EP1611258B1 - Zusammensetzung, die chrom-salze enthält, zum gerben - Google Patents

Zusammensetzung, die chrom-salze enthält, zum gerben Download PDF

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Publication number
EP1611258B1
EP1611258B1 EP04725067A EP04725067A EP1611258B1 EP 1611258 B1 EP1611258 B1 EP 1611258B1 EP 04725067 A EP04725067 A EP 04725067A EP 04725067 A EP04725067 A EP 04725067A EP 1611258 B1 EP1611258 B1 EP 1611258B1
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EP
European Patent Office
Prior art keywords
weight
water
composition
chromium
liquor
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
EP04725067A
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English (en)
French (fr)
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EP1611258A1 (de
Inventor
João Augusto KETTERMANN
Laure Tripot
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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Publication of EP1611258A1 publication Critical patent/EP1611258A1/de
Application granted granted Critical
Publication of EP1611258B1 publication Critical patent/EP1611258B1/de
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
    • C14C3/02—Chemical tanning
    • C14C3/04—Mineral tanning
    • C14C3/06—Mineral tanning using chromium compounds

Definitions

  • the present invention relates to a composition
  • a composition comprising (a) a mononuclear chromium salt having anions of low molecular weight carboxylic acids and sulphate anions, the mononuclear chromium salts having a Schorlemmer basicity of not more than 25%, (b) alkali metal sulphates and (c) optionally water; and a process for tanning unpickled pelts with a strongly addic solution of the composition in water.
  • the one-bath process which comprises the steps of pickling, tanning with chromium salt and basifying, has become established.
  • pickling the animal hide which has been digested and degreased in the beamhouse is treated with strong acids, for example sulphuric acid or hydrochloric acid, and salts, for example sodium chloride.
  • strong acids for example sulphuric acid or hydrochloric acid
  • salts for example sodium chloride.
  • the degree of dissociation of the carboxyl groups in the collagen is reduced so that the animal hide has a low pH of less than 2.
  • the fixing of the chromium salts is greatly reduced and the permeation of the salts is increased.
  • the tanning effect is then displayed by an increase in the pH to about 3.5 to 6.
  • alkaline compositions when basifying the liquor, alkaline compositions are added in amounts (for example magnesium oxide or sodium carbonate) such that the optimum value for the tanning is established.
  • chromium salts have a Schorlemmer basicity of at least 30%.
  • US-A-4,715,861 recommends treating pickled pelts or pelts during the pickling initially with aldehyde- or ketocarboxylic acids, for example glyoxalic acid, in order to increase the exhaustion of the liquor and to reduce the consumption of chromium salts.
  • aldehyde- or ketocarboxylic acids for example glyoxalic acid
  • the steps of pickling and of basifying are, however, still necessary.
  • Aldehyde and keto acids are physiologically unsafe and require special protective measures.
  • the effect of the aldehyde and keto acids consists in the reaction with amino groups of collagen, which leads to an increase in the acidity of the pelt and hence better chromium uptake.
  • EP-A-0 822 263 describes a process for tanning with chromium salts, in which pelts are treated with 3-hydroxybutyraldehyde, and pickling and basifying are dispensed with.
  • the isoelectric point is reduced so that chromium salts penetrate sufficiently and basifying is superfluous.
  • WO 00/66793 discloses the same process using ⁇ - or ß-hydroxyaldehydes.
  • the agents used for the pretreatment are volatile compounds which can be handled only with difficulty in tanneries.
  • aldehydes are physiologically unsafe.
  • the use of these processes requires special protective means, which cancels out the advantages of dispensing with pickling and basifying from economic points of view.
  • GB 547 129 A1 refers to chromium tanning of unpickled animal hide with an aqueous solution comprising caustic soda.
  • the pH is much greater than 2.8.
  • the invention firstly relates to a composition
  • a composition comprising
  • Mono- and polycarboxylic acids are known.
  • the mono- and polycarboxylic acids have a molecular weight of not more than 200, preferably not more than 150 and particularly preferably not more than 120.
  • Some examples of mono- and dicarboxylic acids are formic acid, acetic acid, propionic acid, lactic acid, methoxyacetic acid, monochloro- or monofluoroacetic acid, oxalic acid and malonic acid.
  • the carboxylic acids may be used individually or as a mixture of at least two carboxylic acids.
  • the Schorlemmer basicity of the mononuclear chromium salt is preferably not more than 23% and particularly preferably not more than 21%.
  • the lower limit may be, for example, at least 14% and preferably at least 16%.
  • the pH of the composition according to definition (d) is preferably not more than 2.5.
  • the lower limit of the pH may be, for example, 0.2 and preferably 0.5.
  • the amount of the mononuclear chromium salt in the composition may be, for example, from 5 to 30% by weight and preferably from 10 to 20% by weight, calculated as the content of Cr 2 O 3 .
  • the alkali metal sulphate is preferably potassium sulphate or particularly preferably sodium sulphate.
  • the amount of the alkali metal sulphate may be, for example, the remaining amount up to 100% by weight.
  • the complete drying of the composition is difficult and technically complicated owing to the water of hydration bound to the chromium salt. It is therefore more advantageous if small amounts of water are present in the composition, for example up to 15% by weight and more preferably up to 10% by weight.
  • the composition according to the invention may be present as an aqueous solution, as an aqueous concentrate or as a solid, water-soluble formulation.
  • the amount of the composition according to the invention in aqueous solution and aqueous concentrates may be, for example, from 35 to 85% by weight, preferably from 40 to 70% by weight.
  • the solid composition can, as mentioned above, contain up to 15% by weight and more preferably up to 10% by weight of water, owing to the difficult drying.
  • the solid composition may be powder or granules. Concentrates having a water content of less than about 35% are highly viscous and difficult to handle, particularly when filling and removing from containers. These water contents are therefore less preferred.
  • composition according to the invention may additionally contain agents customary in the tannery, for example solvents, standardizing agents and fungicides.
  • agents customary in the tannery for example solvents, standardizing agents and fungicides.
