EP0572353B1 - Procédé de teinture du cuir - Google Patents

Procédé de teinture du cuir Download PDF

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Publication number
EP0572353B1
EP0572353B1 EP19930810365 EP93810365A EP0572353B1 EP 0572353 B1 EP0572353 B1 EP 0572353B1 EP 19930810365 EP19930810365 EP 19930810365 EP 93810365 A EP93810365 A EP 93810365A EP 0572353 B1 EP0572353 B1 EP 0572353B1
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Prior art keywords
process according
dye
weight
methyl
radical
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German (de)
English (en)
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EP0572353A1 (fr
EP0572353B2 (fr
Inventor
Campbell Thomas Dr. Page
Ernst Dr. Tempel
Alois Dr. Püntener
Roberto Dr. Galli
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BASF Schweiz AG
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Ciba Geigy AG
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/32—Material containing basic nitrogen containing amide groups leather skins
    • D06P3/3206—Material containing basic nitrogen containing amide groups leather skins using acid dyes
    • D06P3/3226—Material containing basic nitrogen containing amide groups leather skins using acid dyes dis-polyazo

Definitions

  • the present invention relates to a method for dyeing leather with anionic dyes and to the leather dyed by the method.
  • the dyes are usually used in the form of solid or liquid commercial forms which contain more or less large amounts of alkali halide which has been added as a coupage to adjust a certain color strength or which is present due to the production process. As a result, the dyeing liquors also contain alkali halide.
  • the invention thus relates to a process for dyeing leather with anionic dyes, characterized in that an aqueous solution is used for dyeing, comprising a polyazo dye with at least 2 sulfo groups and less than 1.5% by weight, based on the weight of the dye , Alkali halide.
  • the diazo residue A leads e.g. from a heterocyclic or carbocyclic aromatic amine, preferably from 1- or 2-naphthylamine or aminobenzene, it being possible for the aromatic amines mentioned to be further substituted by one or more identical or different radicals.
  • Suitable substituents on the phenyl or naphthyl radical A are, for example, C 1 -C 4 -alkyl, which here and in general comprises methyl, ethyl, n- or iso-propyl or n-, iso-, sec.- or tert-butyl ; C 1 -C 4 alkoxy, which generally means methoxy, ethoxy, n- or iso-propoxy or n-, iso-, sec- or tert-butoxy; Halogen, for example fluorine, bromine and especially chlorine; Trifluoromethyl; C 1 -C 4 alkylsulfonyl, especially methyl or ethylsulfonyl; Sulfamoyl; N-mono- or N, N-di-C 1 -C 4 alkylsulfamoyl; Carbamoyl; N-mono- or N, N-di-C 1 -C 4 alkylcar
  • Preferred diazo components are compounds of the formula wherein R 1 and R 2 are each independently hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, nitro, trifluoromethyl, C 1 -C 4 alkylsulfonyl, acetylamino, hydroxyacetylamino, propionylamino, sulfamoyl, carbamoyl , Cyano, carboxy or phenoxy mean.
  • radical R 1 or R 2 is C 1 -C 4 -alkylsulfonyl, it is, for example, ethylsulfonyl and in particular methylsulfonyl.
  • R 1 and R 2 are independently of one another hydrogen, methyl, ethyl, methoxy, ethoxy, chlorine, nitro, trifluoromethyl, methylsulfonyl, ethylsulfonyl, sulfamoyl, carbamoyl, cyano, acetylamino and phenoxy.
  • R 1 and R 2 independently of one another particularly preferably represent hydrogen, methyl, methoxy, nitro or chlorine.
  • Examples of preferred compounds of the formula (3) are: Aniline, 2-, 3- or 4-methylaniline, 2-, 3- or 4-methoxyaniline, 2-, 3- or 4-chloroaniline, 2-, 3- or 4-nitroaniline, 2-chloro-4-nitroaniline, 2-methyl-4-nitroaniline, 2,5-dichloroaniline, 2,5-dimethylaniline, 2,5-dimethoxyaniline or 2-methoxy-5-methylaniline.
  • X is OH and it is also preferred that the group X is not on the same ring as the NH 2 group.
  • B denotes the rest of a coupling component, in particular a coupling component from the benzene or naphthalene series.
  • B is preferably a radical of the formula in which R 3 is hydroxy, amino, N-mono- or N, N-di-C 1 -C 4 -alkylamino, phenylamino or o-, m- or p-methylphenylamino and R 4 and R 5 each independently of one another have the meaning of R 3 have or represent hydrogen, benzoylamino, C 1 -C 4 alkanoylamino, carboxymethylamino, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, phenoxy, carboxy, halogen, nitro or sulfo.
