EP0139039B1 - Stripping bath and process for the electrolytical stripping of metals from titanium as a base metal - Google Patents

Stripping bath and process for the electrolytical stripping of metals from titanium as a base metal Download PDF

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Publication number
EP0139039B1
EP0139039B1 EP83110698A EP83110698A EP0139039B1 EP 0139039 B1 EP0139039 B1 EP 0139039B1 EP 83110698 A EP83110698 A EP 83110698A EP 83110698 A EP83110698 A EP 83110698A EP 0139039 B1 EP0139039 B1 EP 0139039B1
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Prior art keywords
titanium
metals
stripping
base metal
sulfonic acids
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German (de)
French (fr)
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EP0139039A1 (en
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Gernot Dr. Strube
Jürgen Dr. Röder
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Dr Ing Max Schloetter GmbH and Co KG
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Dr Ing Max Schloetter GmbH and Co KG
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Priority to AT83110698T priority Critical patent/ATE30344T1/en
Priority to DE8383110698T priority patent/DE3374140D1/en
Priority to EP83110698A priority patent/EP0139039B1/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F5/00—Electrolytic stripping of metallic layers or coatings

Definitions

  • the invention relates to a method for the electrolytic removal of metals from titanium as the base metal in an electrolytic method using a special demetallization bath.
  • demetallization baths also contain aromatic nitro compounds as oxidizing agents, which interfere with the reprocessing of the solutions used.
  • This object is achieved according to the invention by a method for the electrolytic removal of Cd, Cr, Cu, Cu alloys, Ni, Pb, Pb / Sn. Sn or Zn of titanium as the base metal, which is characterized in that the titanium base body coated with the metals to be removed is at a current density of 0.1 to 100 A / dm 2 , a voltage of 0.1 to 25 V and at a temperature between 15 ° C up to the boiling point of the solution in an aqueous demetallization bath containing one or more alkylsulfonic acids, where the alkyl groups may optionally be hydroxy-substituted, in a concentration of 1 g up to the solubility limit.
  • Alkyl sulfonic acids for the aforementioned purpose are preferably those with 1 to 4 carbon atoms.
  • the alkyl groups can optionally be hydroxy-substituted.
  • Examples of preferred alkyl sulfonic acids are CH 2 (S0 3 H) 2 , CHgSOgH and HOCH 2 -CH 2 SO 3 H.
  • the demetallization baths used according to the invention can contain customary auxiliaries, such as activators, which accelerate the dissolution of the metals, e.g. B. thio compounds and halogens or inhibitors, e.g. B. non-ionic surfactants which favor the compact deposition of the dissolved metals in the alkyl sulfonic acid-containing solution on the cathode. This prevents metal powders from accumulating in the work containers.
  • activators which accelerate the dissolution of the metals
  • halogens or inhibitors e.g. B. non-ionic surfactants which favor the compact deposition of the dissolved metals in the alkyl sulfonic acid-containing solution on the cathode.
  • the titanium base metal with the metal coatings to be removed is switched as an anode and the electrolysis is carried out at a current density of 0.1 to 100 A / dm 2 , a voltage of 0.1 to 25 V and at a temperature between 15 ° C and the boiling point of the solution carried out taking care that the breakdown voltage for titanium is not exceeded under the given conditions.
  • a particular advantage of the demetallization bath used according to the invention for the electrolytic removal of metals from titanium as the base metal is that the titanium is not attacked by the demetallization bath.
  • the attack on titanium is immeasurably small and the base metal can be freed from the metal or metals deposited thereon with practically no damage.
  • Another advantage can also be seen in the fact that the detached metals that have gone into solution anodically can be deposited cathodically in a simple manner. It is therefore not necessary, as is the case with conventional stripper solutions, to discard the stripper solution after saturation.
  • a 20 ⁇ m thick copper layer is alternately placed on a titanium sheet of 100 x 20 x 2 mm and then a 10 ⁇ m thick lead-tin layer is deposited and this is repeated several times until an approximately 1 mm thick layer is present on the titanium sheet.
  • a solution is prepared from 250 g / l of hydroxyethanesulfonic acid and 750 g / l of water.
  • the titanium sheet coated with copper and tin is immersed in this solution and switched anodically.
  • the electrolysis is carried out until the copper and lead-tin coatings are completely detached. This takes about 200 minutes. It is then electrolyzed for a further 60 minutes under the same conditions.
  • the lead tin alloy and the metals copper, tin, silver and zinc are deposited on titanium sheet.
  • the metal is then anodically detached at 25 ° C. in an electrolyte containing 175 g / l methanesulfonic acid and the current efficiency is determined.
  • the lead tin alloy is deposited on titanium sheet.
  • the alloy is then detached from the titanium surface in an electrolyte containing 175 g / l methanesulfonic acid and 40 g / 1 fine grain additive.
  • an electrolyte containing 175 g / l methanesulfonic acid and 40 g / 1 fine grain additive.
  • By varying the temperature, stirring motion and cathodic current density it is determined whether lead tin can be cathodically compact again. With moderate stirring, compact, smooth and firmly adhering lead tin coatings are obtained at 60 ° C. and a cathodic current density of 10 A / dm 2 the cathode. At room temperature, compact and adherent coatings can be obtained up to a cathodic current density of 5 A / dm 2 and otherwise the same conditions.
  • Bright nickel and semi-gloss nickel are cathodically deposited on titanium sheet. These coatings are then anodically dissolved in an electrolyte.
  • the electrolyte contains 100 g / l methanesulfonic acid and various concentrations of halides.
  • the anodic current yield is determined at 20 A / dm 2 (anodic) and a temperature of 25 to 30 ° C. The results are shown in the table below.
  • Titanium anodized, is not attacked under these conditions.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

