EP0985019B1 - Systeme de blanchiment - Google Patents

Systeme de blanchiment Download PDF

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Publication number
EP0985019B1
EP0985019B1 EP98928290A EP98928290A EP0985019B1 EP 0985019 B1 EP0985019 B1 EP 0985019B1 EP 98928290 A EP98928290 A EP 98928290A EP 98928290 A EP98928290 A EP 98928290A EP 0985019 B1 EP0985019 B1 EP 0985019B1
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EP
European Patent Office
Prior art keywords
enzyme
bleaching system
transition metal
bleaching
metal compound
Prior art date
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Expired - Lifetime
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EP98928290A
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German (de)
English (en)
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EP0985019A1 (fr
Inventor
Albrecht Weiss
Ulrich Pegelow
Beatrix Kottwitz
Marita Grothus
Maria Liphard
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38654—Preparations containing enzymes, e.g. protease or amylase containing oxidase or reductase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions

Definitions

  • the present invention relates to a bleaching system made of hydrogen peroxide Enzyme and transition metal compound as well as the use this system as a bleaching component in washing and cleaning agents.
  • Enzymatic bleaching compositions containing a hydrogen peroxide-forming System included are well known in the art. For example are such in the patent applications in EP 553 608, EP 553 607, EP 538 228, EP 537 381 and DE 20 64 146.
  • Such enzymatic bleaching compositions can be found, for example, in Detergent formulations are used for washing textiles, wherein the highest possible bleaching effect at low temperature is desirable.
  • the enzymes catalyze the reaction between the dissolved Oxygen and the substrate.
  • a bleach activator is usually used.
  • One of the most commonly used bleach activator is tetraacetylethylene diamine (TAED), which forms peracetic acid by reaction with the hydrogen peroxide, the Peracetic acid is the actual bleach.
  • TAED tetraacetylethylene diamine
  • oxidases are minimized Concentrations used. Low oxidase or peroxidase concentrations however, also lead to less hydrogen peroxide formation and therefore to a low bleaching capacity.
  • Bleaching catalysts in the form of transition metal complexes for example Manganese (Mn) and / or iron (Fe) are known from the prior art and are described, for example, in European patent applications EP 0 458 397, EP 0 458 398, EP 0 544 519 and EP 0 549 272. In combination with Hydrogen peroxide form a very strong oxidation system.
  • Mn Manganese
  • Fe iron
  • transition metal complexes have the disadvantage that they are not only the bleachable stains but also destroy the dye that is located on the fiber. In some cases, it can also destroy the fiber, to so-called pitting.
  • the object of the present invention was to provide a catalyst system develop that at low temperature without external addition of Oxygen carriers are effective and with bleachable stains that affect them of the fiber or in the wash liquor, reacts and destroys the Soiling leads.
  • the bleaching system should also have free, in the Dye molecules in the wash liquor react to the color on the textile should however be preserved, i.e. a reaction with on the textile Color or with the textile fiber should be avoided.
  • the present invention accordingly relates to a bleaching system Hydrogen peroxide generating enzyme and transition metal compound characterized in that one of atmospheric oxygen and suitable Enzyme substrate Hydrogen peroxide-producing enzyme covalently attached to the Transition metal compound is bound.
  • Another object of the present invention is accordingly Use of the bleaching system as a bleaching component in washing and Detergents and to inhibit color transfer during use such means. Yet another subject relates to the use of the Bleaching system in disinfectants.
  • the bleaching system according to the invention gives very good bleaching performance at low washing temperatures, in particular between 15 and 55 ° C.
