EP1084279B1 - Substances tannantes contenant des unites n-vinyliques - Google Patents

Substances tannantes contenant des unites n-vinyliques Download PDF

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Publication number
EP1084279B1
EP1084279B1 EP99919155A EP99919155A EP1084279B1 EP 1084279 B1 EP1084279 B1 EP 1084279B1 EP 99919155 A EP99919155 A EP 99919155A EP 99919155 A EP99919155 A EP 99919155A EP 1084279 B1 EP1084279 B1 EP 1084279B1
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Prior art keywords
vinyl
weight
acid
monomer
leather
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EP99919155A
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German (de)
English (en)
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EP1084279A1 (fr
Inventor
Anton Negele
Gerhard Wolf
Axel Kistenmacher
Georg Igl
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BASF SE
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BASF SE
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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
    • C14C3/28—Multi-step processes
    • 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
    • C14C1/00—Chemical treatment prior to 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
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents
    • C14C3/22—Chemical tanning by organic agents using polymerisation products

Definitions

  • the present invention relates to the use of N-vinyl units containing polymers of N-vinyl amides and / or N-vinylamines and optionally monoethylenically unsaturated Carboxylic acids or their derivatives, other N-vinyl and / or C-vinyl compounds and other copolymerizable monomers in the form of aqueous solutions or dispersions as leather and Fellgerbstoffe.
  • the main tanning is usually used in leather production mineral tannins such as basic chrome, aluminum and / or Zirconium salts alone or in combination with synthetic Tannins carried out.
  • a subsequent retanning with natural or synthetic tanning agents is mainly used for Improvement of leather properties such as grip, softness, grain texture and abundance.
  • syntans i.e. water-soluble condensation products from e.g. naphthalenesulfonic and formaldehyde or from phenolsulfonic acid, formaldehyde and urea, also lignin sulfonic acids and also polymers and copolymers based on acrylic acid and other unsaturated polymerizable carboxylic acids, usually in combination with the aforementioned Syntanen used.
  • DE 196 12 986 describes copolymers for hydrophobizing leather and fur skins which contain at least 10% by weight of C 2 -C 6 olefins and monomers with alkyl chains which have at least 8 C atoms.
  • From DE-A 32 45 541, DE-A 32 48 019 and DE-A 32 48 031. are copolymers of vinylphosphonic acid esters, unsaturated Sulfonic acid esters, the amount of these two monomers together is at least 10% by weight, acrylamide and optionally up to 30% by weight of further monomers such as N-vinylamides and / or unsaturated Monocarboxylic acids known.
  • the copolymers are et al also recommended as retanning agents.
  • Copolymers of N-vinylcarboxamides and their monoethylenic unsaturated compounds such as acrylic acid, acrylic acid esters, Vinyl acetate, N-vinylpyrrolidone or acrylonitrile generally known as substances, as well as the effects of them modified copolymers obtainable from acids or bases, in which the carbonamide groups are wholly or partly from the polymerized N-vinyl carboxamides can be eliminated and in which the copolymerized comonomers are optionally are hydrolyzed.
  • Those partially or fully hydrolyzed Copolymers of N-vinylformamide are used, for example, as Dry and wet strength in the manufacture of paper, as Fixing agent and used as promoters for diketene sizing.
  • the known polymeric retanning agents for leather are relevant the fullness, fine and firm grain that they give the leather, and also in need of improvement in the dyeing behavior.
  • the present invention was therefore based on the object such retanning agents with improved properties provide.
