EP1299565B1 - Agent de finissage de cuir - Google Patents

Agent de finissage de cuir Download PDF

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Publication number
EP1299565B1
EP1299565B1 EP00940380A EP00940380A EP1299565B1 EP 1299565 B1 EP1299565 B1 EP 1299565B1 EP 00940380 A EP00940380 A EP 00940380A EP 00940380 A EP00940380 A EP 00940380A EP 1299565 B1 EP1299565 B1 EP 1299565B1
Authority
EP
European Patent Office
Prior art keywords
leather
composition
fur
oils
agent
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.)
Expired - Lifetime
Application number
EP00940380A
Other languages
German (de)
English (en)
Other versions
EP1299565A1 (fr
Inventor
Heinrich Francke
Jörg-Detlev STUMM
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.)
Zschimmer and Schwarz GmbH and Co KG
Original Assignee
Zschimmer and Schwarz 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 Zschimmer and Schwarz GmbH and Co KG filed Critical Zschimmer and Schwarz GmbH and Co KG
Publication of EP1299565A1 publication Critical patent/EP1299565A1/fr
Application granted granted Critical
Publication of EP1299565B1 publication Critical patent/EP1299565B1/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
    • 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
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring

Definitions

  • the invention relates to a liquid and storage-stable agent for wet processing of leather, which allows a one-bath, simultaneous retanning, fatliquoring and other equipment of leather.
  • the wet finishing of leather involves several operations. During neutralization, the pH required for further processes is regulated by the use of alkaline, inorganic or organic salts. The fatliquoring is due to the introduction of greasy, the friction between the structural elements of the leather reducing substances for the softness of the leather. Finally, the retannage with vegetable, mineral or synthetic tannins, inter alia leather character, fullness and grain firmness set. These operations are carried out successively, in some separate bathrooms.
  • the current state of development is eg by Magerkurt, B .: "Current aspects and state of the art in the field of wet dressing and dressing", in: The Leather H.1, 1996, pp.
  • the OS DE 196 53 549 Therefore, for such a compact product preferably provides a solid means, ie, the required components must, for example, be subjected to spray drying in order to achieve a storage-stable form.
  • a solid means ie, the required components must, for example, be subjected to spray drying in order to achieve a storage-stable form.
  • the instability of liquid Preparations are expressly indicated.
  • these preparations are commonly used, there are no stable emulsions in which the micelles contain both tanning and Fettungsstoffmoleküle. This can only be achieved temporarily by using ultrasound.
  • ultrasound treatment of the emulsions prepared shortly before use is expensive and is generally not available to the users of these products.
  • Solid products however, have some serious disadvantages.
  • the production requires a high expenditure of energy, which can be achieved by the fact that only dissolved, liquid products can be used, i. That all solids must be dissolved before or during treatment does not appear justified. Handling and dosage require more effort.
  • Dosing devices for powder products are not available in the leather companies in the rule, so that the required large quantities would have to be dosed by hand.
  • the leather factories are equipped with dosing systems for liquids.
  • salts e.g. Sodium sulfate
  • the carrier salts, e.g. Sodium sulfate, used, which pollute the environment, but have no positive application effect. On the contrary, even negative influences on the leather can be exercised.
  • the high salt concentration of the important quality parameter of the leachable inorganic compounds (DIN 53307) is exceeded, which in turn can lead to Salzauellen on the leather or makes additional, water-consuming washing processes required.
  • the liquid, storage and emulsion-stable agent for wet processing of leather and fur which allows the operations of neutralization, retannage and greasing einbadig in a treatment step contains as components fatliquors based on natural or synthetic fats, oils or waxes, the natural or synthetic fats, oils or waxes were subjected to an oxidative treatment before further chemical reaction, retanning and pH-regulating substances and optionally other components.
  • the oxidative treatment according to the invention of the unsaturated fatty, oil and wax starting materials must be carried out in such a way that an iodine number decrease takes place by at least 20 units, but preferably by 30-40 units.
  • the oxidation by introduction of atmospheric oxygen at temperatures between 70 and 120 ° C, or by suitable oxidizing agents, such as. Hydrogen peroxide, done.
  • the further chemical reaction to the fatliquoring agent is carried out in a known manner, e.g. by sulfonation, sulfochlorination, phosphating, ethoxylation, amidation or preparation of the corresponding sulfosuccinates, with the aim of rendering the water-insoluble fats, oils and waxes water-emulsifiable.
  • Fatliquoring component are all natural or synthetic fats, oils and waxes, which have sufficient unsaturation, so that they are accessible to an oxidation process. From the large number of possible starting materials are examples of Fettungskomponenten natural origin called: fish oils, rapeseed oil, soybean oil, lecithin and many others. Fatifying components of synthetic origin are e.g. polyunsaturated hydrocarbons with a chain length> C12, unsaturated fatty alcohols with a chain length> C12, unsaturated fatty acids with a chain length> C12 or esters of unsaturated fatty acids.
  • Suitable retanning agents are the known vegetable and synthetic tanning agents.
  • Herbal tannins are extracts of plants or parts of plants (eg bark, fruits, wood, roots) containing pyrogallol or catechol or their derivatives.
  • the synthetic tannins are for example Condensation products of formaldehyde with aromatic compounds, which may optionally be present in their sulfonated form.
  • the condensation products can be further processed in the form of the free sulfonic acid or its lithium, sodium, potassium or ammonium salt.