1. Process for the electrolytic stripping of Cd, Cr, Cu, Cu alloys, Ni, Pb, Pb/Sn, Sn or Zn from titanium as a base metal, characterized in that the titanium base covered with the metals to be stripped is anodically switched at a current density of 0.1 to 100 A/dm**2 , a voltage of 0.1 to 25 V and at a temperature between 15 degrees C up to the boiling point of the solution in an aqueous demetallization bath containing one or more alkyl sulfonic acids in which the alkyl groups may be hydroxy substituted if required at a concentration of 1 g up to the limit of solubility.

Description

Die Erfindung betrifft ein Verfahren zum elektrolytischen Abziehen von Metallen von Titan als Grundmetall in einem elektrolytischen Verfahren unter Anwendung eines speziellen Entmetallisierungsbades.The invention relates to a method for the electrolytic removal of metals from titanium as the base metal in an electrolytic method using a special demetallization bath.

Bei der Herstellung von Leiterplatten werden Gestelle, an denen die Leiterplatten befestigt werden, verwendet. Diese Gestelle dienen zur Übertragung des elektrischen Stromes auf die Leiterplatten. Bei der praktischen Anwendung scheiden sich auf den Gestellkontakten, d. h. an den Verbindungsstellen zwischen dem Gestell zur Leiterplatte die bei der Herstellung der Leiterplatten verwendeten Metalle ab. Bei der Metall-Resist-Technik wendet man üblicherweise die Reihenfolge Kupfer, Zinn oder Bleizinn oder Nickel an. Dabei dienen die Metalle Zinn, Bleizinn oder Nickel als Ätzresiste. Da sich diese Metalle zwangsläufig auch auf dem Gestell abscheiden, baut sich im Laufe der Zeit auf den Gestellen eine Metallschicht auf, wodurch die Funktionsweise der Kontaktierung negativ beeinflußt wird. Daher muß man die Gestelle nach einer gewissen Betriebszeit von den abgeschiedenen Metallen reinigen. Hierfür sind mehrere Stunden oder sogar Tage notwendig.In the manufacture of printed circuit boards, racks to which the printed circuit boards are attached are used. These frames are used to transfer the electrical current to the circuit boards. In practical use, the frame contacts differ. H. from the metals used in the manufacture of the printed circuit boards at the connection points between the frame and the printed circuit board. In the metal resist technique, the order of copper, tin or lead tin or nickel is usually used. The metals tin, lead tin or nickel serve as etching resists. Since these metals inevitably also deposit on the frame, a metal layer builds up on the frames over time, which negatively influences the functioning of the contact. Therefore, the frames have to be cleaned of the separated metals after a certain period of operation. This takes several hours or even days.

