EP1576196B1 - Verfahren zur herstellung eines synthetischen aluminiumgerbmittels - Google Patents

Verfahren zur herstellung eines synthetischen aluminiumgerbmittels Download PDF

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Publication number
EP1576196B1
EP1576196B1 EP02781713A EP02781713A EP1576196B1 EP 1576196 B1 EP1576196 B1 EP 1576196B1 EP 02781713 A EP02781713 A EP 02781713A EP 02781713 A EP02781713 A EP 02781713A EP 1576196 B1 EP1576196 B1 EP 1576196B1
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Prior art keywords
aluminium
acid
range
tanning
per mole
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Expired - Lifetime
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EP02781713A
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English (en)
French (fr)
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EP1576196A1 (de
Inventor
Central Leather Research Inst KANTHIMAHI Mookandi
P. Central Leather Research Inst. THANIKAIVELAN
Jonnalagadda R. Central Leather Research Inst RAO
Balachandran U. Central Leather Research Inst NAIR
T. Central Leather Research Institute RAMASAMI
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Council of Scientific and Industrial Research CSIR
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Council of Scientific and Industrial Research CSIR
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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
    • C14C3/08—Chemical tanning by organic agents
    • C14C3/18—Chemical tanning by organic agents using polycondensation products or precursors thereof
    • C14C3/20—Chemical tanning by organic agents using polycondensation products or precursors thereof sulfonated
    • 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