  • condensation products of formaldehyde with nitrogen bases such as urea, melamine, thiourea and dicyandiamide as the tanning component.
  • the synthetic tannins are also the Polymergerbstoffe be expected that represent water-soluble polymers based on acrylate, polyurethane or polybutadiene. Also suitable are aldehydic tannins such as glutaric, acetaldehyde and propionaldehyde or other aliphatic aldehydes, but also aldehyde carboxylic acids such as glyoxylic acid.
  • aldehydic tannins such as glutaric, acetaldehyde and propionaldehyde or other aliphatic aldehydes, but also aldehyde carboxylic acids such as glyoxylic acid.
  • a detailed description and description of eligible vegetable and synthetic tanning agents is included Kurt Faber "Tanning, Tanning and Retanning" from the series “Library of the Leather", Volume 3 (Umschau Verlag, Frankfurt 1985 ).
  • pH-regulating substances examples include alkaline earth oxides, alkali and alkaline earth hydroxides, ammonium compounds and other basic inorganic and organic salts.
  • substances which need not necessarily be components of the composition according to the invention, but in individual cases may be necessary for the formulation.
  • these include, for example, solvents such as alcohols or hydrocarbons, preservatives, antioxidants, adjusting agents such as urea or common salt, viscosity regulators such as mineral oils of various viscosities, etc.
  • the agent according to the invention accordingly contains the following constituents (in% by weight): a) fatliquoring agent 10 - 90%, preferably 20 - 80% b) tanning agent 10 - 90%, preferably 20 - 80% c) pH-regulating substances and optionally 1 - 30% d) other additives 0 - 30%
  • the components are stirred, e.g. in a stirred reactor at temperatures between 20 and 90 ° C, preferably at temperatures between 30 and 60 ° C, mixed and homogenized.
  • the formulations for the wet processing of the leather simplify considerably.
  • the leathers After washing the leather to remove shavings and possibly dirt, the leathers have an amount of water of 20-200%, preferably 50-150% (based on the shaved weight) and 5-30%, preferably 10-25%.
  • the agent according to the invention added.
  • the agent according to the invention is pre-emulsified with four to eight times the amount of water. This results in a completely stable, opaque emulsion whose micelles contain both tanning agent and fatliquoring molecules. These emulsions are stable for a long time without separation into the components. But it is also a direct dosage without the previous production of an emulsion possible.
  • the process temperatures are 20-60 ° C, preferably 30-50 ° C.
  • a pH of 3.5 to 3.8 is set with organic acids, and the leathers are finished in the usual way.
  • the leather can be dyed either by the addition of dye during the above process or in a subsequent additional operation.
  • Virtually all types of leather such as furniture leather, car upholstery leather, leather for shoe production, clothing leather but also technical leather can be produced with the composition according to the invention.
  • the composition of the agent according to the invention can be varied. For example, for firmer, more stable types of leather require a higher tanning agent and a lower amount of fatliquor. For soft leathers dominated according to the fatliquoring. Of course, the nature of the components entering the product will also affect the leather character of the resulting leather. Such variations of the composition have no negative influence on the stability properties of the compositions of the invention and their emulsions.
  • liquid agent according to the invention offers a multiplicity of advantages for the user.
  • the very short process time represents a capacity gain and saves any investment costs.
  • the simultaneous process management saves significant amounts of water and wastewater, which represents both a cost and an ecological advantage.
  • Component A (fatliquoring agent): Rape oil with an iodine value of 110 is oxidized at 90 ° C with atmospheric oxygen up to an iodine value of 80. After completion of the oxidation, ethoxylation is carried out with 10 mol of ethylene oxide and subsequent sulfonation up to a content of organically bound SO 3 of about 2.0%.
  • Component B (tanning agent): Synthetic tanning agent based on a condensation product of phenol sulfonic acid, phenol, urea and formaldehyde with a dry matter content of 50%.
  • Component C (pH regulating agent): sodium formate, monoethanolamine
  • Component A (fatliquoring agent): Fish oil with an iodine value of 130 is homogeneously mixed in a ratio of 1: 1 with tall oil fatty acid methyl ester with an iodine value of 155 and subjected to oxidation with atmospheric oxygen at 110 ° C. The reaction is carried out until an iodine number of the mixture of 100 is reached. The reaction product is then subjected to sulfonation and neutralized with triethanolamine. The product has a content of organically bound SO 3 of 4.5%.
  • Component B (tanning agent): A condensation product of formaldehyde and dihydroxydiphenylsulfone having a dry matter content of 45% and a sodium polyacrylate having an average molecular weight of 25,000 g / mol and a dry matter content of 35% are homogeneously mixed at room temperature.
  • Component C (pH-regulating agent): ammonium acetate, triethanolamine
  • Component D urea, chloroacetamide
  • a stirred reactor 35 parts of component A, 50 parts of component B, 5 parts of ammonium acetate, 0.5 parts of triethanolamine, 9 parts of urea and 0.5 parts of chloroacetamide are homogeneously mixed at 50 ° C and with decarbonated water to a water content of 60 % set.
  • the pH is controlled and optionally adjusted to 7.8 to 8.2 with triethanolamine.
  • the result is a dark brown clear and storage-stable product. Diluting with water 1:10 results in a milky-opaque, stable emulsion.
  • the leathers were finished in the usual way and were soft, scar-resistant and had a level coloration.
  • the leathers were finished as usual.
  • the finished leather was characterized by high softness combined with grain firmness and fine leveled millet grain.
  • the color was uniform in area and cross section.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Claims (5)