  • Examples of monomers (A) of the formula I are as follows Vinyl carboxamides into consideration: N-vinylformamide, N-vinyl-N-methylformamide, N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl propionamide, N-vinyl-N-methyl propionamide and N-vinyl butyramide. Used from this group of monomers one prefers N-vinylformamide.
  • Suitable monomers (A) of the formula II are, for example, the vinylamines corresponding to the vinylcarboxamides mentioned above (H instead of R 1 ) with the same radical R 2 .
  • Monoethylenically unsaturated carboxylic acids are suitable as monomers (B) with 3 to 8 C atoms, in particular with 3 to 6 C atoms, such as acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, Maleic acid, citraconic acid, methylene malonic acid, allylacetic acid, Vinylacetic acid, crotonic acid, fumaric acid, mesaconic acid and Itaconic acid.
  • the monoethylenically unsaturated carboxylic acids can in the form of the free acid and - if available - the Anhydrides or in partially or fully neutralized Form used in the copolymerization.
  • ammonia or amines e.g. caustic soda, Potash lye, soda, potash, sodium hydrogen carbonate, magnesium oxide, Calcium hydroxide, calcium oxide, gaseous or aqueous ammonia, Triethylamine, ethanolamine, diethanolamine, triethanolamine, Morpholine, diethylene triamine or tetraethylene pentamine.
  • Suitable monomers (B) are, for example, the esters, Amides and nitriles of the above carboxylic acids, e.g. Acrylic acid methyl ester, acrylic acid ethyl ester, methacrylic acid methyl ester, Methyl methacrylate, hydroxyethyl acrylate, Hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, Hydroxypropyl methacrylate, hydroxyisobutylacrylate, Hydroxyisobutyl methacrylate, maleic acid monomethyl ester, maleic acid dimethyl ester, Maleic acid monoethyl ester, maleic acid diethyl ester, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, acrylamide, Methacrylamide, N-dimethylacrylamide, N-tert-butylacrylamide, Acrylonitrile, methacrylonitrile, dimethylamino
  • the monomers (B) used are Acrylic acid, methacrylic acid, maleic acid, maleic anhydride or Mixtures of these.
  • styrene and methylstyrenes i.e. ⁇ -methylstyrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene and p-methylstyrene, preferred.
  • Examples of other copolymerizable monomers (D) are Acrylamidoglycolic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, Styrene sulfonic acid, acrylic acid (3-sulfopropyl) ester, Methacrylic acid (3-sulfopropyl) ester and acrylamidomethylpropanesulfonic acid as well as containing phosphonic acid groups Monomers such as vinylphosphonic acid, allylphosphonic acid and acrylamidomethane propanephosphonic acid, to call.
  • graft copolymers are also those described above Homo- or copolymers containing N-vinyl units as a graft base with, for example, styrene and / or methylstyrenes, Acrylonitrile, n-butyl acrylate, n-butyl methacrylic acid or further monomers already mentioned in the above part to subsume under the demanding polymers. It is of course also possible, mixtures of all already mentioned Monomers for grafting the polymers containing N-vinyl units use.
  • the monomers (A) are preferably used in an amount of 5 to 95 wt .-%, in particular 10 to 70 wt .-%, especially 20 to 60 wt .-%, used.
  • the monomers (B) are preferably used in an amount of 5 to 95% by weight, in particular 10 to 90% by weight, especially 25 to 75% by weight.
  • the monomers (C) are preferably used in an amount of 0 to 50 wt .-%, in particular 1 to 50 wt .-%, used.
  • the monomers (D) are preferably used in an amount of 0 to 9% by weight, in particular from 0 to 5% by weight, especially from 0.1 to 5 wt .-%, used.
  • the polymers described are prepared by known methods Processes, e.g. the solution, precipitation, suspension or Emulsion polymerization, using radical-forming Links.
  • the polymerization temperatures are usually in the range from 30 to 200 ° C, preferably 40 to 110 ° C.
  • the polymerization takes place in the presence of polymerization inhibitors form radicals under the given polymerization conditions.