Definitions

  • the present invention relates to a process for the preparation of a novel synthetic aluminium tanning agent. More particularly the present invention provides a process for the preparation of a synthetic organo-aluminum tanning agent without using formaldehyde, which forms an alternative to chrome tanning material.
  • the compound has use as a self-tanning agent for hides and skins. Additionally, it is envisaged to be capable to produce fuller leathers with adequate shrinkage temperature for producing leathers with desirable properties. It is also envisaged that the white base of the leathers enhances dyeability and acts as dye saver apart from ample production of white leathers.
  • chrome tanning has been the most predominant method of tannage for the commercial purpose.
  • the major limitation associated with this is that the chrome tanned leathers are empty in nature and hence need heavy retanning for its final performance.
  • chrome tanned leather does not provide any lubrication among the fibres. Hence strong fatliquoring becomes mandatory for the desired level of softness.
  • chrome tanning practices employ basic chromium sulphate salt, a progenitor of several chromium species, having various charges and degree of polymerisation.
  • the kinetic inertness of certain chromium species lends itself to poor exhaustion (50-70%) of chrome tanning salt.
  • the commercial chrome tanning activities release chromium in the range of 2000-5000 ppm.
  • Aluminum tanning is one of the oldest methods of tanning. An old name 'tawing' has been used for this process, which consists of treating the skin with potassium alum in the form of paste including sodium chloride, egg yolk, flour and water.
  • Aluminum tanned leathers are sensitive to water and heat. Aluminum tanned leather has a shrinkage temperature in the range of 75-82°C depending on the method of tanning used. Its water resistance is unsatisfactory, since even a wash with the cold water slowly removes aluminium compounds from leather. Aluminium being d° element, its complexes are much less stable than those of chromium; and thus their binding to collagen is much weaker. This is the reason why aluminium salts are used in contemporary tanning almost exclusively in combined tannage processes. Generally aluminium tanning is done in floats of zero basicity at high concentrations in the presence of sodium chloride to prevent swelling, because the pH of the float is as low as 2.5 - 3.5. No washing is employed after tanning.
  • Aluminium based tanning agents like Lutan B and ATC - 21 have not found much commercial acceptability because of the ready reversal of aluminium as aluminium hydroxide at pH values in the range of 5.0-6.0.
  • Lipowski US Patent 4,443,382 , 1984
  • the polymeric matrix is made using formaldehyde.
  • the high cationic potential of Al(III) makes such salts useful for enhancing the color yield.
  • US-A-4723001 describes general background art in the field of dyeing nitrogen containing or hydroxy-containing materials. Certain chromium complexes having a radical of a bidentate bianionic compound water or an amine-type compound, a benzene or naphthalene diazo component and other groups attached to the chromium atom are described.
  • Derwert abstract number 1988 - 153443 (SH1348372A ) describes the treatment in adrumona semi-finished cattle leather after chrome-tanning and neutralisation by treating with a water soluble antiseptic. Thereafter, dyeing and fat liquoring processes are carried out and acetic or formic acid is then added to fix the resin into the structure of the derma followed by drying.
  • GB-A-1554886 discloses thrombocytes which have been reacted with a tanning agent.
  • a suspension of thrombocytes is also disclosed.
  • GB-A-2069694 discloses immunological reagents for detecting rheumatoid factor.
  • the reagent disclosed comprises a complex of red blood cells and antibodies soluble with respect to the cells and immunologically fixed thereto.
  • the reagent is stable and capable of providing hemaglutination subject to contacting it with detectable concentrations of rheumatoid factor.
  • the reagent may be compared by subjecting red cells and antibodies to successive treatments with aldehydes or tanning agents and with proteinic substances having dispersive properties, for example albumin.
  • US-A-4830632 relates to aqueous compositions from a sulfonated phenol, and amine and the tanning salt.
  • the tanning salt is mixed with a composition containing the sulfonated phenol, and the amine and optionally a salt of EDTA or pyrophosphate.
  • GB-A-2068999 which relates to tanning leather.
  • Animal skins are treated in a bath containing a polyvalent metal salt and polymer or oligomer containing carboxyl, hydroxy or carboxyl derivative functional groups capable of reacting with the polyvalent ion.
  • the colour, or lack of it in the animal skin is stabilised by the polymer or oligomer.
  • the main pre-requisite for conventional chrome tanning process carried out using either basic chromium sulphate (BCS) or high exhaust chrome tanning salt, is to pickle the pelt by employing acid and salt in aqueous medium whereby the emanated liquor is loaded with dissolved solids, chlorides and sulphates, leading thereby to the environmental pollution.
  • BCS basic chromium sulphate
  • high exhaust chrome tanning salt is to pickle the pelt by employing acid and salt in aqueous medium whereby the emanated liquor is loaded with dissolved solids, chlorides and sulphates, leading thereby to the environmental pollution.
