatliquoring by addition of appropriate conventional agents known from the prior art, characterized in that all process steps are effected in a common liquor and without neutralization.
  • the production of leather by the process according to the invention is effected, for example, by initially introducing pretanned leather at 10 - 50°C, preferably 20 - 40°C, particularly preferably at 25 - 30 0 C, into 50 to 300% of water, preferably 50 - 150%, particularly preferably 50 - 100%, of water, based on the weight of the substrate. After some operating time, a pH of about 3 to not more than 4 results, depending on the type of pretanning, and about 2.8 - 3.8 are typical and a range of 2.8 - 3.4 is particularly typical. The temperature of the liquor is now adjusted to about 30 0 C.
  • composition according to the invention is now added as 50% strength aqueous solution in an amount of 1 - 20, particularly preferably 5 - 10, % by weight to the liquor.
  • the pH decreases by about 0.5 to about 2.5 to not more than 3.5, depending on the starting value.
  • the agent With unchanged liquor temperature of about 30 0 C, the agent is allowed to act on the leather for the duration of 30 to 60 minutes with circulation. As a rule, 30 to 45 minutes are sufficient.
  • retanning agent, fatliquoring agent and dyes are now added in succession without liquor change and without neutralization of the aqueous acidic liquor, and these are allowed to act on the substrate in the presence of the agent according to the invention.
  • retanning agent and dyes are added in succession, and these are allowed to act on the substrate at about 30 0 C, for example for 2 hours.
  • 100% of water heated to 60 0 C are then added to the liquor, and the liquor temperature is increased to 50°C with addition of the fatliquoring agent and treatment is effected for about one hour.
  • 1 - 2% of formic acid are now added and treatment is continued for a further 40 min.
  • the liquor is discharged, washing is effected for about 10 min with 200% of cold water altogether and the leather is finished in the usual manner.
  • Suitable retanning agents are in principle the agents known from the prior art and for the most part commercially available: chromium, aluminium, iron or zirconium salts, such as chlorides and sulphates, as mineral tanning agents; polymeric tanning agents, such as polyacrylates or copolymers containing acrylates, polyurethanes and polybutadienes; reactive tanning agents, such as aldehydes, isocyanates, alkyl sulphochlorides, relatively high molecular weight alkanesulphonates, aromatic tanning agents and vegetable tanning agents may be mentioned by way of example and in a non-limiting manner.
  • Preferred retanning agents are polymeric tanning agents, synthetic aromatic tanning agents and vegetable tanning agents.
  • Suitable fatliquoring agents are in principle the agents known from the prior art and for the most part commercially available.
  • the most customary ones are agents which are based on animal, vegetable or synthetic fats, oils and waxes, and which are generally present in a form modified so that they are soluble or at least emulsifiable in water.
  • Suitable dyes are all customary natural and synthetic leather dyes, such as anionic or cationic dyes, metal complex or direct dyes, anionic, metal complex and sulphur dyes being particularly preferred.
  • Preferably used dyes are anionic dyes and metal complex dyes.
  • the present invention furthermore relates to the leathers produced by the process according to the invention or leathers produced using a composition according to the invention.
  • the leather obtained is substantially fuller and stronger than leather produced in a conventional manner, with prior neutralization.

Abstract

L'invention concerne un procédé pour le traitement du cuir en blanc humide, du cuir en bleu humide ou du cuir de prétannage végétal, caractérisé en ce que, pour les besoins dudit traitement, une composition contenant a) 1-95 % en poids d'un produit de la réaction d'un phénol et d'un agent sulfonant, la proportion molaire (phénol):(SO3) étant de (1):(1,1-2,2), b) 1-95 % en poids d'un produit de la réaction d'un acide naphtalènesulfonique et de formaldéhyde et c) 5-50 % en poids de c1) un produit de condensation formaldéhyde d'un acide dihydroxydiarylsulfonique avec un acide arylsulfonique ou (hydroxy)arylsulfonique et/ou c2) un produit de condensation urée/formaldéhyde d'un phénol et d'acide phénolsulfonique, la somme des composants a), b), c1) et/ou c2) étant de 100 % en poids, est ajoutée sous la forme d'une solution aqueuse à la liqueur aqueuse et, si elle est ajustée à une concentration de 50 %, est ajoutée à la liqueur en quantité de 1-20 % en poids, sur la base du poids raclé des cuirs bruts ou des peaux servant de substrat, après le premier tannage et avant le traitement subséquent, lequel comprend une ou plusieurs étapes de retannage, de teinture et de nourriture en bain, et sans une étape de neutralisation ni un changement de liqueur. L'invention concerne également les cuirs obtenus par ce procédé ou obtenus en utilisant ladite composition.
EP05850465A 2004-12-17 2005-12-16 Composition pour le traitement du cuir Not-in-force EP1831405B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH20982004 2004-12-17
PCT/EP2005/056875 WO2006064054A1 (fr) 2004-12-17 2005-12-16 Composition pour le traitement du cuir

Publications (2)

Publication Number Publication Date
EP1831405A1 true EP1831405A1 (fr) 2007-09-12
EP1831405B1 EP1831405B1 (fr) 2009-03-11

Family

ID=36130144

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05850465A Not-in-force EP1831405B1 (fr) 2004-12-17 2005-12-16 Composition pour le traitement du cuir

Country Status (6)

Country Link
EP (1) EP1831405B1 (fr)
AR (1) AR055546A1 (fr)
AT (1) ATE425269T1 (fr)
DE (1) DE602005013287D1 (fr)
TW (1) TW200641140A (fr)
WO (1) WO2006064054A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110263893A1 (en) * 2010-04-21 2011-10-27 Basf Se Products, process for producing them, and their use
WO2011131542A1 (fr) * 2010-04-21 2011-10-27 Basf Se Produits, procédés pour leur préparation et leur utilisation
CN104450993B (zh) * 2014-12-24 2017-11-10 上海金狮化工有限公司 一种复鞣剂及其制备方法
ITTV20150055A1 (it) * 2015-04-21 2016-10-21 Osmo S R L Processo di concia delle pelli
CN105541672B (zh) * 2015-12-15 2017-06-20 浙江闰土研究院有限公司 一种染料分散剂mf的清洁生产工艺
CN112746137A (zh) * 2020-12-31 2021-05-04 晋江市永建皮革制品有限公司 立体压纹皮革的制备工艺

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB425037A (en) * 1933-08-28 1935-02-28 Ig Farbenindustrie Ag Improvements in and relating to improving the properties of synthetic tanning agents
EP0554218B1 (fr) * 1992-01-28 1996-07-24 Ciba-Geigy Ag Procédé pour piquage de peaux
DE19746445A1 (de) * 1997-10-21 1999-04-22 Tfl Ledertechnik Gmbh & Co Kg Mittel zur Herstellung von Leder

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006064054A1 *

Also Published As

Publication number Publication date
WO2006064054A1 (fr) 2006-06-22
DE602005013287D1 (de) 2009-04-23
EP1831405B1 (fr) 2009-03-11
ATE425269T1 (de) 2009-03-15
AR055546A1 (es) 2007-08-22
TW200641140A (en) 2006-12-01

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