  • Suitable initiators are, for example, hydrogen peroxide, Peroxides, hydroperoxides, redox catalysts and in particular non-oxidizing initiators, such as radicals Azo compounds such as 2,2'-azo-bis (2-amidinopropane) dihydrochloride, 2,2'-azo-bis (N, N-dimethyleneisobutyramidine) dihydrochloride, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] or 2,2'-azobisisobutyronitrile. It is of course also possible to use mixtures different initiators.
  • the amount of starter for the radical polymerization that is used is in the range from 0.001 to 5%
  • the initiator amounts which in the Polymerization are usually used, increase so that one outside the range given above for the initiator amounts lies.
  • Low molecular weight copolymers can also do this can be obtained in the presence of polymerization regulators works or polymerization regulator and higher amounts of initiators than usually required.
  • Suitable polymerization regulators can be in amounts of 0.05 to 20 wt .-%, based on the total amount of monomers, are added and are, for example, formic acid, dodecyl mercaptan, thioglycolic acid, Thioacetic acid and mercapto alcohols, such as mercaptoethanol, Mercaptopropanols and mercaptobutanols.
  • the polymers described have K values of at least 7, they are preferably from 10 to 250, in particular from 20 to 100. However, the polymers can also assume K values of up to 300.
  • the K values are determined according to H. Fikentscher, CelluloseChemie, Volume 13, pages 58 to 64 and 71 to 74 (1932), in aqueous Solution at 25 ° C at concentrations depending on the K value range are between 0.1% and 5% by weight.
  • the substituents R 1 and R 2 each have the meaning given above.
  • the comonomers used can also be chemically changed depending on the chosen hydrolysis condition, for example vinyl alcohol units are formed from vinyl acetate units, methyl acrylate units from acrylic acid units and acrylamide units from acrylonitrile units. acrylic acid units.
  • the units of the formula IIa can thus either be used of N-vinylamines II as monomers (A) or by the described Hydrolysis of the units derived from the N-vinylamide monomers I.
  • Formula Ia arise.
  • Suitable hydrolysis agents are mineral acids, for example hydrogen halides, which can be used in gaseous form or in aqueous solution. Hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid and organic acids, for example C 1 -C 5 -carboxylic acids and aliphatic or aromatic sulfonic acids, are preferably used. 0.05 to 2, preferably 1 to 1.5 molar equivalents of an acid are required per acyl group equivalent which is to be split off from the copolymerized units Ia.
  • Hydrolysis of the polymerized units of structure Ia can also be done using bases, e.g. of Metal hydroxides, especially alkali metal or alkaline earth metal hydroxides. Sodium hydroxide or is preferably used Potassium hydroxide. The hydrolysis can also take place in the presence of ammonia or amines can be carried out.
  • bases e.g. of Metal hydroxides, especially alkali metal or alkaline earth metal hydroxides.
  • the hydrolysis can also take place in the presence of ammonia or amines can be carried out.
  • the present invention thus also relates to a method for single tanning, pre-tanning and co-tanning of bare and Hide and for retanning leather and fur, which thereby is characterized in that the tanning agents described are the N-vinyl units containing polymers in the form of aqueous solutions or uses dispersions.
  • the polymers used according to the invention can be tanned of bare and pelts together with the tanning agents of the main tanning process, which, for example, a chrome, aluminum, titanium or Zirconium tanning can be used.
  • the working conditions regarding pH value, temperature and Duration of treatment based on the requirements of the main components tanning is stopped, the same applies to the treatment apparatus and the length of the liquor as well as for post-treatment.
  • the required amount of copolymer used according to the invention is usually 0.1, based on the weight of the nakedness up to 20% by weight, in particular 0.5 to 15% by weight.
  • the polymers used according to the invention for retanning already tanned leather and fur for example Chrome leather (so-called wet blue), wet white (with e.g. aldehydes or synthetic tanning agents, pre-tanned bare skin or bare skin) or vegetable tanned leather or fur, in water Fleet can be used.