  • R 3 as N-mono- or N, N-di-C 1 -C 4 -alkylamino is, for example, methyl-, ethyl-, n- or iso-propyl- or n-, iso-, sec.- or tert.
  • R 3 are hydroxy, amino, N-methyl- and N-ethylamino, N, N-dimethyl- and N, N-diethylamino and phenylamino.
  • R 3 particularly preferably represents hydroxy or amino.
  • R 4 and / or R 5 as well as the variables below as C 1 -C 4 alkyl are generally methyl, ethyl, n- or iso-propyl or n-, iso-, sec.- or tert-butyl.
  • R 4 and / or R 5 or the following variables stand for C 1 -C 4 alkoxy, then methoxy, ethoxy, n- or iso-propoxy or n-, iso-, sec.- or tert.- Butoxy includes.
  • R 4 and / or R 5 as halogen is generally, for example, fluorine, bromine and in particular chlorine, as in the following.
  • R 4 and / or R 5 with the meaning C 1 -C 4 alkanoylamino are, for example, propionylamino, hydroxyacetylamino and in particular acetylamino.
  • Sulfo generally includes the free acid form (-SO 3 H) as well as the salt form, alkali metal salts (Li, Na, K) or ammonium salts being particularly suitable.
  • R 4 and R 5 independently of one another preferably represent hydrogen, sulfo, acetylamino, methyl, ethyl, methoxy, ethoxy, chlorine, carboxy, hydroxy, amino, N-methyl- or N-ethylamino, N, N-dimethyl- or N, N-diethylamino or phenylamino and particularly preferably for hydrogen, amino, hydroxy, methyl, methoxy, phenylamino or N, N-dimethyl- or N, N-diethylamino.
  • R 3 is hydroxyl, amino, N-methyl- or N-ethylamino, N, N-dimethyl- or N, N-diethylamino or phenylamino
  • R 4 and R 5 each independently represent hydrogen, acetylamino, methyl, ethyl, methoxy, ethoxy, chlorine, carboxy, hydroxy, amino, N-methyl- or N-ethylamino, N, N-dimethyl- or N, N-diethylamino or phenylamino.
  • Suitable compounds of the formula (4) are: phenol, 4-methylphenol, 1,3-dihydroxybenzene (resorcinol), 3-aminophenol, 1,3-phenylenediamine, 3-N, N-diethylaminophenol, 3-phenylaminophenol, 2, 5-dimethylaniline, 2-methoxy-5-methylaniline, salicylic acid, 2- or 3-methylaniline, 2-methoxyaniline, 1,3-diamino-4-methylbenzene, 1,3-diamino-4-chlorobenzene and 1,3-diamino -4-methoxybenzene.
  • a particularly preferred embodiment of the present invention relates to the use of 3-aminophenol, resorcinol or 1,3-phenylenediamine as the coupling component.
  • n is preferably 2 and m is preferably 1.
  • the dyes of the formula (1) and (2) are known or can be prepared in a known manner.
  • the dyes of the formula (1) or (2) prepared in the customary manner normally contain about 5 to 30% by weight of alkali metal halide, based on the weight of the dye.
  • This alkali halide is formed in the synthesis of the dye and / or added to the dye solution obtained for the deposition of the dye.
  • the solid or liquid commercial form of the dye is often adjusted to the desired color strength by adding alkali halide.
  • an aqueous solution containing a dye with less than 1.5% by weight, based on the weight of the dye, of alkali metal halide is used.
  • the dyes which are commercially available or prepared in the customary manner must therefore be largely freed from the alkali halide before they are used in the dyeing process according to the invention. This is done in a manner known per se, for example by reverse osmosis, ultrafiltration or dialysis. Such desalination processes are known, e.g. from EP-A 0 059782. Also known are the membranes used in these processes, e.g. from EP-A 0 061 424.
  • the process conditions for this desalination are selected so that dye solutions are obtained which contain less than 1.5% by weight, based on the weight of the dye, of alkali metal halide.
  • Dye salts and salts with higher molecular weight cations and / or anions are not or only slightly removed.
  • alkali halide is to be understood as meaning lithium, sodium and potassium fluoride, chloride, bromide and iodide.
  • the dye is in the form of an aqueous solution, which, if desired, can be concentrated or evaporated to dryness, for example by spray drying.
  • a preferred embodiment of the dyeing process according to the invention is characterized in that an aqueous solution is used for dyeing, containing a polyazo dye of the formula (2) and less than 1.0% by weight, based on the weight of the dye, of alkali metal halide.
  • the dyes are preferably used as aqueous dye preparations. These preparations preferably contain 5 to 40% by weight of dye, 65 to 95% by weight of water, 0 to 20% by weight of further additives and less than 1.5% by weight, based on the weight of the dye, of alkali halide.