  • the bleaching system continuously forms H 2 O 2 and thus achieves a uniform bleaching performance without causing fiber damage. Although it reacts with the bleachable stains on the fiber and in the wash liquor and also with free dye molecules in the wash liquor, it does not react with textile dyes on the textile.
  • the system is due to thermal Enzyme lability essentially inactive. Due to the high solubility of the enzymatic system according to the invention can deposit on the Fibers are minimized. Deposits of the enzyme bound Metal complexes on a piece of laundry were not found.
  • transition metal compounds used according to the invention in the form bound to the enzyme are preferably copper, manganese, iron, cobalt, Ruthenium and / or molybdenum compounds, because with these compounds the Bleaching reaction particularly good and controllable within certain limits is.
  • bleach catalyst compounds of this type are manganese complexes, as are described in US Pat. Nos. 5,246,621 and 5,244,594. Preferred examples of these complexes are Mn IV 2 ( ⁇ -O) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 - (PF 6 ) 2 , Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 - (ClO 4 ) 2 , Mn IV 4 ( ⁇ -O) 6 (1,4,7-triazacyclononane) 4 - ( ClO 4 ) 2 , Mn III Mn IV 4 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 - (ClO 4 ) 3 and their mixtures. Other examples of transition metal compounds are described in European patent application EP 0 549 272.
  • Suitable compounds contain 1,5,9-trimethyl-1,5,9-triazacyclododecane as ligands, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane and their Mixtures.
  • Water-soluble manganese (II), (III), and (IV) complexes are also suitable, in which the ligand is a carboxylate-polyhydroxy compound with at least three successive C-OH groups, such as compounds with sorbitol, iditol, Dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol, meso-inositol, Lactose and mixtures thereof as ligands.
  • the ligand is a carboxylate-polyhydroxy compound with at least three successive C-OH groups, such as compounds with sorbitol, iditol, Dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol, meso-inositol, Lactose and mixtures thereof as ligands.
  • a suitable transition metal complex with Mn, Co, Fe or Cu as transition metals and a non- (macro) -cyclic ligand is described in US Pat. No. 5,114,611.
  • Preferred ligands are pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. Possibly. the rings can be substituted with substituents such as alkyl, aryl, alkoxy, halogen and nitro.
  • a particularly preferred ligand is 2,2'-bispyridylamine.
  • Co, Cu, Mn, Fe bispyridylmethane and bispyridylamine complexes are preferred.
  • Very particularly preferred complexes are Co (2,2'-bispyridylamine) Cl 2 , di (isothiocyanato) bispyridylamine cobalt (II), tris-dipyridylamine cobalt (II) perchlorate, Co (2,2-bispyridylamine) 2 O 2 ClO 4 , bis (2,2'-bispyridylamine) copper (II) perchlorate, tris (di-2-pyridylamine) iron (II) perchlorate and mixtures thereof.
  • Mn-glyconate Mn (CF 3 SO 3 ) 2 , Co (NH 3 ) 5 Cl 3 and dinuclear Mn complexes with tetra-N-dentate and Bi-N-dentate ligands, such as N 4 Mn III ( ⁇ -O) 2 Mn IV 4 ) + and [Bipy 2 Mn III ( ⁇ -O) 2 Mn IV Bipy 2 ] - (ClO 4 ) 3
  • bleaching catalysts are, for example, in the European patent applications EP 0 408 131 (catalysts based on cobalt complexes), EP 0 384 503 and EP 0 306 089 (metal porphyrin catalysts), in the US patent US 4,728,455 (manganese catalyst with multidentate ligand), the US patent US 4,711,748 and. European patent application EP 0 224 952 (Manganese absorbed on aluminosilicate), in US Pat. No. 4,601,845 (aluminosilicate carrier with manganese and zinc or magnesium salt), US Pat. No. 4,626,373 (Manganese / ligand catalyst), US Pat. No.
  • An example of a preferred ligand is 1,2-bis (4,7-dimethyl-1,4,7-triaza-1-cyclononyl) ethane, ([EB (Me 3 TACN) 2 ]).
  • the ligands mentioned above can be as described by K. Wieghardt et al in Inorganic Chemistry, 1985, 24, p. 1230 ff. And J Chem Soc, Chem Comm. 1987, P. 886, or by simply modifying this synthesis.
  • the ligands can also be in the form of their acid salts, such as the HCl or H 2 SO 4 salts, for example as 1,4,7-Me 3 TACN hydrochloride. Possibly. the iron and / or manganese ions can be added to the ligand separately or in a single product.
