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EP1831405B1 - Composition pour le traitement du cuir - Google Patents

Composition pour le traitement du cuir Download PDF

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Publication number
EP1831405B1
EP1831405B1 EP05850465A EP05850465A EP1831405B1 EP 1831405 B1 EP1831405 B1 EP 1831405B1 EP 05850465 A EP05850465 A EP 05850465A EP 05850465 A EP05850465 A EP 05850465A EP 1831405 B1 EP1831405 B1 EP 1831405B1
Authority
EP
European Patent Office
Prior art keywords
weight
leather
component
composition according
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.)
Not-in-force
Application number
EP05850465A
Other languages
German (de)
English (en)
Other versions
EP1831405A1 (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
  • 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).
  • 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): in which n and m are each 0, 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 with an ammonia solution.
  • 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.
  • 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. There are therefore substantial economic advantages through the overall shorter process duration and the lower water demand.
  • the quality of the leathers obtained is particularly convincing, and said leathers are substantially fuller and stronger than leathers produced by conventional processes.
  • the good tight-grained character (particularly in the case of stronger leathers) and better embossability of the finished leather are further achievable positive results. It may be possible to explain this by the fact that the possibility of a "one-pot process" not only permits a simplified distribution but also a particularly good distribution of the retanning agents, colorants and fatliquoring agents, so that, for example, particularly complete dyeing is also observable.
  • 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
  • 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°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°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°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°C, for example for 2 hours.
  • 100% of water heated to 60°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.
  • 500 ml of water are initially introduced into a sulphonation flask at room temperature, and initially 250 g of component a), 200 g of component b) and 50 g of component c2) are added with vigorous stirring. After some time, a clear, brown solution which has a pH of 0.7 is obtained.
  • the leather obtained is substantially fuller and stronger than leather produced in a conventional manner, with prior neutralization.

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)

Claims (10)

  1. Composition contenant
    a) de 1 à 95 % en poids d'un produit de la réaction d'un phénol et d'un agent de sulfonation, le rapport molaire (phénol):(SO3) étant de (1):(1,1-2,2),
    b) de 1 à 95 % en poids d'un produit de la réaction d'un acide naphtalènesulfonique et du formaldéhyde, et
    c) de 5 à 50 % en poids
    c1) d'un produit de condensation formaldéhyde d'une dihydroxydiarylsulfone avec un acide
    aryl- ou (hydroxy)arylsulfonique et/ou
    c2) d'un produit de condensation urée/formaldéhyde d'un phénol et de l'acide phénolsulfonique,
    la somme des composants a), b), c1) et/ou c2) étant de 100 % en poids.
  2. Composition selon la revendication 1, contenant
    de 10 à 60 % en poids du composant a),
    de 20 à 80 % en poids du composant b) et
    de 5 à 40 % en poids du composant c).
  3. Composition selon la revendication 1, contenant en tant que composant a), des produits de réaction du phénol et d'un agent de sulfonation, le rapport molaire (phénol):(SO3) étant de (1):(1,4-1,8).
  4. Composition selon la revendication 1, contenant en tant que composant c1), des produits de condensation formaldéhyde de 4,4'-dihydroxydiphénolsulfones avec des acides arylsulfoniques.
  5. Composition selon la revendication 4, caractérisée en ce que l'acide arylsulfonique est l'acide naphtalènesulfonique.
  6. Composition selon la revendication 1, contenant en tant que composant c), exclusivement un composant c1) selon l'une des revendications 4 et 5.
  7. Procédé de traitement du cuir en blanc humide, en bleu humide ou de prétannage végétal en tant que substrat, caractérisé en ce qu'une composition selon l'une quelconque des revendications 1 à 6, sous la forme d'une solution aqueuse, est ajoutée à la liqueur aqueuse, et on laisse ladite composition agir sur le substrat.
  8. Procédé selon la revendication 7, caractérisé en ce que la composition est ajoutée sous la forme d'une solution aqueuse à 50 % en une quantité de 1 à 20 % en poids, de préférence de 3 à 12, particulièrement préférablement de 5 à 10 % en poids, par rapport au poids raclé du cuir à traiter, à la liqueur.
  9. Procédé de pré-traitement et de finissage à l'état humide du cuir prétanné, comprenant les étapes de
    a) traitement du cuir selon l'une ou l'autre des revendications 7 et 8,
    b) traitement subséquent du cuir, qui comprend l'une ou plusieurs des étapes de retannage, de teinture et de nourriture en bain par l'addition d'agents appropriés,
    caractérisé en ce que toutes les étapes du procédé sont réalisées dans une liqueur commune et sans la neutralisation de la liqueur acide aqueuse.
  10. Cuir produit en utilisant une composition selon l'une quelconque des revendications 1 à 6 ou par un procédé selon l'une quelconque des revendications 7 à 9.
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 EP1831405A1 (fr) 2007-09-12
EP1831405B1 true 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)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105541672A (zh) * 2015-12-15 2016-05-04 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
ITTV20150055A1 (it) * 2015-04-21 2016-10-21 Osmo S R L Processo di concia delle pelli

Families Citing this family (4)

* 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
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
DE59303282D1 (de) * 1992-01-28 1996-08-29 Ciba Geigy Ag Verfahren zum Pickeln von Hautblössen
DE19746445A1 (de) * 1997-10-21 1999-04-22 Tfl Ledertechnik Gmbh & Co Kg Mittel zur Herstellung von Leder

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITTV20150055A1 (it) * 2015-04-21 2016-10-21 Osmo S R L Processo di concia delle pelli
WO2016170503A1 (fr) * 2015-04-21 2016-10-27 Osmo S.R.L. Procédé de tannage de peaux
CN105541672A (zh) * 2015-12-15 2016-05-04 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
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

Also Published As

Publication number Publication date
AR055546A1 (es) 2007-08-22
ATE425269T1 (de) 2009-03-15
WO2006064054A1 (fr) 2006-06-22
EP1831405A1 (fr) 2007-09-12
TW200641140A (en) 2006-12-01
DE602005013287D1 (de) 2009-04-23

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