  • the main objective of the invention is to provide a process for the preparation of a novel synthetic aluminium tanning agent, which obviates the drawbacks stated above.
  • Another objective of this invention is to provide an organo aluminium complex for direct tanning of delimed pelts without the conventional pickling process thereby reducing the total dissolved solids in the effluent.
  • Yet another objective of the invention is to provide a method for the preparation of Al(III) tanning salt in homogenous chemical formulation in which Al(III) binds irreversibly with skin/hide matrix and resists washing even at a pH 7.
  • Still another objective of the invention is to provide a method for the preparation of Al(III) tanning salt which when used in tanning gives leathers with shrinkage temperature more than 80°C unlike the conventional aluminum tanned leathers.
  • Still another objective of the invention is to provide a product for the manufacture of white leathers through an eco-friendly application procedure.
  • Yet another objective of the invention is to provide a product, which serves as dye saver and efficient chrome saver.
  • Still another objective of the invention is to provide aluminium based syntan, which offers soft and fuller leathers unlike the conventional chrome tanned leather.
  • the present invention provides a process for the preparation of a novel synthetic aluminium tanning agent, which comprises
  • the sulfonation in step (i) is carried out at a temperature in the range of 25-160°C.
  • the aqueous mixture of organic ligands and polyfunctional polymer is added to the sulfonated aromatic compound at a temperature in the range of 60 - 80°C.
  • the addition of trivalent aluminium salt along with water to the reaction mixture formed in step(i) is carried out at a temperature in the range of 60 - 80°C.
  • the addition of sulfosalicylic acid to the reaction mixture formed in step(ii) is done at a temperature in the range of 60 - 80°C.
  • the slurry obtained in step (iv) is aerated for a period of 30 - 60 min before drying at a temperature in the range of 130-260°C to get the tanning agent in powder form.
  • the aromatic compound used is selected from the group consisting of phenol, phenolic acid, naphthol, naphthalene and anthracene.
  • the amount of the aromatic compound used is in the range of 0.5 - 2.0 moles per mole aluminium.
  • sulfonation is carried out using sulfuric acid in an amount in the range of 1 - 5 moles per mole of aluminium.
  • the organic ligand used is selected from the group consisting of formic acid, citric acid, phthalic acid, poly carboxylic acid, oxalic acid, salicylic acid, sodium salts thereof and any mixture thereof.
  • the amount of organic ligands used is in the range of 0.001 - 0.05 mole per mole of aluminium.
  • the polyfunctional polymer used is selected from the group consisting of polyacrylic acid, polyacryl amide, polymethacrylic acid, and any mixture thereof.
  • the amount of the polyfunctional polymer used is in the range of 0.0001- 0.001 mole per mole of aluminium.
  • the trivalent aluminium salt is selected from the group consisting of aluminium sulfate, aluminium chloride, aluminium ammonium sulfate and aluminium potassium sulfate.
  • the amount of water added to the reaction mixture is in the range of 5 - 30 moles per mole of aluminium.
  • the amount of sulfosalicylic acid used is in the range of 0.001- 0.01 moles per mole of aluminium.
  • the amount of sulfuric acid used for sulfonating aromatic compound is in the range of 0.001 - 0.01 moles per mole of aluminium.
  • drying of the slurry is done by drum drying or spray drying.
  • An aromatic hydrocarbon having up to 14 carbon atoms, calculated as 0.5-2.0 moles per mole of aluminium to be used, is sulfonated by known method using 1 to 5 moles sulphuric acid per mole of aluminium for a period of not less than 60 minutes at a temperature in the range 25-160°C.
  • An aqueous mixture of 0.001 - 0.05 mole of organic ligand per mole of aluminium is then added to the sulfonated mass along with 0.0001- 0,001 moles polyfunctional polymer per mole of aluminium at a temperature of 60 - 80°C with continuous stirring whereby the organic matrix is built up.
  • Trivalent aluminium salt is then added to the resulting mixture along with 5 - 30 moles of water per mole of aluminium while maintaining the temperature in the range of 60 - 80°C.
  • Al(III) being a d 0 non-transition element, needs a critical additive that is capable of converting it to a pseudo-transition element by transferring the electrons to 3s, 3p and 3d orbitals. Hence, the reaction is continued for a period of 60 minutes.
  • a critical additive in the range of 0.001 - 0.01 mole per mole of aluminium is sulfonated by known method using 0.001 - 0.01 moles sulphuric acid per mole of aluminium for a period of not less than 3 hours at a temperature in the range 25 - 28°C.
  • the sulfonated critical additive is then added to the reaction mixture.
  • the heating and stirring was continued for another 30 min. after which the completion of the reaction is confirmed by known solublization technique.
  • the resulting mixture is then adjusted to a pH of 2.5 - 3.0 by conventional method.
  • the slurry is dried conventionally at a temperature range of 130 - 260°C to obtain the organo aluminium complex as a white powder.
  • the novelty and non obviousness of the present development lies in using polyfunctional polymer for providing a polymeric matrix without ethylene bridge with suitable critical additive that is capable of anchoring a d 0 non-transition element, Al(III), by charge transfer mixing of 3s, 3p and 3d orbitals.