  • Dye preparations used with preference contain 10 to 25% by weight of dye, 70 to 90% by weight of water, 0 to 20% by weight of further additives and less than 1.0% by weight, based on the weight of the dye, of alkali metal halide.
  • the dye preparations can e.g. contain surface-active substances, buffer substances, foam-suppressing aids, antifreezing agents and substances that inhibit fungal and / or bacterial growth.
  • the amounts in which the dyes are used in the dye baths can vary within wide limits depending on the desired depth of color. In general, amounts of dye of 0.1 to 10, preferably 0.5 to 4,% by weight, based on the weight of the leather to be colored, are advantageous.
  • the dye liquor can also contain other additives, e.g. Acids or bases for setting the desired pH value, as well as auxiliaries such as Wetting agents, greasing agents, color-deepening aids, leveling agents, and / or anti-foaming agents.
  • additives e.g. Acids or bases for setting the desired pH value
  • auxiliaries such as Wetting agents, greasing agents, color-deepening aids, leveling agents, and / or anti-foaming agents.
  • the process according to the invention has the great advantage that less dye is required to achieve a certain depth of color than when using dyeing liquors which contain larger amounts of alkali metal halides, since the dyestuff capacity is greater.
  • the method according to the invention is not only suitable for a certain type of leather, but can also be applied to the different types of leather, for example chrome leather. retanned leather or suede from goat, beef or pork.
  • the dyeing is preferably carried out by the exhaust process, e.g. at a liquor ratio of 1: 1.5 to 1:20, preferably 1: 2 to 1:10, and at temperatures of 20 to 100 ° C, preferably 30 to 60 ° C.
  • the leather can be pretreated be subjected, for example, to a neutralization or roll.
  • the dyeing time varies depending on the type of leather and the desired depth of color, but is generally between 30 and 180 minutes. After the dyeing, the leather is rinsed and finished as usual.
  • the process according to the invention gives leather dyeings in the same shades and fastness properties as when dyeing with dye liquors which are richer in alkali halide.
  • This solution is desalinated in a laboratory reverse osmosis system under the following conditions: polysulfone membrane, approx. 40 ° C, feed: 12 l / h, 25 bar, flux 1289 l / m 2 d (average). After 4.5 hours, 1.9 kg of a solution with a dye content of 18.0% by weight and a sodium chloride content of 0.05% by weight (0.9% by weight, based on dye) are obtained. This desalted and concentrated solution is adjusted to a dye content of 15% after filtration through a 10 ⁇ m sieve with water.
  • the leather is dyed in a float of 1000 parts of water, 2 parts of 24% ammonia and 13.33 parts of the dye solution described above at 50 ° C.
  • the mixture After a dyeing time of 60 minutes, the mixture is acidified with 4 parts of 85% formic acid and then dyeing is continued for 20 minutes.
  • the dyed leather is finished after treatment in a fresh bath with 1000 parts of water, 2.5 parts of a condensation product of formaldehyde, dicyandiamide, ammonium chloride and ethylenediamine and 0.5 part of 85% strength Formic acid for 45 minutes at 50 ° C.
  • the leather obtained is dyed black. It has good fastness properties and good hiding power.
  • 100 parts of chrome-tanned cowhide with a fold thickness of 1.4 mm are drummed in a fleet consisting of 200 parts of water, 1 part of sodium bicarbonate and 1 part of sodium formate for 45 minutes at 30 ° C. and then washed twice with 300 parts of water at the same temperature.
  • the leather neutralized in this way is then dyed in a liquor composed of 1000 parts of water, 2 parts of 24% ammonia and 15 parts of the dye solution described in Example 1 at 50 ° C.
  • the dyeing liquor is 3 parts of a synthetic fatliquor (mixture of alkylbenzenes, aliphatic hydrocarbons, alkanesulfonic acids and surfactants) and, after a further 30 minutes, 0.5 part of 85% formic acid, diluted with 5 parts of water, is added. Thereafter, the treatment is continued at 50 ° C. for 20 minutes
  • the result is leather of any color black with excellent fastness properties, in particular good diffusion fastness to soft PVC.
  • the color matches the color obtained in Example 1.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Claims (22)