  • Chrome leather is preferably retanned.
  • the pecked Bare and hides for example cowhide with gaps of 1.5 to 4 mm, for example with a chrome-containing tannin such as a chromium III salt, e.g.
  • the leather is or fur usually adjusted to a pH of 3 to 5, including an organic acid such as formic acid or their salts, carbonic acid salts, or synthetic Tanning agents with a neutralizing effect are used, and against Colors and greases at the end or after treatment if desired.
  • an organic acid such as formic acid or their salts, carbonic acid salts, or synthetic Tanning agents with a neutralizing effect are used, and against Colors and greases at the end or after treatment if desired.
  • the leather or fur retanned in this way can be retanned with the polymers used according to the invention additionally with other tanning agents like other polymer tanning agents, synthetic or vegetable tannins. Can too the polymers used according to the invention simultaneously with such additional tanning agents are used.
  • tanning agents all usual agents with a tanning effect on the bare and fur bare in Consideration.
  • a comprehensive treatment of such tanning agents is found for example, in Ullmann’s encyclopedia of technical chemistry, 3rd edition, 11th volume, pages 585 to 612 (1960).
  • Tannin classes mentioned are the mineral tannins, e.g. Chromium, aluminum, titanium and zirconium salts, the synthetic Tannins, vegetable tannins and polymer tannins.
  • the polymer solution was then in the same glass reactor heated to 80 ° C and within an hour 80 g of a 50% sodium hydroxide solution were added dropwise. Subsequently was stirred for 2 hours at this temperature, cooled and adjusted to pH 7.0 with concentrated hydrochloric acid. The Degree of hydrolysis of the polymer was 100%.
  • Example A Retanning from chrome leather to shoe upper leather
  • a 1.5 mm thick beef blue was used in the usual Rinsed, washed and then with sodium formate and deacidified sodium bicarbonate at 30 ° C to pH 4.5. After washing, 1% of the hydrolyzed copolymer from Example 1, based on the Solids content, drummed at 35 ° C for 30 minutes and then at 4% a commercially available synthetic tanning agent based on of a phenolsulfonic acid-formaldehyde condensate and walked for another 90 minutes. After that, the leather was again washed and in 100% liquor at 50 ° C with 1% of a commercial Dye dyed within 20 minutes. It followed in the same fleet, the greasing with 5% of a commercially available Fat liquor.
  • Example A Analogously to Example A, the unhydrolyzed or partially hydrolyzed copolymers from Examples 2 to 4 used, depending on the composition of the products Properties varied in depth, color depth and fine grain.
  • the leathers were full-grain, especially in the flames and flanks.
  • the colors were the usual ones Superior polymers in color depth and levelness.
  • Example B Retanning chrome leather in combination with vegetable Tanning agents for upper leather
  • Example A Analogous to Example A, a beef wetting blue of fold thickness was used Washed 1.5 mm and deacidified. After that the treatment followed of the leather in 100% liquor with 1%, based on the Active substance content of the hydrolyzed copolymer Example 1 within 30 minutes at 40 ° C. Thereupon became the same fleet 5% of a commercially available vegetable tanning agent (Mimosa) and 2% of a commercially available resin tanning agent added and tumbled for 90 minutes. The fleet was with Formic acid adjusted to pH 4.2 and again 20 minutes fulled. Washing was then carried out analogously to Example A, colored, greased and acidified. You got a constant Leather with excellent fullness and firmness, in particular suitable for the firmer shoe type. The coloring was despite the Use of vegetable tannin very brilliant, no matter and deeply colored.
  • Mimosa commercially available vegetable tanning agent
  • Example B shows this extremely well good combinability of the polymers according to the invention with the synthetic materials commonly used in leather production or vegetable tannins.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (6)