Aus der europäischen Patentanmeldung 0 077 582 ist es bekannt, Zinn oder Legierungen aus Zinn-Blei von einem Substrat unter Verwendung einer Lösung, die Alkylsulfonsäuren oder Oxycarbonsäuren sowie organische Oxidationsmittel enthält, zu entfernen. Nachteile dieser Lösungen sind :

  • (a) Verwendung irreversibler, teurer Oxidationsmittel.
  • (b) Die Lösungen sind erschöpft, wenn ca 40 bis 60 g/I Metall abgezogen worden sind. Die Lösung muß dann verworfen werden. Eine Wiederaufarbeitung ist nicht möglich.
  • (c) Die nicht mehr brauchbaren Lösungen müssen einem besonderen Standentgiftungsverfahren unterworfen werden, da sie Komplexbildner, wie Thioharnstoff, enthalten. Diese Entgiftungsverfahren sind sehr kostspielig.
From European patent application 0 077 582 it is known to remove tin or tin-lead alloys from a substrate using a solution containing alkylsulfonic or oxycarboxylic acids and organic oxidizing agents. Disadvantages of these solutions are:
  • (a) Use of irreversible, expensive oxidizing agents.
  • (b) The solutions are exhausted when about 40 to 60 g / l of metal have been removed. The solution must then be discarded. Refurbishment is not possible.
  • (c) The no longer usable solutions have to be subjected to a special detoxification process because they contain complexing agents such as thiourea. These detoxification procedures are very expensive.

Außerdem enthalten diese Entmetallisierungsbäder als Oxidationsmittel aromatische Nitroverbindungen, die bei der Wiederaufarbeitung der verwendeten Lösungen stören.These demetallization baths also contain aromatic nitro compounds as oxidizing agents, which interfere with the reprocessing of the solutions used.

Aufgabe der Erfindung ist es, ein Verfahren zum Entmetallisieren von mit Metallüberzügen versehenem Titan-Grundmetall zur Verfügung zu stellen, das ein einfaches elektrolytisches Abziehen der Metalle von dem Titan-Grundmetall ermöglicht...The object of the invention is to provide a method for demetallizing titanium base metal provided with metal coatings, which enables simple electrolytic removal of the metals from the titanium base metal ...

Diese Aufgabe wird erfindungsgemäß gelöst durch ein Verfahren zum elektrolytischen Abziehen von Cd, Cr, Cu, Cu-Legierungen, Ni, Pb, Pb/Sn. Sn oder Zn von Titan als Grundmetall, das dadurch gekennzeichnet ist, daß man den mit den abzuziehenden Metallen überzogenen Titangrundkörper bei einer Stromdichte von 0,1 bis 100 A/dm2, einer Spannung von 0,1 bis 25 V und bei einer Temperatur zwischen 15 °C bis zum Siedepunkt der Lösung anodisch in einem wässrigen Entmetallisierungsbad, enthaltend eine oder mehrere Alkylsulfonsäuren, wobei die Alkylgruppen gegebenenfalls hydroxysubstituiert sein können, in einer Konzentration von 1 g bis zur Löslichkeitsgrenze, schaltet.This object is achieved according to the invention by a method for the electrolytic removal of Cd, Cr, Cu, Cu alloys, Ni, Pb, Pb / Sn. Sn or Zn of titanium as the base metal, which is characterized in that the titanium base body coated with the metals to be removed is at a current density of 0.1 to 100 A / dm 2 , a voltage of 0.1 to 25 V and at a temperature between 15 ° C up to the boiling point of the solution in an aqueous demetallization bath containing one or more alkylsulfonic acids, where the alkyl groups may optionally be hydroxy-substituted, in a concentration of 1 g up to the solubility limit.

Alkylsulfonsäuren für den vorgenannten Zweck sind vorzugsweise solche mit 1 bis 4 C-Atomen. Gegebenenfalls können die Alkylgruppen hydroxysubstituiert sein. Beispiele für bevorzugte Alkylsulfonsäuren sind CH2(S03H)2, CHgSOgH und HOCH2-CH2SO3H.Alkyl sulfonic acids for the aforementioned purpose are preferably those with 1 to 4 carbon atoms. The alkyl groups can optionally be hydroxy-substituted. Examples of preferred alkyl sulfonic acids are CH 2 (S0 3 H) 2 , CHgSOgH and HOCH 2 -CH 2 SO 3 H.