  • suitable critical additive that is capable of anchoring a d 0 non-transition element, Al(III), by charge transfer mixing of 3s, 3p and 3d orbitals.
  • the irreversible binding of aluminium to the organic matrix is achieved by using organic ligands in combination with critical additive having ligating sites capable of anchoring trivalent aluminium ion.
  • the naphthalene sulfonic acid, prepared in flask was allowed to cool down to 60°C and transferred to a reactor fitted with a thermometer, stirrer and a dropping funnel. The mass was stirred continuously for a period of 10 min. while maintaining the temperature at 60°C with the help of the thermostat.
  • a mixture of 0.2 gm poly acrylic acid, 0.25 gm phthalic acid, 1 gm citric acid and 0.14 gm salicylic acid was dissolved in 10 ml water in a beaker and the same was added to the reaction mass in the reactor through the dropping funnel. The mixture was heated at 65°C for 20 min.
  • the product was used for tanning the delimed goat skins at an offer of 1.5% as Al 2 O 3 on pelt weight.
  • the tanned leather was left over night and the shrinkage temperature was found to be 85°C exhibiting 80-82% exhaustion of aluminium.
  • the anthracene sulfonic acid was cooled to 60°C and transferred to the reactor fitted with a condenser, stirrer and a dropping funnel.
  • the reactor was fitted into a thermostated water bath and the sulfonated mass was stirred for 10 min. at a temperature of 60°C.
  • a mixture of 1 gm citric acid, 0.06 gm oxalic acid, 0.01 gm phthalic acid, 0.03 gm sodium formate and 0.1 gm poly acrylic acid was dissolved in 15 ml water and added to the reaction mixture keeping the temperature at 60°C. The mass was heated at 65°C for 40 minutes.
  • the product was used for tanning the delimed goat skins at an offer of 1.5% as Al 2 O 3 on pelt weight.
  • the tanned leather was left over night and the shrinkage temperature was found to be 84°C, exhibiting an uptake of 80% aluminium.
  • the phenol sulfonic acid prepared in the flask was allowed to cool down to 60°C and transferred to the reactor fitted with a thermostat, stirrer and a dropping funnel. The mass was stirred for 10 min. at 60°C. A mixture of 0.6 gm poly acrylic acid, 0.05 gm of phthalic acid in 2 ml water was added to the reactor through the dropping funnel. The mixture was stirred for 30 min. maintaining the temperature at 60°C. 136 gms of ammonium aluminium sulfate was added to the above mass along with 100 ml water with vigorous stirring. The temperature of the bath was gradually raised to 70°C and heating continued for 1 hr.
  • the pre made sulfo salicylic acid was added to the reactor and the heating was continued for 1 hour.
  • the reaction mixture was transferred to a bucket and the pH was adjusted to 3.0 using sodium bicarbonate.
  • the solution was filtered and dried using a spray drier at a temperature of 260°C. The dried product was packed in a plastic container.
  • This product was used for tanning the delimed goatskins at an offer of 1.5% as Al 2 O 3 on pelt weight.
  • the tanned leathers were aged for one day and the shrinkage temperature of the tanned leather was found to be 85°C, exhibiting 78% exhaustion of aluminium.
  • the sulfonated phenolic acid prepared in the flask was allowed to cool down to 60°C and transferred to the reactor fitted with a thermostat, stirrer and a dropping funnel. The mass was stirred for 10 min. at 60°C. A mixture of 0.6 gm poly acrylic acid, 0.05 gm of phthalic acid in 2 ml water was added to the reactor through the dropping funnel. The mixture was stirred for 30 min. maintaining the temperature at 60°C. 72 gms of aluminium chloride was added to the above mass along with 100 ml water with vigorous stirring. The temperature of the bath was gradually raised to 70°C and heating continued for 1 hr. The pre made sulfo salicylic acid was added to the reactor and the heating was continued for 1 hour. The reaction mixture was transferred to a bucket and the pH was adjusted to 3.0 using sodium bicarbonate. The solution was filtered and dried using a spray drier at a temperature of 260°C. The dried product was packed in a plastic container.
  • This product was used for tanning the delimed goatskins at an offer of 1.5% as Al 2 O 3 on pelt weight.
  • the tanned leathers were aged for one day and the shrinkage temperature of the tanned leather was found to be 84°C, exhibiting 78% exhaustion of aluminium.
  • the naphthol sulfonic acid prepared in the flask was allowed to cool down to 60°C and transferred to the reactor fitted with a thermostat, stirrer and a dropping funnel. The mass was stirred for 10 min. at 60°C. A mixture of 0.6 gm poly acrylic acid, 0.05 gm of phthalic acid in 2 ml water was added to the reactor through the dropping funnel. The mixture was stirred for 30 min. maintaining the temperature at 60°C. 136gms of ammonium aluminium sulfate was added to the above mass along with 100ml water with vigorous stirring. The temperature of the bath was gradually raised to 70°C and heating continued for 1 hr.
  • the pre made sulfo salicylic acid was added to the reactor and the heating was continued for 1 hour.
  • the reaction mixture was transferred to a bucket and the pH was adjusted to 3.0 using sodium bicarbonate.
  • the solution was filtered and dried using a spray drier at a temperature of 260°C. The dried product was packed in a plastic container.
  • This product was used for tanning the delimed goatskins at an offer of 1.5% as Al 2 O 3 on pelt weight.
  • the tanned leathers were aged for one day and the shrinkage temperature of the tanned leather was found to be 85°C, exhibiting 80% exhaustion of aluminium.