  1. Utilisation de polymères contenant des unités N-vinyliques, qui peuvent être obtenus par polymérisation initiée par voie radicalaire d'un monomère ou d'un mélange de monomères de
    (A) un N-vinylamide de formule générale I
    Figure 00190001
    et/ou une N-vinylamine de formule générale II H2C=CH-NH-R2
    dans lesquelles R1 et R2 désignent, indépendamment l'un de l'autre, l'hydrogène ou un alkyle en C1 à C6,
    tandis que les groupes N-acyle provenant des N-vinylamides I peuvent être éliminés partiellement ou totalement des polymères obtenus, par élimination hydrolytique avec des acides ou des bases,
    sous forme de solutions ou dispersions aqueuses en tant que substances tannantes pour tannage isolé, prétannage ou tannage conjoint de cuirs et de peaux et pour le post-tannage de cuir et de peau.
  2. Utilisation selon la revendication 1, caractérisée par le fait qu'on met en oeuvre des polymères qui peuvent être obtenus par polymérisation initiée par voie radicalaire d'un mélange de monomères de
    (A) 5 à 100 % en poids d'un N-vinylamide de formule générale I
    Figure 00200001
    et/ou d'une N-vinylamine de formule générale II H2C=CH-NH-R2 dans lesquelles R1 et R2 désignent, indépendamment l'un de l'autre, l'hydrogène ou un alkyle en C1 à C6,
    (B) 0 à 95 % en poids d'acides carboxyliques à insaturation monoéthylénique ayant 3 à 8 atomes de carbone, leurs sels de métal alcalin, de métal alcalino-terreux ou d'ammonium, anhydrides, esters, amides et/ou nitriles.
    (C) 0 à 95 % en poids d'autres composés N-vinyliques et/ou C-vinyliques du groupe de la N-vinylpyrrolidone, du N-vinylcaprolactame, du N-vinylimidazole, du N-vinyl-2-méthylimidazole, du N-vinyl-4-méthylimidazole, du chlorure de N,N-diallylammonium, de l'acétate de vinyle, du propionate de vinyle, du styrène et du méthylstyrène, et
    (D) 0 à moins de 10 % en poids d'autres monomères copolymérisables,
    tandis que la somme des monomères (A) à (D) est de 100 % en poids.
  3. Utilisation de polymères contenant des unités N-vinyliques selon la revendication 1 ou 2, qui peuvent être obtenus par polymérisation initiée par voie radicalaire d'un mélange de monomères comportant
    10 à 70 % en poids des monomères (A),
    10 à 90 % en poids des monomères (B),
    0 à 50 % en poids des monomères (C) et
    0 à 5 % en poids des monomères (D).
  4. Utilisation de polymères contenant des unités N-vinyliques selon les revendications 1 à 3, qui peuvent être obtenus par polymérisation initiée par voie radicalaire avec utilisation d'acide acrylique, d'acide méthacrylique, d'acide maléique, d'anhydride d'acide maléique ou de leurs mélanges, en tant que monomères (B).
  5. Utilisation de polymères contenant des unités N-vinyliques selon les revendications 1 à 4, dans laquelle les polymères présentent des indices K selon Fikentscher de 7 à 250.
  6. Procédé pour le tannage isolé, le prétannage et le tannage conjoint de peaux et de cuirs et pour le post-tannage de cuir et de peau, caractérisé par le fait qu'on utilise comme substances tannantes des polymères contenant des unités N-vinyliques selon les revendications 1 à 5, sous forme de solutions ou dispersions aqueuses.
EP99919155A 1998-04-09 1999-03-29 Substances tannantes contenant des unites n-vinyliques Expired - Lifetime EP1084279B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19815946A DE19815946A1 (de) 1998-04-09 1998-04-09 N-Vinyleinheiten enthaltende polymere Gerbstoffe
DE19815946 1998-04-09
PCT/EP1999/002147 WO1999053104A1 (fr) 1998-04-09 1999-03-29 Substances tannantes contenant des unites n-vinyliques