  • composition according to the invention is obtainable by reacting an aqueous solution of chromium sulphates having a Schorlemmer basicity of, for example, from 30 to 50%, which contains alkali metal sulphates, with low molecular weight mono- or polycarboxylic acids.
  • Chromium salts for tanning have long been known and are commercially available as solid or liquid formulations. They are sulphates of trivalent chromium. The products available are generally mixtures of basic chromium sulphates and alkali metal sulphates, such as, for example, sodium sulphate, since the basicity is established by adding alkali metal hydroxides. The basicity is established by means of the amount of alkali metal hydroxides, which is stated in percent Schorlemmer. In this context, a basicity of 0% is assigned to pure chromium sulphate and a basicity of 100% to pure chromium hydroxide. Forms in between, such as, for example, Cr(OH)SO 4 , have a basicity of 33.3%.
  • the chromium sulphates used for the preparation of the composition preferably have a Schorlemmer basicity of from 30 to 50%, more preferably from 30 to 45%, and particularly preferably from 30 to 42%.
  • Such chromium sulphates are standard products for the tanneries and are commercially available or can be prepared in a simple manner.
  • the preparation of the composition according to the invention can be effected in a simple manner by dissolving chromium sulphates in water and adding the desired amount of alkali metal hydroxides.
  • Commercially available products are advantageously used.
  • Heating may mean up to 100°C and preferably up to 50°C.
  • the reaction is expediently carried out at room temperature.
  • the basicity of the chromium sulphate and, on the other hand, the pH are adjusted with the amount of the mono- and polycarboxylic acids. It is possible to add less than stoichiometric amount or an excess, based on the Cr 2 O 3 present in the solution.
  • the molar ratio of chromium sulphate, based on Cr 2 O 3 , to carboxylic acid may be, for example, from 1:0.1 to 1:1.5, preferably from 1:0.2 to 1:1.
  • a typical composition according to the invention can be prepared from an amount of water of, for example, 45-55% by weight, an amount of chromium sulphate, calculated as Cr 2 O 3 , of, for example, 10-20% by weight, and an amount of carboxylic acid of, for example, 4-10% by weight, the remaining amount to 100% by weight being an alkali metal sulphate.
  • the reaction product obtained can, if necessary and desired, be worked up by removing water to give aqueous solutions, aqueous concentrates or solid formulations.
  • the removal of water can be effected by heating, optionally in vacuo.
  • Solid formulations can be obtained by means of freeze-drying, spray-drying, fluidized-bed drying, granulation or removal of water with heating, optionally in vacuo, and milling of the dried product to give powders.
  • Liquid and solid compositions according to the invention have no substantial differences with regard to their outstanding tanning effect.
  • Aqueous concentrates can be prepared in a simple manner directly in the tannery. Such concentrates can, however, also be supplied as the prepared solution. Pulverulent or granulated solid compositions are preferred delivery forms, owing to the smaller volume. However, it is also possible to supply dilute aqueous solutions which can be used directly as tanning liquor, particularly if the amount of hides to be tanned is not too large.
  • kit consisting of two containers, which each contain:
  • the molar ratios and amounts are preferably chosen so that the pH of the aqueous solution is not more than 2.5 and, for example, from 2.5 to 0.2 and in particular from 2.5 to 0.5.
  • the composition according to the invention is outstandingly suitable for tanning pelts in aqueous liquor, it being possible completely to dispense with pickling and basifying, and optionally only smaller amounts of electrolyte salts are added to the water, for example up to 5% by weight, based on the dry weight of the pelt.
  • the electrolyte salt used is mainly sodium chloride.
  • the pH of the liquor at the beginning of the process is strongly acidic.
  • the optimum pH required for effective tanning in the aqueous liquor is automatically established after addition of the composition, since basic components present in the pelt as a result of the pretreatment increase the pH. After the end of the tanning, the pH has increased to about 3 to 3.5.
  • the invention furthermore relates to a process for tanning unpickled pelts by the action of chromium(III) sulphates in aqueous liquor, which is characterized in that an effective amount of a composition comprising
  • chromium trioxide Cr 2 O3
  • the amount is calculated in the tannery, usually on the basis of the theoretical content of chromium trioxide.
  • the process according to the invention can be carried out by introducing washed pelts into water, adding a salt, for example sodium chloride, to the liquor, and allowing to act for a short time on the pelts.
  • the composition according to the invention for tanning is then added, which composition can be allowed to act, for example, for about 2 to 10 hours at room temperature. Heating is then effected and the reaction time is allowed to continue, for example for up to 10 hours.
  • the temperature may be up to 50°C and preferably up to 45°C.
  • the pH of the liquor after the tanning may be from 3 to 5.5.
  • the invention also relates to the use of a composition containing
  • Example A1 Solution of chromium sulphate, lactic acid and formic acid
  • Example A2 Solution of chromium sulphate, lactic acid and formic acid
  • Example A3 Solution of chromium sulphate and oxalic acid and formic acid
  • the composition contains 14.49% by weight of Cr 2 O 3 and has a Schorlemmer basicity of 19.2% and a density of 1.63 g/cm 3 .
  • the pH of the composition is 0.98 and the pH of a 10 percent strength by weight solution in water is 2.27.
  • Example A4 Powder comprising chromium sulphate, lactic acid and formic acid
  • Example A5 Powder comprising chromium sulphate, lactic acid and formic acid
  • Example A6 Powder product comprising chromium sulphate and oxalic acid and formic acid 109.3 g of a solution of 28.5 g of oxalic acid in water are added to a solution of 830 g of chromium(III) sulphate and sodium sulphate [Schorlemmer basicity 33% (theoretically Cr(OH)SO 4 ; 15% by weight content of Cr 2 O 3 )]. Stirring is then effected for 30 minutes at from 40 to 50°C. Thereafter, after cooling to 30°C, 32.8 g of formic acid (85% strength) are added and stirring is effected for a further 15 minutes. The composition is dried in a water jet vacuum at 60°C. The green residue is then milled to give a powder. The pH of a 10 percent strength by weight solution in water is 2.45.
  • Example B1 Tanning of hides (Swiss bull)
  • Example B3 Tanning of hides (Brazilian zebu)
  • Example B5 Tanning of hides (Swiss bull)
  • Example B6 Tanning of hides (Swiss bull)
  • Example B7 Tanning of hides (Swiss bull)