  • their acid salts such as the HCl or H 2 SO 4 salts, for example as 1,4,7-Me 3 TACN hydrochloride.
  • the iron and / or manganese ions can be added to the ligand separately or in a single product.
  • the iron or manganese ions can be used as water-soluble salt as or manganese nitrate, chloride, sulfate or acetate, or as Coordination compound, as present as manganese acetylacetonate.
  • Such iron and / or manganese compounds are preferably used, from which the transition metal complex can be quickly formed.
  • the bleaching catalyst can also be in the form of 1-, 2- or tetranuclear manganese or iron complexes.
  • Preferred mononuclear complexes have the general formula (IV): [L Mn X p ] z Y q wherein Mn is manganese in the oxidation state II, III or IV, X each represents a coordination ligand which can be selected independently from UR ", wherein R" is a C 1 to C 20 radical which is selected from the group of alkyl, cycloalkyl, aryl, benzyl and their combinations, which may or may not be substituted, or at least 2 R "radicals may be connected to one another so as to form a bridge between the two oxygen atoms which are associated with the manganese, Cl - , Br - , J - , F - , NCS - , N 3 - , J 3 - , NH "OH-, O 2 2- , HOO, H 2 O,
  • Preferred multinuclear complexes have the formulas V or VI shown below wherein Mn each independently have the oxidation state III or IV and L, X, Y, z and q have the meanings given in the formulas I to III.
  • dinuclear manganese complexes are those in which X is each independently selected from CH 3 COO - , O 2 2- and O 2- and particularly preferably those in which the manganese is in the oxidation state IV and XO 2- .
  • Examples of such ligands are: i) [Mn iv 2 ( ⁇ -O) 3 (1,4,7-Me 3 TACN) 2 ] (PF 6 ) 2 ii) (Mn iv 2 ( ⁇ -O) 3 (1,2,4,7-Me 4 TACN) 2 ] (PF 6 ) 2 iii) [Mn iii 2 ( ⁇ -OAc) 2 ( ⁇ -O) (1,4,7-Me 3 TACN) 2 ] (PF 6 ) 2 iv) [Mn iii 2 ( ⁇ -O) ( ⁇ -OAc) 2 (1,2,4,7-Me 4 TACN) 2 ] (PF 6 ) 2 v) [Mn iv 2 ( ⁇ -O) 2 ( ⁇ -O 2 ) (1,4,7-Me 3 TACN) 2 ] (PF 6 ) 2 vi) [Mn iv Mn iii ( ⁇ -O) 2 ( ⁇ -OAc) (EB- (Me 3
  • the preferred compounds according to formula (VII) include those in which R 20 is a methylene group, 1,2-ethylene group, 1,3-propylene group, in position 2 hydroxy or nitro-substituted 1,3-propylene group, 1,2-cycloalkylene group 4 to 6 carbon atoms, in particular a 1,2-cyclohexylene group, or an o-phenylene group.
  • the electron-shifting substituents Y 1 and Y 2 in formula (VII) include the hydroxyl group, alkoxy groups with 1 to 4 carbon atoms, arylox groups, the nitro group, halogens such as fluorine, chlorine, bromine and iodine, the amino group, which are also mono- or can be dialkylated or -arylated, linear or branched chain alkyl groups with 1 to 4 C atoms, cycloalkyl groups with 3 to 6 C atoms, linear or branched chain alkenyl groups with 2 to 5 C atoms, and aryl groups, which in turn can carry the aforementioned substituents .
  • the alkenyl groups which may contain 1 or 2 CC double bonds, preferably have at least one double bond conjugated to the benzene ring.
  • the preferred alkenyl substituents include the allyl and vinyl groups.
  • the substituents Y 1 and Y 2 are preferably in the 5-position.
  • the compounds of formula (VII) used with preference include those in which Y 1 and Y 2 are identical.
  • the alkyl radicals having 1 to 4 carbon atoms include in particular the methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl and tert-butyl group.
  • the charge-balancing anion ligand A in the compounds of the formula (VII) can be of one or more values, in the latter case correspondingly several Neutralize transition metal atoms with the organic ligands mentioned can. It is preferably a halide, in particular chloride Hydroxide, hexafluorophosphate, perchlorate or around the anion of a carboxylic acid, such as formate, acetate, benzoate or citrate.
  • the compounds of the formula (VII) used according to the invention can be prepared by known processes in the principle by the reaction of salicylaldehyde or corresponding ketones (if R 21 and / or R 22 are not hydrogen), which optionally have the substituents Y 1 , Y 2 , Z 1 defined above and / or Z 2 , with diamines H 2 NR 20 -NH 2 and the reaction of the salen ligand thus obtainable with transition metal salts, as described, for example, in European patent application EP 0 630 694 or by BB De, BB Lohraj, S. Sivaram and PK Dhal in Macromolecules 27 (1994), 1291-1296.