Die erfindungsgemäß verwendeten Entmetallisierungsbäder können übliche Hilfsstoffe, wie Aktivatoren, welche die Auflösung der Metalle beschleunigen, z. B. Thioverbindungen und Halogene oder Inhibitoren, z. B. nicht-ionogene Tenside, die die kompakte Abscheidung der gelösten Metalle in der alkylsulfonsäurehältigen Lösung auf der Kathode begünstigen, enthalten. Dadurch kann die Ansammlung von Metallpulvern in den Arbeitsbehältern vermieden werden.The demetallization baths used according to the invention can contain customary auxiliaries, such as activators, which accelerate the dissolution of the metals, e.g. B. thio compounds and halogens or inhibitors, e.g. B. non-ionic surfactants which favor the compact deposition of the dissolved metals in the alkyl sulfonic acid-containing solution on the cathode. This prevents metal powders from accumulating in the work containers.

Beim erfindungsgemäßen Verfahren wird das Titan-Grundmetall mit den zu entfernenden Metallüberzügen als Anode geschaltet und die Elektrolyse wird bei einer Stromdichte von 0,1 bis 100 A/dm2, einer Spannung von 0,1 bis 25 V und bei einer Temperatur zwischen 15 °C und dem Siedepunkt der Lösung durchgeführt wobei darauf zu achten ist, daß die Durchschlagsspannung für Titan unter den gegebenen Bedingungen nicht überschritten wird.In the method according to the invention, the titanium base metal with the metal coatings to be removed is switched as an anode and the electrolysis is carried out at a current density of 0.1 to 100 A / dm 2 , a voltage of 0.1 to 25 V and at a temperature between 15 ° C and the boiling point of the solution carried out taking care that the breakdown voltage for titanium is not exceeded under the given conditions.

Ein besonderer Vorteil des erfindungsgemäß eingesetzten Entmetallisierungsbades zum elektrolytischen Abziehen von Metallen von Titan als Grundmetall ist darin zu sehen, daß das Titan durch das Entmetallisierungsbad nicht angegriffen wird. Während beispielsweise Edelstahl, sofern er nicht hoch legiert ist, durch eine alkylsulfonsäurehaltige Lösung angegriffen wird, ist der Angriff auf das Titan unmeßbar klein und das Grundmetall kann praktisch ohne jede Schädigung von dem darauf abgeschiedenen Metall oder Metallen befreit werden. Ein weiterer Vorteil ist auch darin zu sehen, daß die· anodisch in Lösung gegangenen abgelösten Metalle in einfacher Weise kathodisch abgeschieden werden können. Es ist deshalb nicht erforderlich, wie dies bei üblichen Stripperlösungen der Fall ist, nach Sättigung der Stripperlösung diese zu verwerfen.A particular advantage of the demetallization bath used according to the invention for the electrolytic removal of metals from titanium as the base metal is that the titanium is not attacked by the demetallization bath. For example, while stainless steel, if it is not high alloyed, is attacked by a solution containing alkyl sulfonic acid, the attack on titanium is immeasurably small and the base metal can be freed from the metal or metals deposited thereon with practically no damage. Another advantage can also be seen in the fact that the detached metals that have gone into solution anodically can be deposited cathodically in a simple manner. It is therefore not necessary, as is the case with conventional stripper solutions, to discard the stripper solution after saturation.

Beispiel 1example 1

Auf ein Titanblech von 100 x 20 x 2 mm werden abwechselnd eine 20 µm dicke Glanzkupferschicht und darauf eine 10 µm dicke Blei-Zinn-Schicht abgeschieden und dies wird mehrfach wiederholt, bis eine etwa 1 mm starke Auflage auf dem Titanblech vorhanden ist.A 20 µm thick copper layer is alternately placed on a titanium sheet of 100 x 20 x 2 mm and then a 10 µm thick lead-tin layer is deposited and this is repeated several times until an approximately 1 mm thick layer is present on the titanium sheet.

