EP1299565A1 - Agent de finissage de cuir - Google Patents

Agent de finissage de cuir

Info

Publication number
EP1299565A1
EP1299565A1 EP00940380A EP00940380A EP1299565A1 EP 1299565 A1 EP1299565 A1 EP 1299565A1 EP 00940380 A EP00940380 A EP 00940380A EP 00940380 A EP00940380 A EP 00940380A EP 1299565 A1 EP1299565 A1 EP 1299565A1
Authority
EP
European Patent Office
Prior art keywords
leather
agent
retanning
fur
stable
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
EP00940380A
Other languages
German (de)
English (en)
Other versions
EP1299565B1 (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

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
    • 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 the wet finishing of leather, which enables a one-bath, simultaneous retanning, greasing and other finishing of 5 leather.
  • the wet finishing of leather involves several operations. During neutralization, the use of alkaline, inorganic or organic salts regulates the pH value required for the further processes. The greasing is responsible for the softness of the leather due to the introduction of greasy substances that reduce the friction between the structural elements of the leather. Finally, retanning with vegetable, mineral or synthetic tanning agents Leather character, fullness and grain resistance set. These operations are carried out one after the other in partially separate baths. The current state of development is e.g. 5 by Magerkurt, B .: “Current aspects and state of the art in the field of wet dressing and dressing", in: Das Leder H.1, 1996, pp.
  • OS DE 196 53 549 therefore preferably provides a solid agent for such a compact product, ie the necessary components have to be spray dried, for example, in order to achieve a shape which is stable in storage.
  • a solid agent for such a compact product ie the necessary components have to be spray dried, for example, in order to achieve a shape which is stable in storage.
  • Preparations are expressly indicated.
  • ultrasound treatment of the emulsions prepared shortly before use is complex and is generally not available to the users of these products.
  • Solid products have some serious disadvantages.
  • the production requires a large amount of energy, which is due to the fact that only dissolved, liquid products can be used, i.e. that all solids must be dissolved before or during treatment does not appear to be justified. Handling and dosing require more effort.
  • Dosing devices for powder products are generally not available in the leather factories, so that the required large quantities would have to be dosed by hand.
  • the leather factories are equipped with dosing systems for liquids. Salts such as e.g. Sodium sulfate, used that pollute the environment, but have no positive application effects. On the contrary, negative influences can even be exerted on the leather. It is therefore possible that the important quality parameter 20 of the washable inorganic compounds (DIN 53307) is exceeded due to the high salt concentration, which in turn can lead to salt build-up on the leather or make additional, water-consuming washing processes necessary.
  • the liquid, storage- and emulsion-stable agent according to the invention for wet dressing of leather and fur which enables the neutralization, retanning and greasing operations to be carried out in one treatment step, contains, as components, fatliquoring agents, retanning agents and pH-regulating substances and optionally further components and is characterized in that unsaturated fats, oils or waxes of natural or synthetic origin are used as the starting material for the production of the fatliquoring agent and are subjected to an oxidative treatment before a further chemical reaction.
  • the oxidative treatment of the unsaturated fat, oil and wax starting materials according to the invention must be carried out in such a way that the iodine number is reduced by at least 5 units, but preferably by 30-40 units.
  • the oxidation can be carried out by introducing atmospheric oxygen at temperatures between 70 and 120 ° C, or by suitable oxidizing agents, e.g. Hydrogen peroxide.
  • the further chemical conversion to the degreasing agent takes place in a known manner, e.g. by sulfation, sulfochlorination, phosphating, ethoxylation, amidation or preparation of the corresponding sulfosuccinates, with the aim of making the water-insoluble fats, oils and waxes water-emulsifiable.
  • the basis for the fatliquor component are all natural or synthetic fats, 5 oils and waxes, which have sufficient unsaturated bonds, so that they are accessible to an oxidation process. From the large number of possible starting materials, the following are examples of fat components of natural origin: fish oils, rapeseed oil, soybean oil, lecithin and many others. Fat 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.
  • the known vegetable and synthetic tanning agents come in as retanning agents
  • Vegetable tannins are extracts from plants or 5 parts of plants (e.g. bark, fruit, wood, roots) that contain pyrogallol or pyrocatechol or their derivatives.
  • the synthetic tanning agents are, for example Condensation products of formaldehyde with aromatic compounds, which may also be present in their sulfonated form.
  • the condensation products can be processed further 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, are also suitable as tannin components.
  • the synthetic tanning agents also include the polymer tanning agents, which are 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 glyoxalic acid. Kurt Faber "Tanning agents, tanning and retanning" from the series “Library of leather", volume 3 (Umschau Verlag, Frankfurt 1985) provides a detailed description and description of the vegetable and synthetic tanning agents that are considered.
  • polymer tanning agents which are water-soluble polymers based on acrylate, polyurethane or polybutadiene.
  • aldehydic tannins such as glutaric, acetaldehyde and propionaldehyde or other aliphatic aldehydes, but also aldehyde carboxylic acids such as glyox