  1. Composition liquide, stable au stockage et en émulsion pour le finissage du cuir et de la peau, comprenant comme composant
    a) un agent de graissage à base de graisses, huiles ou cires insaturées naturelles ou synthétiques, lesdites graisses, huiles ou cires insaturées naturelles ou synthétiques étant soumises à un traitement d'oxydation avant une autre transformation chimique,
    b) un agent de retannage et
    c) une substance régulant le pH,
    ainsi que facultativement d'autres composants, ladite composition permettant de réaliser, en une seule étape de traitement, les opérations de neutralisation, de retannage et de graissage en un seul bain.
  2. Composition pour le finissage du cuir et de la peau selon la revendication 1, caractérisée en ce que lors du traitement d'oxydation, la quantité d'iode est réduite d'au moins 20 unités et en ce que le traitement d'oxydation se produit grâce à l'oxygène de l'air ou à d'autres agents d'oxydation appropriés.
  3. Composition pour le finissage du cuir et de la peau selon la revendication 1 ou 2, caractérisée en ce que ladite autre transformation chimique des graisses, huiles ou cires traitées par oxydation est la sulfuration, la phosphatation, l'éthoxylation, l'amidation et/ou la transformation en sulfosuccinates ou la combinaison de ces procédés.
  4. Composition pour le finissage du cuir et de la peau selon les revendications 1 à 3, comprenant :
    a) 10-90 % en poids d'un agent de graissage,
    b) 10-90 % en poids d'un agent de retannage,
    c) 1-10 % en poids d'une substance régulant le pH et
    d) 0-30 % en poids d'autres additifs.
  5. Utilisation de la composition selon les revendications 1 à 4 sous forme d'une solution ou dispersion aqueuse pour le finissage en un seul bain du cuir ou de la peau en une seule étape de traitement.
EP00940380A 2000-06-16 2000-06-16 Agent de finissage de cuir Expired - Lifetime EP1299565B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2000/005560 WO2001096613A1 (fr) 2000-06-16 2000-06-16 Agent de finissage de cuir

Publications (2)

Publication Number Publication Date
EP1299565A1 EP1299565A1 (fr) 2003-04-09
EP1299565B1 true EP1299565B1 (fr) 2007-11-28

Family

ID=8163990

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00940380A Expired - Lifetime EP1299565B1 (fr) 2000-06-16 2000-06-16 Agent de finissage de cuir

Country Status (4)

Country Link
EP (1) EP1299565B1 (fr)
DE (1) DE50014822D1 (fr)
ES (1) ES2296627T3 (fr)
WO (1) WO2001096613A1 (fr)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2056345A1 (de) * 1970-11-17 1972-05-18 Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen Verfahren zur Nachgerbung und Fettung von Leder
DE3617691A1 (de) * 1986-05-26 1987-12-03 Henkel Kgaa Sulfitierte fettstoffe
DE19746445A1 (de) * 1997-10-21 1999-04-22 Tfl Ledertechnik Gmbh & Co Kg Mittel zur Herstellung von Leder

Also Published As

Publication number Publication date
DE50014822D1 (de) 2008-01-10
EP1299565A1 (fr) 2003-04-09
WO2001096613A1 (fr) 2001-12-20
ES2296627T3 (es) 2008-05-01

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