Man stellt eine Lösung aus 250 g/I Hydroxyäthansulfonsäure und 750 g/I Wasser her. Das mit Kupfer und Bleizinn beschichtete Titanblech wird in diese Lösung eingetaucht und anodisch geschaltet. Bei einer anodischen Stromdichte von 20 A/dm2 und bei einer Temperatur von 20 °C wird die Elektrolyse bis zur vollständigen Ablösung der Kupfer und Bleizinn-Überzüge durchgeführt. Hierzu benötigt man etwa 200 Minuten. Anschließend wird weitere 60 Minuten unter den gleichen Bedingungen elektrolysiert. Durch Auswiegen des Titanbleches vor der Beschichtung mit Kupfer und Bleizinn und nach dem anodischen Ablösen der Metalle und der zusätzlichen Elektrolysezeit von 60 Minuten stellt man fest, daß sich das Gewicht praktisch nicht verändert hat, und daß ein Abtrag von Titan nicht oder nur in unmeßbar geringem Maße erfolgte.A solution is prepared from 250 g / l of hydroxyethanesulfonic acid and 750 g / l of water. The titanium sheet coated with copper and tin is immersed in this solution and switched anodically. At an anodic current density of 20 A / dm 2 and at a temperature of 20 ° C, the electrolysis is carried out until the copper and lead-tin coatings are completely detached. This takes about 200 minutes. It is then electrolyzed for a further 60 minutes under the same conditions. By weighing the titanium sheet before coating with copper and lead tin and after the anodic detachment of the metals and the additional electrolysis time of 60 minutes, it is found that the weight has practically not changed, and that removal of titanium does not, or only to an immeasurably small extent Dimensions took place.

Beispiel 2Example 2

Die Legierung Bleizinn und die Metalle Kupfer, Zinn, Silber und Zink werden auf Titanblech abgeschieden. Anschließend wird in einem Elektrolyten, der 175 g/I Methansulfonsäure enthält, bei 25 °C das Metall anodisch abgelöst und die Stromausbeute ermittelt.The lead tin alloy and the metals copper, tin, silver and zinc are deposited on titanium sheet. The metal is then anodically detached at 25 ° C. in an electrolyte containing 175 g / l methanesulfonic acid and the current efficiency is determined.

Folgende Werte wurden gefunden :

Figure imgb0001
The following values were found:
Figure imgb0001

Beispiel 3Example 3

Die Legierung Bleizinn wird auf Titanblech abgeschieden. Anschließend löst man die Legierung von der Titanoberfläche in einem Elektrolyten ab, der 175 g/I Methansulfonsäure und 40 g/1 Feinkornzusatz enthält. Durch Variation von Temperatur, Rührbewegung und kathodische Stromdichte wird ermittelt, ob sich Bleizinn kathodisch wieder kompakt abscheiden läßt. Bei mäßiger Rührung erhält man bei 60 °C und einer kathodischen Stromdichte von 10 A/dm2 kompakte, glatte und festhaftende Bleizinnüberzüge auf der Kathode. Bei Raumtemperatur sind bis zu einer kathodischen Stromdichte von 5 A/dm2 und sonst gleichen Bedingungen noch kompakte und festhaftende Überzüge zu erhalten.The lead tin alloy is deposited on titanium sheet. The alloy is then detached from the titanium surface in an electrolyte containing 175 g / l methanesulfonic acid and 40 g / 1 fine grain additive. By varying the temperature, stirring motion and cathodic current density, it is determined whether lead tin can be cathodically compact again. With moderate stirring, compact, smooth and firmly adhering lead tin coatings are obtained at 60 ° C. and a cathodic current density of 10 A / dm 2 the cathode. At room temperature, compact and adherent coatings can be obtained up to a cathodic current density of 5 A / dm 2 and otherwise the same conditions.