  1. Procédé pour la teinture de cuir à l'aide de colorants anioniques, caractérisé en ce que l'on utilise pour la teinture une solution aqueuse contenant un colorant polyazoïque comportant au moins 2 groupes sulfo ainsi que moins de 1,5 % en poids, rapporté au poids du colorant, d'halogénure de métal alcalin.
  2. Procédé conforme à la revendication 1, caractérisé en ce que l'on utilise pour la teinture une solution aqueuse contenant un colorant de formule
    Figure imgb0018
     dans lequel
    A représente le résidu d'un composant diazo aromatique,
    B représente le résidu d'un copulant,
    X représente un résidu OH ou NH2,
    Y représente un groupe NH, O ou SO2NH,
    n est égal à 1 ou 2,
    m est égal à 0,1 ou 2.
  3. Procédé conforme à la revendication 2, caractérisé en ce que l'on utilise pour la teinture une solution aqueuse contenant un colorant de formule
    Figure imgb0019
     dans laquelle
    A représente le résidu d'un composant diazo aromatique,
    B représente le résidu d'un copulant,
    X représente un résidu OH ou NH2,
    n est égal à 1 ou 2,
    m est égal à 0,1 ou 2.
  4. Procédé conforme à une des revendications 1 à 3, caractérisé en ce que l'on utilise un colorant de formule (1) ou (2) dans lequel le résidu diazo A est dérivé de la 1-naphtylamine ou de la 2-naphtylamine ou de l'aminobenzène, les amines aromatiques indiquées pouvant être substituées par un ou plusieurs résidus identiques ou différents.
  5. Procédé conforme à une des revendications 1 à 4, caractérisé en ce que l'on utilise un colorant de formule (1) à (2) dans lequel le résidu diazo A est dérivé d'une amine de formule
    Figure imgb0020
     dans laquelle R1 et R2 représentent indépendamment l'un de l'autre un atome d'hydrogène, un groupe alkyle en C1-4, alcoxy en C1-4, halogéno, nitro, trifluorométhyle, (alkyle en C1-4)sulfonyle, acétylamino, hydroxyacétylamino, propionylamino, sulfamoyle, carbamoyle, cyano, carboxy ou phénoxy.
  6. Procédé conforme à la revendication 5, caractérisé en ce que R1 et R2 représentent indépendamment l'un de l'autre un atome d'hydrogène, un groupe méthyle, éthyle, méthoxy, éthoxy, chloro, nitro, trifluorométhyle, méthylsulfonyle, éthylsulfonyle, sulfamoyle, carbamoyle, cyano, acétylamino ou phénoxy.
  7. Procédé conforme à la revendication 6, caractérisé en ce que R1 et R2 représentent indépendamment l'un de l'autre un atome d'hydrogène, un groupe méthyle, méthoxy, nitro ou chloro.
  8. Procédé conforme à la revendication 7, caractérisé en ce que le résidu diazo A est dérivé d'aniline, de 2-, 3- ou 4-méthylaniline, de 2-, 3- ou 4-méthoxyaniline, de 2-, 3- ou 4-chloroaniline, de 2-, 3- ou 4-nitroaniline, de 2-chloro-4-nitroaniline, de 2-méthyl-4-nitroaniline, de 2,5-dichloroaniline, de 2,5-diméthylaniline, de 2,5-diméthoxyaniline ou de 2-méthoxy-5-méthylaniline.
  9. Procédé conforme à une des revendications 1 à 8, caractérisé en ce que X représente un groupe OH.
  10. Procédé conforme à une des revendications 1 à 9, caractérisé en ce que X n'est pas lié au même noyau que le groupe NH2.
  11. Procédé conforme à une des revendications 1 à 10, caractérisé en ce que B représente un résidu de formule
    Figure imgb0021
     dans laquelle R3 représente un groupe hydroxy, amino, N-mono-(alkyle en C1-4)-amino ou N,N-di-(alkyle en C1-4)-amino, phénylarnino ou o-, m- ou p-méthylphénylamino et R4 et R5 représentent indépendamment un résidu R3 ou un atome d'hydrogène, un groupe benzoylamino, (alcanoyle en C1-4)-amino, carboxyméthylamino, alkyle en C1-4, alcoxy en C1-4, phénoxy, carboxy, halogéno, nitro ou sulfo.