  • Hydrogen peroxide-forming system can be of various such Systems are selected as they are already from the prior art are known.
  • an amine oxidase and an amine a Amino acid oxidase and an amino acid
  • cholesterol oxidase and Cholesterol uric acid U oxidase and uric acid or xanthine oxidase and Xanthine can be used.
  • ethanol oxidases are those which are isolated from a catalase-negative strain of Hansenula Polymorpha (see for example EP 0 244 920).
  • carrier-fixed enzymes are used.
  • the enzymes can be fixed on any supports in a known manner.
  • activated carbon aluminum oxide, titanium activated glass, synthetic resins, silica gel, glasses, cellulose and Cellulose derivatives, starch derivatives, wood chips, silicon dioxide or organic polymers, like polyurethanes in question.
  • the transition metal complex is bound to the enzyme via a covalent compound.
  • the covalent bond is preferably carried out via reactive groups which are located on the surface of the enzymes and on the complex ligands.
  • Reactive functional groups on the enzymes are, for example, ⁇ - and ⁇ -amino groups, carboxy, hydroxyl and sulfhydryf, imidazole and phenolic groups, amino groups, hydroxyl groups and sulfhydryl groups being particularly suitable. If the enzymes used do not have such groups, it is possible to modify the surface in a manner known per se by protein engineering, for example by exchanging suitable amino acids on the surface of the enzymes to introduce appropriately functionalized amino acids to which the metal complex is covalently bound can.
  • the reactive groups on the enzymes are directly linked to suitable reactive groups on the transition metal complex.
  • OH, NH 2 , COOH and (-S -) groups are particularly suitable as reactive groups on the transition metal complex, with NH 2 and COOH groups being preferred.
  • the link between the enzyme and the transition metal complex can be carried out according to methods known from enzyme technology for immobilizing enzymes (cf. Römpp, Biotechnologie, p. 388, keyword: immobilization, with further references; "industrial enzymes", Heinz Ruttrance, 1994, Behr's Verlag; Industrial Enzymology, 2nd ed., 1994, pp. 269-272, Godfrey & West. If necessary, the enzyme and the metal complex can be added via a spacer, a so-called spacer, as is also used in enzyme immobilization will be used, connected form.
  • the invention Bleaching system of oxidase and metal compound on a surface charge, which is positive near the metal connection.
  • Charge distribution can avoid dimerization via metal compounds become.
  • binding or enrichment of the bleachable stains can be improved.
  • the surface of the enzyme in a manner known per se by protein engineering modified.
  • this makes it possible to connect to stabilize and thus dimerization or further aggregations, to prevent and on the other hand the bleaching of the bleachable stains to optimize, especially considering the specificity to dirt optimize tissue protection.
  • Another object of the present invention relates to the use of The bleaching system described above as a bleaching component in washing and cleaning agents, in particular in universal detergents for textiles, and to inhibit color transfer in textile washing.
  • detergents or cleaning agents can all be used as additional components such components contain usual components, e.g. anionic, nonionic, cationic and amphoteric surfactants, inorganic and organic Framework substances, auxiliaries such as optical brighteners, graying inhibitors, Salts.
  • auxiliaries such as optical brighteners, graying inhibitors, Salts.
  • Another object of the present invention is a washing or Cleaning agent that the bleaching system according to one of claims 1 to 7 contains.
  • the bleaching system consisting of derivatized enzyme and Enzyme substrate, can be in the agents in an amount of 0.1 wt .-% to 20 wt .-%, based on the total agent, contained in detergents or cleaning agents his.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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Claims (11)