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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)
  • Chemical Treatment Of Metals (AREA)

Claims (19)

  1. Ein Verfahren zur Herstellung eines neuartigen synthetischen Aluminiumgerbmittels, welches umfasst:
    i) Sulfonieren einer aromatischen Verbindung mit bis zu 14 Kohlenstoffatomen und anschließend die Zugabe eines wässrigen Gemisches aus organischen Liganden und polyfunktionellem Polymer,
    ii) Zugabe von dreiwertigem Aluminiumsalz zusammen mit Wasser zu dem in Schritt (i) gebildeten Reaktionsgemisch und Mischen der Reaktionsmasse zur Bildung eines Komplexes,
    iii) Zugabe von Sulfosalicylsäure zu dem in Schritt (ii) gebildeten Reaktionsgemisch zur Bildung einer Aufschlämmung,
    iv) Einstellen des pH der in Schritt (iii) gebildeten Aufschlämmung auf einen Bereich von 2,5-3,0 mit einem alkalisierenden Agens,
    v) Trocknen der Aufschlämmung zum Erhalt des Gerbmittels in Pulverform.
  2. Ein Verfahren wie in Anspruch 1 beansprucht, worin die Sulfonierung in Schritt (i) bei einer Temperatur im Bereich von 25-160°C durchgeführt wird.
  3. Ein Verfahren wie in Anspruch 1 beansprucht, worin das wässrige Gemisch aus organischen Liganden und polyfunktionellem Polymer zu der sulfonierten aromatischen Verbindung bei einer Temperatur im Bereich von 60-80°C gegeben wird.
  4. Ein Verfahren wie in Anspruch 1 beansprucht, worin die Zugabe von dreiwertigem Aluminiumsalz zusammen mit Wasser zu dem in Schritt (i) gebildeten Reaktionsgemisch bei einer Temperatur im Bereich von 60-80°C durchgeführt wird.
  5. Ein Verfahren wie in Anspruch 1 beansprucht, worin die Zugabe von Sulfosalicylsäure zu dem in Schritt (ii) gebildeten Reaktionsgemisch bei einer Temperatur im Bereich von 60-80°C erfolgt.
  6. Ein Verfahren wie in Anspruch 1 beansprucht, worin die in Schritt (iv) erhaltene Aufschlämmung über einen Zeitraum von 30-60 Minuten vor dem Trocknen bei einer Temperatur im Bereich von 130-260°C belüftet wird, zum Erhalt des Gerbmittels in Pulverform.
  7. Ein Verfahren wie in Anspruch 1 beansprucht, worin die eingesetzte aromatische Verbindung aus der Gruppe ausgewählt ist, bestehend aus Phenol, Phenolsäure, Naphthol, Naphthalen und Anthracen.
  8. Ein Verfahren wie in Anspruch 1 beansprucht, worin die Menge an eingesetzter aromatischer Verbindung im Bereich von 0,5-2,0 Mol pro Mol Aluminium liegt.
  9. Ein Verfahren wie in Anspruch 1 beansprucht, worin die Sulfonierung unter Verwendung von Schwefelsäure in einer Menge im Bereich von 1-5 Mol pro Mol Aluminium durchgeführt wird.
  10. Ein Verfahren wie in Anspruch 1 beansprucht, worin der eingesetzte organische Ligand aus der Gruppe ausgewählt ist, bestehend aus Ameisensäure, Citronensäure, Phthalsäure, Polycarbonsäure, Oxalsäure, Salicylsäure, Natriumsalzen davon und einem beliebigen Gemisch davon.
  11. Ein Verfahren wie in Anspruch 1 beansprucht, worin die Menge eingesetzter organischer Liganden im Bereich von 0,001-0,05 Mol pro Mol Aluminium liegt.
  12. Ein Verfahren wie in Anspruch 1 beansprucht, worin das eingesetzte polyfunktionelle Polymer aus der Gruppe ausgewählt ist, bestehend aus Polyacrylsäure, Polyacrylamid, Polymethacrylsäure und einem beliebigen Gemisch davon.
  13. Ein Verfahren wie in Anspruch 1 beansprucht, worin die Menge an eingesetztem polyfunktionellen Polymer im Bereich von 0,0001-0,001 Mol pro Mol Aluminium liegt.
  14. Ein Verfahren wie in Anspruch 1 beansprucht, worin das dreiwertige Aluminiumsalz aus der Gruppe ausgewählt ist, bestehend aus Aluminiumsulfat, Aluminiumchlorid, Aluminiumammoniumsulfat und Aluminiumkaliumsulfat.
  15. Ein Verfahren wie in Anspruch 1 beansprucht, worin die zu dem Reaktionsgemisch gegebene Wassermenge im Bereich von 5-30 Mol pro Mol Aluminium liegt.
  16. Ein Verfahren wie in Anspruch 1 beansprucht, worin die Menge an eingesetzter Sulfosalicylsäure im Bereich von 0,001-0,01 Mol pro Mol Aluminium liegt.
  17. Ein Verfahren wie in Anspruch 1 beansprucht, worin die Menge der zur Sulfonierung der aromatischen Verbindung eingesetzten Schwefelsäure im Bereich von 0,001-0,01 Mol pro Mol Aluminium liegt.
  18. Ein Verfahren wie in Anspruch 1 beansprucht, worin die Trocknung der Aufschlämmung mittels Trommeltrocknung oder Sprühtrocknung erfolgt.
  19. Ein Verfahren wie in Anspruch 1 beansprucht, worin das in Schritt (iv) eingesetzte alkalisierende Agens aus der Gruppe ausgewählt ist, bestehend aus Natriumbicarbonat, Natriumsulfit und NaOH.
EP02781713A 2002-12-23 2002-12-23 Verfahren zur herstellung eines synthetischen aluminiumgerbmittels Expired - Lifetime EP1576196B1 (de)