  12. Procédé conforme à la revendication 11, caractérisé en ce que R3 représente un groupe hydroxy, amino, N-méthylamino et N-éthylamino, N,N-diméthylamino et N,N-diéthylamino ou phénylamino, en particulier un groupe hydroxy ou amino.
  13. Procédé conforme à une des revendications 1 à 12, caractérisé en ce que R4 et R5 représentent indépendamment l'un de l'autre un atome d'hydrogène, un groupe sulfo, acétylamino, méthyle, éthyle, méthoxy, éthoxy, chloro, carboxy, hydroxy, amino, N-méthylamino ou N-éthylamino, N,N-diméthylamino ou N,N-diéthylamino ou phénylamino et en particulier un atome d'hydrogène, un groupe amino, hydroxy, méthyle, méthoxy, phénylamino ou N,N-diméthylamino ou N,N-diéthylamino.
  14. Procédé conforme à une des revendications 1 à 13, dans lequel B représente un résidu de formule (4) dans laquelle R3 représente un groupe hydroxy, amino, N-méthylamino ou N-éthylamino, N,N-diméthylamino ou N,N-diéthylamino ou phénylamino et R4 et R5 représentent indépendamment l'un de l'autre un atome d'hydrogène, un groupe acétylamino, méthyle, éthyle, méthoxy, éthoxy, chloro, carboxy, hydroxy, amino, N-méthyl ou N-éthylamino, N,N-diméthyl- ou N,N-diéthylamino ou phénylamino.
  15. Procédé conforme à la revendication 14, caractérisé en ce que B représente un résidu dérivé du phénol, 4-méthylphénol, 1,3-dihydroxybenzène (résorcinol), 3-aminophénol, 1,3-phénylénediamine, 3-N,N-diéthylaminophénol, 3-phénylaminophénol, 2,5-diméthylaniline, 2-méthoxy-5-méthylaniline, acide salicylique, 2-méthylaniline ou 3-méthylaniline, 2-méthoxyaniline, 1,3-diamino-4-méthylbenzène, 1,3-diamino-4-chlorobenzène et 1,3-diamino-4-méthoxybenzène.
  16. Procédé conforme à une des revendications 1 à 15, caractérisé en ce que B représente un résidu de formule
    Figure imgb0022
     où R3' représente un groupe arnino ou hydroxy, R4' un groupe amino, hydroxy, méthyle, méthoxy, phénylamino ou N,N-diméthyl- ou N,N-diéthylamino et R5' un atome d'hydrogène, un groupe méthyle ou méthoxy.
  17. Procédé conforme à une des revendications 1 à 16, caractérisé en ce que B représente un résidu 3-aminophénol, résorcinol ou 1,3phénylènediamine.
  18. Procédé conforme à une des revendications 1 à 17, caractérisé en ce que l'on utilise un colorant de formule (1) ou (2) dans lequel n vaut 2.
  19. Procédé conforme à une des revendications 1 à 18, caractérisé en ce que l'on utilise un colorant de formule (1) ou (2) dans lequel m vaut 1.
  20. Procédé conforme à une des revendications 1 à 19, caractérisé en ce que l'on utilise pour la teinture une solution aqueuse contenant un colorant polyazoïque de formule (1) ou (2) ainsi que moins de 1,0 % en poids, rapporté au poids du colorant, d'halogénure de métal alcalin.
  21. Procédé conforme à une des revendications 1 à 20 caractérisé en ce que l'on utilise pour la teinture une préparation de colorant liquide contenant de 5 à 40 % en poids de colorant, de 65 à 95 % en poids d'eau et de 0 à 20 % en poids d'autres additifs et moins de 1,5 % en poids, rapporté au poids du colorant, d'halogénure de métal alcalin.
  22. Procédé conforme à une des revendications 1 à 21, caractérisé en ce que l'on utilise pour la teinture une préparation de colorant liquide contenant de 10 à 25 % en poids de colorant, de 70 à 90 % en poids d'eau et de 0 à 20 % en poids d'autres additifs et moins de 1,0 % en poids, rapporté au poids du colorant, d'halogénure de métal alcalin.
EP19930810365 1992-05-26 1993-05-18 Procédé de teinture du cuir Expired - Lifetime EP0572353B2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH1687/92 1992-05-26
CH168792 1992-05-26
CH168792A CH685251A5 (de) 1992-05-26 1992-05-26 Verfahren zum Färben von Leder.