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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. Zusammensetzung enthaltend:
    a) ein mononukleares Chromsalz aufweisend Anionen von Mono- und Polycarbonsäuren mit einem Molekulargewicht von nicht mehr als 200 und Sulfatanionen, das mononukleare Chromsalz hat eine Schorlemmer Basizität von nicht mehr als 25%.
    b) ein Alkalimetallsufat, und
    c) optional Wasser,
    d) der pH-Wert einer 10 gewichtsprozentigen Lösung der Zusammensetzung in Wasser ist nicht mehr als 2.8.
  2. Zusammensetzung gemäß Anspruch 1, dadurch gekennzeichnet, daß die Mono- und Polycarbonsäuren Ameisensäure, Essigsäure, Propionsäure, Milchsäure, Methoxyessigsäure, Monochlor- oder Monofluoressigsäure, Oxalsäure und Malonsäure sind.
  3. Zusammensetzung gemäß Anspruch 1, dadurch gekennzeichnet, daß die Schorlemmer Basizität des mononuklearen Chromsalzes von 16 % bis nicht mehr als 23% ist.
  4. Zusammensetzung gemäß Anspruch 1, dadurch gekennzeichnet, daß der Anteil des Chromsalzes 5 bis 30 Gewichtsprozent ist, bezogen auf den Anteil an Cr2O3, und der verbleibende Anteil ist das Alkalimetallsulfat in optional Wasser.
  5. Zusammensetzung gemäß Anspruch 1, dadurch gekennzeichnet, daß sie eine wässrige Lösung, ein wässriges Konzentrat oder eine feste, wasserlösliche Formulierung ist.
  6. Zusammensetzung gemäß Anspruch 5, dadurch gekennzeichnet, daß der Anteil der Zusammensetzung in der wässrigen Lösung und wässrigem Konzentrat 25 bis 85 Gewichtsprozent ist.
  7. Zusammensetzung gemäß Anspruch 6, dadurch gekennzeichnet, daß das wässrige Konzentrat mehr als 40 und bis zu 70 Gewichtsprozent Wasser enthält.
  8. Zusammensetzung gemäß Anspruch 6, dadurch gekennzeichnet, daß sie als feste Zusammensetzung, ein Pulver oder ein Granulat enthaltend bis zu 15 Gewichtsprozent Wasser ist.
  9. Verfahren zum Gerben von nicht-gepickelten Fellen durch Einwirkung von Chrom(III)sulfaten in wässriger Flotte, dadurch gekennzeichnet, dass ein wirksamer Anteil einer Zusammensetzung enthaltend
    a) ein mononukleares Chromsalz aufweisend Anionen von Mono- und Polycarbonsäuren mit einem Molekulargewicht von nicht mehr als 200 und Sulfatanionen, das mononukleare Chromsalz hat eine Schorlemmer Basizität von nicht mehr als 25%.
    b) ein Alkalimetallsufat, und
    c) optional Wasser,
    d) der pH-Wert einer 10 gewichtsprozentigen Lösung der Zusammensetzung in Wasser ist nicht mehr als 2.8,
    zu den Fellen in wässriger Flotte zugegeben wird und auf die Felle einwirkt, wobei ein wirksamer Anteil von 1 bis 8 Gewichtsprozent an Chromtrioxid (Cr2O3), basierend auf dem Gewicht der Felle, in der Flotte vorhanden ist.
  10. Verwendung einer Zusammensetzung enthaltend
    a) ein mononukleares Chromsalz aufweisend Anionen von Mono- und Polycarbonsäuren mit einem Molekulargewicht von nicht mehr als 200 und Sulfatanionen, das mononukleare Chromsalz hat eine Schorlemmer Basizität von nicht mehr als 25%.
    b) ein Alkalimetallsufat, und
    c) optional Wasser,
    d) der pH-Wert einer 10 gewichtsprozentigen Lösung der Zusammensetzung in Wasser ist nicht mehr als 2.8,
    zum Gerben von Fellen in wässriger Flotte.
EP04725067A 2003-04-04 2004-04-01 Zusammensetzung, die chrom-salze enthält, zum gerben Expired - Lifetime EP1611258B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH6122003 2003-04-04
PCT/EP2004/050408 WO2004087967A1 (en) 2003-04-04 2004-04-01 Composition comprising chromium salts for tanning