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EP1084279A1 EP1084279A1 (fr) 2001-03-21
EP1084279B1 true EP1084279B1 (fr) 2003-09-17

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US (1) US6652597B1 (fr)
EP (1) EP1084279B1 (fr)
JP (1) JP2002511523A (fr)
KR (1) KR20010042484A (fr)
BR (1) BR9909538A (fr)
DE (2) DE19815946A1 (fr)
ES (1) ES2212847T3 (fr)
WO (1) WO1999053104A1 (fr)

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DE10321628A1 (de) * 2003-05-13 2004-12-02 Basf Ag Verwendung von Copolymerisaten als Hilfsmittel für die Lederherstellung
DE10333749A1 (de) * 2003-07-23 2005-02-10 Basf Ag Verfahren zur Herstellung von Leder unter Verwendung von Polymerisaten
CN101942532A (zh) * 2009-07-06 2011-01-12 内蒙古际华森普利服装皮业有限公司 一种铬复合鞣剪绒直毛羊皮的加工工艺
AU2011225122B8 (en) * 2010-03-12 2013-12-12 Nippon Soda Co., Ltd. Compound containing pyridine ring and method for producing halogenated picoline derivative and tetrazolyloxime derivative
FI20115664A0 (fi) * 2011-06-23 2011-06-23 Kemira Oyj Polymeerituote ja sen käyttö dispergointiaineena
CN103276118B (zh) * 2013-05-08 2014-10-29 陕西科技大学 一种两性丙烯酸树脂皮革鞣剂
EP3695051B1 (fr) 2017-10-11 2024-06-19 Solenis Technologies Cayman, L.P. Procédé de fabrication à partir du papier ou du carton
CN111961768B (zh) * 2020-07-24 2023-07-28 汤普勒新材料嘉兴有限公司 一种两性聚丙烯酸复鞣剂的制备方法
CN112126025B (zh) * 2020-10-20 2023-03-24 汤普勒新材料嘉兴有限公司 一种两性聚合物复鞣加脂剂的制备方法
CN114369183A (zh) * 2021-11-30 2022-04-19 兄弟科技股份有限公司 一种阳离子化改性sma复鞣剂及其制备方法

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US2205883A (en) 1938-06-16 1940-06-25 Du Pont Tanning
DE3364923D1 (en) 1982-06-14 1986-09-04 Alcan Int Ltd Metal production by electrolysis of a molten metal electrolyte
DE3245541A1 (de) * 1982-12-09 1984-06-14 Cassella Ag, 6000 Frankfurt Wasserloesliche copolymerisate, ihre herstellung und ihre verwendung
EP0113438B1 (fr) * 1982-12-09 1989-03-08 CASSELLA Aktiengesellschaft Polymères solubles dans l'eau, leur préparation et leur usage
DE3248031A1 (de) 1982-12-24 1984-06-28 Cassella Ag, 6000 Frankfurt Wasserloesliche copolymerisate, ihre herstellung und ihre verwendung
DE3248019A1 (de) 1982-12-24 1984-06-28 Cassella Ag, 6000 Frankfurt Wasserloesliche copolymerisate, ihre herstellung und ihre verwendung
BR8605597A (pt) * 1985-11-13 1987-08-18 Cassella Farbwerke Mainkur Ag Tanino e processo para a sua obtencao e sua utilizacao
JPS6366205A (ja) * 1986-09-05 1988-03-24 Mitsubishi Chem Ind Ltd 水溶性ポリマ−の製造法
DE4201452A1 (de) * 1992-01-21 1993-07-22 Basf Ag Polymere gerbstoffe
DE19612986A1 (de) * 1996-04-01 1997-10-02 Basf Ag Verwendung von Copolymerisaten auf Basis ethylenisch ungesättigter Dicarbonsäuren oder Dicarbonsäureanhydride, niederer Olefine und hydrophober Comonomerer zum Nachgerben, Fetten oder Hydrophobieren von Leder und Pelzfellen

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EP1084279A1 (fr) 2001-03-21
WO1999053104A1 (fr) 1999-10-21
DE19815946A1 (de) 1999-10-14
JP2002511523A (ja) 2002-04-16
DE59907026D1 (de) 2003-10-23
KR20010042484A (ko) 2001-05-25
US6652597B1 (en) 2003-11-25
ES2212847T3 (es) 2004-08-01
BR9909538A (pt) 2000-12-12

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