Beispiel 4Example 4

Glanznickel und Halbglanznickel wird auf Titanblech kathodisch abgeschieden. Anschließend werden diese Überzüge in einem Elektrolyten wieder anodisch aufgelöst. Der Elektrolyt enthält 100 g/I Methansulfonsäure und verschiedene Konzentrationen an Halogeniden. Bei 20 A/dm2 (anodisch) und einer Temperatur von 25 bis 30 °C wird die anodische Stromausbeute emittelt. Die Ergebnisse sind in der folgenden Tabelle enthalten.

Figure imgb0002
Bright nickel and semi-gloss nickel are cathodically deposited on titanium sheet. These coatings are then anodically dissolved in an electrolyte. The electrolyte contains 100 g / l methanesulfonic acid and various concentrations of halides. The anodic current yield is determined at 20 A / dm 2 (anodic) and a temperature of 25 to 30 ° C. The results are shown in the table below.
Figure imgb0002

Titan, anodisch geschaltet, wird unter diesen Bedingungen nicht angegriffen.Titanium, anodized, is not attacked under these conditions.

Claims (4)

1. Process for the electrolytic stripping of Cd, Cr, Cu, Cu alloys, Ni, Pb, Pb/Sn, Sn or Zn from titanium as a base metal, characterized in that the titanium base covered with the metals to be stripped is anodically switched at a current density of 0.1 to 100 A/dm2, a voltage of 0.1 to 25 V and at a temperature between 15 °C up to the boiling point of the solution in an aqueous demetallization bath containing one or more alkyl sulfonic acids in which the alkyl groups may be hydroxy substituted if required at a concentration of 1 g up to the limit of solubility.
2. Process according to claim 1 characterized in that alkyl sulfonic acids with 1 to 4 C atoms are used.
3. Process according to claim 1 or 2 characterized in that CH2(SO3H)2, CH3S03H and/or HOCH2―CH2S03H are used as sulfonic acids.
4. Process according to claims 1 to 3 characterized in that halogenides and/or NaSCN are. additionally contained in the aqueous demetallization bath as activators.
EP83110698A 1983-10-26 1983-10-26 Stripping bath and process for the electrolytical stripping of metals from titanium as a base metal Expired EP0139039B1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AT83110698T ATE30344T1 (en) 1983-10-26 1983-10-26 DEMETALLIZING BATH AND PROCESS FOR ELECTROLYTIC DRAWING METALS FROM TITANIUM AS BASE METAL.
DE8383110698T DE3374140D1 (en) 1983-10-26 1983-10-26 Stripping bath and process for the electrolytical stripping of metals from titanium as a base metal
EP83110698A EP0139039B1 (en) 1983-10-26 1983-10-26 Stripping bath and process for the electrolytical stripping of metals from titanium as a base metal

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EP83110698A EP0139039B1 (en) 1983-10-26 1983-10-26 Stripping bath and process for the electrolytical stripping of metals from titanium as a base metal

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EP0139039B1 true EP0139039B1 (en) 1987-10-21

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Publication number Priority date Publication date Assignee Title
US4678552A (en) * 1986-04-22 1987-07-07 Pennwalt Corporation Selective electrolytic stripping of metal coatings from base metal substrates
TWI231831B (en) * 2001-10-11 2005-05-01 Shipley Co Llc Stripping solution

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0051415A1 (en) * 1980-10-31 1982-05-12 Warner-Lambert Company Water-soluble salts of 2,4-diamino-5-methyl-6-((3,4,5-trimethoxyanilino)methyl)quinazoline, compositions containing such salts and the production of such salts
EP0062136A1 (en) * 1981-03-30 1982-10-13 Pennwalt Corporation Process for the preparation of anhydrous alkane sulfonic acids

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1144797B (en) * 1981-10-14 1986-10-29 Alfachimici Spa SOLUTION FOR THE REMOVAL OF POND OR LEAD POND ALLOY FROM A SUBSTRATE BY SPRAY OPERATION

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0051415A1 (en) * 1980-10-31 1982-05-12 Warner-Lambert Company Water-soluble salts of 2,4-diamino-5-methyl-6-((3,4,5-trimethoxyanilino)methyl)quinazoline, compositions containing such salts and the production of such salts
EP0062136A1 (en) * 1981-03-30 1982-10-13 Pennwalt Corporation Process for the preparation of anhydrous alkane sulfonic acids

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DE3374140D1 (en) 1987-11-26
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