  1. Système de blanchiment à base d'enzyme producteur de peroxyde d'hydrogène et d'un composé métallique de transition,
    caractérisé en ce qu'
    un enzyme producteur de peroxyde d'hydrogène à partir de l'oxygène atmosphérique et d'un substrat d'enzyme approprié, est lié d'une manière covalente au composé métallique de transition.
  2. Système de blanchiment selon la revendication 1,
    caractérisé en ce que
    le composé métallique de transition contient comme ligand L un composé organique macrocyclique de formule II
    Figure 00210001
    dans laquelle t est le nombre entier 2 ou 3, s est un nombre allant de 3 à 4 et est égal à zéro ou 1, R8, R9 et R10, respectivement, indépendamment les uns des autres, sont choisis dans le groupe de H, alkyle, aryle, alkyle ou aryle substitué.
  3. Système de blanchiment selon la revendication 1,
    caractérisé en ce que
    comme composés métalliques de transition on met en oeuvre des complexes de Salène ayant la formule suivante VII
    Figure 00210002
    dans laquelle
    U représente du manganèse, du fer, du cobalt, du ruthénium ou du molybdène,
    R20 représente un reste alkylène, alkényléne, phénylène ou cycloalkylène, qui peut être en supplément éventuellement alkyl-et/ou aryl-substitué vers le substituant X, avec au total de 1 à 12 atomes de carbone, à l'intérieur de R20 l'intervalle le plus court entre les atomes de N qui se complexent avec UM, s'élève à 1 à 5 atomes de carbone,
    X représente -H, -OR23, -NO2, -F, -Cl, -Br ou -I,
    R21, R22 et R23 indépendamment l'un de l'autre, représentent de l'hydrogène, ou un reste alkyle ayant de 1 à 4 atomes de carbone,
    Y1 et Y2 indépendamment l'un de l'autre, représentent de l'hydrogène ou un substituant qui repousse les électrons,
    Z1 et Z2 indépendamment l'un de l'autre, représentent de l'hydrogène, -CO2M, -SO3M ou -NO2,
    M représente de l'hydrogène ou un métal alcalin comme le lithium, le sodium ou le potassium et
    A représente un ligand d'anion qui assure l'équilibre de la charge.
  4. Système de blanchiment selon l'une des revendications 1 à 3,
    caractérisé en ce que
    le composé métallique de transition est choisi parmi les complexes du manganèse et les complexes du fer.
  5. Système de blanchiment selon l'une des revendications 1 à 4,
    caractérisé en ce que
    l'enzyme est immobilisé sur un support.
  6. Système de blanchiment selon l'une des revendications 1 à 5,
    caractérisé en ce que
    le composé métallique de transition est lié à l'enzyme par l'intermédiaire de groupes réactifs qui se trouvent à la surface de l'enzyme, en particulier par des groupes α- et ε-amino, carboxy, hydroxy et sulfhydryle, imidazol et phénoliques.
  7. Système de blanchiment selon l'une des revendications 1 à 6,
    caractérisé en ce que
    la surface de l'enzyme est modifiée d'une manière connue en soi, par le génie des protéines.
  8. Système de blanchiment selon la revendication 7,
    caractérisé en ce que
    la surface de l'enzyme possède à proximité de l'endroit de liaison du composé métallique de transition, une charge positive de surface.
  9. Utilisation du système de blanchiment selon l'une des revendications 1 à 8, comme composant de blanchiment dans des produits de lavage et de nettoyage.
  10. Utilisation du système de blanchiment selon l'une des revendications 1 à 8, dans des produits de lavage et de nettoyage, en vue de l'inhibition du transfert de couleur.
  11. Utilisation du système de blanchissement selon l'une des revendications 1 à 8, dans des produits de désinfection.
EP98928290A 1997-05-26 1998-05-18 Systeme de blanchiment Expired - Lifetime EP0985019B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19721886 1997-05-26
DE19721886A DE19721886A1 (de) 1997-05-26 1997-05-26 Bleichsystem
PCT/EP1998/002920 WO1998054282A1 (fr) 1997-05-26 1998-05-18 Systeme de blanchiment

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EP0985019A1 EP0985019A1 (fr) 2000-03-15
EP0985019B1 true EP0985019B1 (fr) 2001-12-05

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US (1) US6479450B1 (fr)
EP (1) EP0985019B1 (fr)
JP (1) JP2001526729A (fr)
AT (1) ATE210178T1 (fr)
DE (2) DE19721886A1 (fr)
ES (1) ES2169525T3 (fr)
WO (1) WO1998054282A1 (fr)

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BR0108772A (pt) 2000-02-29 2002-11-26 Unilever Nv Composição alvejante, método para alvejar um substrato, e, ligando
GB0004988D0 (en) 2000-03-01 2000-04-19 Unilever Plc Composition and method for bleaching a substrate
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DE59802351D1 (de) 2002-01-17
WO1998054282A1 (fr) 1998-12-03
US6479450B1 (en) 2002-11-12
ES2169525T3 (es) 2002-07-01
EP0985019A1 (fr) 2000-03-15
ATE210178T1 (de) 2001-12-15
JP2001526729A (ja) 2001-12-18

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