  • the pH-regulating substances include, for example: alkaline earth oxides, alkali and alkaline earth hydroxides, ammonium compounds and other basic inorganic and organic salts.
  • Substances are to be understood as optional further components which do not necessarily have to be constituents of the agent according to the invention, but in individual cases can be constituents 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 different viscosities etc.
  • the agent according to the invention accordingly contains the following constituents (in% by weight): a) fatliquor 10-90%, preferably 20-80% b) tannin 10-90%, preferably 20-80% c) pH-regulating substances 1 - 30% 5 and if necessary d) further additives 0 - 30%
  • the components are removed by stirring e.g. mixed and homogenized in a stirred reactor at temperatures between 20 and 90 ° C., preferably at temperatures between 30 and 60 ° C. There are no special requirements for the design of the agitators. Completely stable, clear, liquid products are created. The storage stability is both at low temperatures, e.g. down to -30 ° C, as well as at high temperatures, e.g. up to 60 ° C.
  • the recipes for the wet finishing of the leather are considerably simplified.
  • the leather After washing the leather in order to remove shavings and possibly dirt, the leather is given an amount of water of 20-200%, preferably 50 to 150% (based on the shaved weight) and 5-30%, preferably 10-25%, of 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. The result is a completely stable, opaque emulsion, the micelles of which contain both tannin and fat molecules. These emulsions are stable for a long time without being separated into the components. However, direct metering is also possible without the prior preparation of an emulsion.
  • the process temperatures are 20 - 60 5 ° 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 normal manner.
  • the leather can be dyed either by adding dye during the above-mentioned process or in a subsequent additional operation.
  • composition of the agent according to the invention can be varied. For example, for firmer, more permanent types of leather require a higher tannin and a lower fat content. For soft types of leather, the proportion of fat and grease dominates. The type of components used in the product naturally also influences the leather character of the resulting leather. Such variations in the composition have no negative influence on the stability properties of the agents according to the invention and their emulsions.
  • liquid agent according to the invention offers the user a multitude of advantages. Only one product is required for wet dressing, which o can be stored in the tank and dosed automatically. This offers both logistical and cost advantages. The very short process time represents a gain in capacity and saves any investment costs. The simultaneous process control saves significant amounts of water and wastewater, which represents both a cost and an ecological advantage. 5
  • Component A (fatliquor): Turnip oil with an iodine number of 110 is oxidized at 90 ° C with atmospheric oxygen up to an iodine number of 80. After completion of the oxidation, ethoxylation with 10 moles of ethylene oxide followed by sulfonation to an organically bound SO 3 content of approximately 2.0%. 5
  • Component B (tanning agent): synthetic tanning agent based on a condensation product of phenolsulfonic acid, phenol, urea and formaldehyde with a dry substance of 50%.
  • component A At 60 ° C., 58 parts of component A, 30 parts of component B are mixed with 10 parts of sodium formate and 2 parts of triethanolamine in a stirred reactor and stirred until homogeneous.
  • a water content of 40% 5 is set by adding decarbonated water.
  • a golden yellow oily product is formed, which is stored in a temperature range from -20 to +50 ° C is completely stable in storage and results in completely stable finely dispersed emulsions when diluted with water.
  • Component A (fatliquor): Fish oil with an iodine number of 130 is mixed in a 1: 1 ratio with tall oil fatty acid methyl ester with an iodine number of 155 and subjected to oxidation with atmospheric oxygen at 110 ° C. The reaction is carried out until the mixture reaches an iodine number of 100. The reaction product is then subjected to sulfonation and neutralized with triethanolamine. The product has an organically bound SO 3 content of 4.5%.
  • Component B (tanning agent): A condensation product of formaldehyde and dihydroxydiphenyl sulfone with a dry substance of 45% and a Na polyacrylate with an average molecular weight of 25000 g / mol and a dry substance of 35% are mixed homogeneously at room temperature.
  • Component C (pH-regulating agent): ammonium acetate, triethanolamine
  • Component D urea, chloroacetamide
  • Lubrication 1 5 pre-emulsified with water
  • the leathers were completed in the normal way.
  • the finished leather was characterized by high softness with simultaneous grain resistance and fine level mill grain.
  • the coloring 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)

Abstract

La présente invention concerne des agents liquides de corroyage humide de cuir, permettant en un bain et simultanément le retannage, la nourriture et d'autres finissages. Cette invention est caractérisée en ce que des graisses, des huiles ou des cires insaturées, d'origine naturelle ou synthétique, sont utilisées en tant que matières premières dans la production de l'agent de nourriture et ont été soumises à un traitement oxydant avant tout autre transformation chimique.
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 true EP1299565A1 (fr) 2003-04-09
EP1299565B1 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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0196613A1 *

Also Published As

Publication number Publication date
WO2001096613A1 (fr) 2001-12-20
ES2296627T3 (es) 2008-05-01
EP1299565B1 (fr) 2007-11-28
DE50014822D1 (de) 2008-01-10

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