Publications (2)

Publication Number Publication Date
EP1611258A1 EP1611258A1 (de) 2006-01-04
EP1611258B1 true EP1611258B1 (de) 2012-10-03

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EP04725067A Expired - Lifetime EP1611258B1 (de) 2003-04-04 2004-04-01 Zusammensetzung, die chrom-salze enthält, zum gerben

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EP (1) EP1611258B1 (de)
WO (1) WO2004087967A1 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1317395C (zh) * 2005-09-13 2007-05-23 四川大学 一种清洁化的高吸收铬鞣方法
TR200708916A1 (tr) * 2007-12-25 2009-07-21 Soda Sanay� A.�. Krom komplekslerinin dericilikte kullanılması.
WO2012153203A1 (en) * 2011-05-10 2012-11-15 Council Of Scientific & Industrial Research Chrome tanning process for leather making reusing exhaust chrome liquor
ES2632994B1 (es) * 2016-03-16 2018-06-28 Council Of Scientific & Industrial Research Un procedimiento mejorado de curtido al cromo
CN114277202A (zh) * 2021-11-12 2022-04-05 宁夏西部皮草有限公司 一种高密度羊剪绒生产加工工艺

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB547129A (en) * 1941-02-07 1942-08-14 John Burchill Improved tanning process
DE3516842A1 (de) * 1985-05-10 1986-11-13 Hoechst Ag, 6230 Frankfurt Verfahren zur chromspargerbung
DE3726796A1 (de) * 1987-08-12 1989-02-23 Bayer Ag Verfahren zur hochauszehrenden chromgerbung

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WO2004087967A1 (en) 2004-10-14
EP1611258A1 (de) 2006-01-04

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