Publications (3)

Publication Number Publication Date
EP0572353A1 EP0572353A1 (fr) 1993-12-01
EP0572353B1 true EP0572353B1 (fr) 1996-06-19
EP0572353B2 EP0572353B2 (fr) 1999-06-09

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EP (1) EP0572353B2 (fr)
JP (1) JPH0665869A (fr)
CH (1) CH685251A5 (fr)
DE (1) DE59302989D1 (fr)
ES (1) ES2089774T3 (fr)
MX (1) MX9303069A (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8192791B2 (en) 2006-07-25 2012-06-05 Joseph Mellini Leather-surface repair-composition and the method for surface repair of leather surfaces

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004027812A1 (de) 2004-06-08 2006-01-05 Basf Ag Verfahren zum Reaktiv-Färben von Leder
TWI540186B (zh) * 2015-07-16 2016-07-01 臺灣永光化學工業股份有限公司 黑色染料組成物及其用途

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Publication number Priority date Publication date Assignee Title
FR2360634A1 (fr) * 1976-08-03 1978-03-03 Ugine Kuhlmann Nouveaux colorants trisazoiques hydrosolubles
EP0433229B1 (fr) * 1989-12-11 1994-01-26 Ciba-Geigy Ag Procédé de teinture du cuir
DE4124437A1 (de) * 1990-07-26 1992-01-30 Ciba Geigy Ag Polyazofarbstoffe

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8192791B2 (en) 2006-07-25 2012-06-05 Joseph Mellini Leather-surface repair-composition and the method for surface repair of leather surfaces
US8481107B2 (en) 2006-07-25 2013-07-09 Joseph Mellini Leather-surface repair-composition and the method for surface repair of leather surfaces

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DE59302989D1 (de) 1996-07-25
MX9303069A (es) 1994-06-30
EP0572353A1 (fr) 1993-12-01
ES2089774T3 (es) 1996-10-01
CH685251A5 (de) 1995-05-15
JPH0665869A (ja) 1994-03-08
EP0572353B2 (fr) 1999-06-09

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