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Application Number Priority Date Filing Date Title
PCT/IB2002/005611 WO2004057036A1 (en) 2002-12-23 2002-12-23 Process for preparing a synthetic aluminium tanning agent

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EP1576196A1 EP1576196A1 (de) 2005-09-21
EP1576196B1 true EP1576196B1 (de) 2008-09-03

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EP (1) EP1576196B1 (de)
CN (1) CN100375789C (de)
AT (1) ATE407225T1 (de)
AU (1) AU2002348767B2 (de)
DE (1) DE60228767D1 (de)
WO (1) WO2004057036A1 (de)

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JP4638558B2 (ja) * 2008-12-22 2011-02-23 パナソニック株式会社 語音明瞭度評価システム、その方法およびそのコンピュータプログラム
CN102719571B (zh) * 2012-06-12 2014-10-29 陕西科技大学 一种含铝单宁的制备方法
CN103757148A (zh) * 2014-01-22 2014-04-30 烟台昊煜标本有限公司 一种制作毛皮动物标本的鞣皮工艺
CN104450991B (zh) * 2014-09-26 2017-02-22 山东力厚轻工新材料有限公司 一种不浸酸铬粉及其制备方法
CN113073160A (zh) * 2021-04-29 2021-07-06 陕西科技大学 一种具有稳定框架结构的羧酸配体MOFs纳米鞣剂及其制备方法和应用

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DE2546166A1 (de) * 1975-10-15 1977-04-28 Behringwerke Ag Gegerbte thrombozyten
GB2068999B (en) * 1980-02-11 1984-02-22 British Leather Mfg Res Tanning leather
FR2476320B1 (fr) * 1980-02-15 1985-10-25 Guffroy Rene Nouveau reactif immunologique pour la detection en tubes du facteur rhumatoide dans un echantillon biologique et procede de preparation de ce nouveau reactif
CH656140A5 (de) * 1983-11-04 1986-06-13 Ciba Geigy Ag Faserreaktive chromkomplexe und deren herstellung.
SU1348372A1 (ru) * 1986-03-07 1987-10-30 Центральный научно-исследовательский институт кожевенно-обувной промышленности Способ противоплесневой обработки кожи
US4830632A (en) * 1986-05-05 1989-05-16 Ciba-Geigy Corporation Aqueous composition from a sulfonated phenol, an amine and a tanning salt, process for the production thereof and use thereof as a tanning agent
JPH0488100A (ja) * 1990-08-01 1992-03-19 Yoshikawa Seiyu Kk 鞣剤およびその製造方法

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WO2004057036A1 (en) 2004-07-08
CN1720337A (zh) 2006-01-11
DE60228767D1 (de) 2008-10-16
AU2002348767A1 (en) 2004-07-14
EP1576196A1 (de) 2005-09-21
AU2002348767B2 (en) 2006-11-23
CN100375789C (zh) 2008-03-19
ATE407225T1 (de) 2008-09-15

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