EP0538734A1 - Storage stable cyanoacrylate adhesive in aluminum tubes - Google Patents

Storage stable cyanoacrylate adhesive in aluminum tubes Download PDF

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Publication number
EP0538734A1
EP0538734A1 EP92117603A EP92117603A EP0538734A1 EP 0538734 A1 EP0538734 A1 EP 0538734A1 EP 92117603 A EP92117603 A EP 92117603A EP 92117603 A EP92117603 A EP 92117603A EP 0538734 A1 EP0538734 A1 EP 0538734A1
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EP
European Patent Office
Prior art keywords
fatty acid
cyanoacrylate adhesive
tubes
storage
lubricant
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Granted
Application number
EP92117603A
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German (de)
French (fr)
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EP0538734B1 (en
Inventor
Rolf Lier
Herbert Densky
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP0538734A1 publication Critical patent/EP0538734A1/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/22—Carboxylic acids or their salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
    • C10M105/68—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/003—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/103—Carboxylix acids; Neutral salts thereof used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/2606—Overbased carboxylic acid salts used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • C10M2207/2623—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C10M2215/0806—Amides used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C10M2215/082—Amides containing hydroxyl groups; Alkoxylated derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/10—Amides of carbonic or haloformic acids
    • C10M2215/1006—Amides of carbonic or haloformic acids used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C10M2215/285—Amides; Imides used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/241—Manufacturing joint-less pipes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/242—Hot working
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/243—Cold working
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/245—Soft metals, e.g. aluminum
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/246—Iron or steel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/247—Stainless steel

Definitions

  • the invention relates to a storage-stable cyanoacrylate adhesive in Al tubes, the Al tubes, the Al semi-finished product and a lubricant for Al forming.
  • Cyanoacrylate adhesives contain 2-cyanoacrylic acid esters as an essential component. Their polymerization is initiated very easily and quickly by traces of anions. Because of this reaction in seconds, the storage of cyanoacrylate adhesive can be difficult. This applies in particular to storage in aluminum tubes. If you fill the Al tubes with a cyanoacrylate adhesive of the same composition as for plastic vials, you will often see an undesired polymerization after less than 6 months at 20 ° C. The adhesive is therefore unusable. To avoid this premature polymerization, the adhesive is overstabilized with 1,000 ppm of an acid (e.g. phosphonic acid). The premature polymerization can thus largely be avoided, but the bonding then takes considerably longer, e.g. 2 minutes instead of 5 seconds.
  • an acid e.g. phosphonic acid
  • the object of the invention is therefore to stabilize the cyanoacrylate adhesive in Al tubes without accepting the disadvantage of an extended reaction time.
  • R denotes an
  • cyanoacrylates are known to the person skilled in the adhesive, cf. Ullmann's Encyclopaedia of Industrial Chemistry, vol. Al, p. 240, Verlag Chemie Weinheim (1985) as well as US Pat. No. 3,254,111 and US Pat. No. 3,654,340.
  • Preferred monomers are the methoxyethyl, ethoxyethyl, methyl, ethyl, propyl or butyl esters of 2-cyanoacrylic acid.
  • Tubes are closable containers for storing cyanoacrylate adhesive, regardless of their size, shape or type of closure.
  • the main thing is tubular, flexible containers with a screw cap that run out flat at one end.
  • the tubes are made of "aluminum”. This means pure aluminum with the different degrees of purity, but above all aluminum alloys based on Al / Mn, Al / Mg, Al / Mn / Mg, Al / Si / Mg, Al / Zn / Mg, Al / Zn / Mg / Cu and Al / Cu / Mg.
  • the Al semi-finished product preferably has a thickness of 2 to 5 mm, in particular 4.0 to 4.5 mm
  • stearates are used as extrusion agents, especially metal stearates and especially zinc stearate. It is powdered onto the blanks and burned out after extrusion at approx. 300 to 400 ° C. What remains is an invisible zinc oxide, which normally does not interfere with the contents. For cyanoacrylates, however, the metal oxides or metal hydroxides trigger the polymerization.
  • Stearic acid amides can also be used as extrusion agents for Al tubes for cyanoacrylates. It is applied to the Al discs and, after extrusion at temperatures above 460 ° C, decomposes in more than 10 minutes in the presence of air. Dark brown spots remain clearly visible on the inside of the aluminum. The more of them there are, the less the cyanoacrylate adhesive can be stored. Their frequency depends on the grain size of the stearic acid amide, the thickness and uniformity of its application, the decomposition conditions, etc. Such irregularities cannot be avoided in large-scale production. Therefore, extruded Al tubes are not suitable for filling with conventional cyanoacrylate adhesives. An undesired polymerization occurs prematurely.
  • the aluminum tubes are very suitable for storing cyanoacrylate adhesive.
  • Fatty acid amides are understood to mean amides of the general formula R3-CO-NR1R2, in which R3 represents an alkyl radical with more than 9 carbon atoms, in particular with 11 to 21 carbon atoms.
  • the fatty acid amides can also carry alkyl substituents with 1 to 6 carbon atoms on the nitrogen atom.
  • the fatty acid amides are usually mixtures.
  • the stearic acid amide is preferred.
  • Long-chain fatty acids of the general formula CH3- (CH2) n -COOH are expediently used, where n is> 10 and preferably 16. These are also usually mixtures of different fatty acids such as undecane, lauric, tridecane, myristic, Pentadecane, palmitic, margarine, stearic, nonadecane, arachinic and behenic acid.
  • the fatty acid In order to achieve both a sufficient storage stability and a sufficient lubricating effect, the fatty acid must be present in the fatty acid amide in a certain concentration. In general, there are 10 to 70 parts by weight of fatty acid, preferably 20 to 50 parts by weight, per 100 parts by weight of fatty acid amide. However, the exact limits still depend on the fatty acid amides and fatty acids used, in particular on the amount of the contaminating bases in the fatty acid amide.
  • the fatty acid amide and the fatty acid are mixed by mixing both substances in powder form in a mixing drum.
  • the extrusion agent according to the invention is applied to the Al circular blank by powdering the extrusion agent onto the Al circular blanks in a mixing drum.
  • the round blank with the extrusion agent applied is extruded, in that a stamp hits the round blank and the aluminum lies between the stamp and the outer wall of the mold.
  • the extruded aluminum blank is further processed into a tube by trimming the rear edges and applying a thread to the front part.
  • Extrusion is preferably followed by heating in the presence of air to about 300 ° C. for at least 10 minutes.
  • the extrusion agent according to the invention not only enables the production of Al tubes without problems during extrusion, but above all also the storage of cyanoacrylate adhesives over a very long period of more than 12 months at room temperature and at the same time enables a very fast reaction within approx. 3 seconds when gluing. Further advantages are that you get tubes that are optically stain-free, bare and absolutely residue-free. This is also required in the pharmaceutical industry.
  • the invention is illustrated by the following example.
  • stearic acid amide with the trade name COSMIC-WAX 84 from Abril Industrial Waxes Ltd. are mixed with A) 50 parts by weight and B) 25 parts by weight of a stearic acid by mixing both substances in the pulverulent state in a mixing drum.
  • the Al tubes were heated in air at 460 ° C for about 10 minutes.
  • the extrusion agents according to the invention led to bright, high-gloss, spot-free surfaces, the stearic acid amide, on the other hand, to tubes with brown spots.
  • the Al tubes were filled with cyanoacrylate adhesive of the following composition: 95 cyanoacrylate, 5% polymethyl methacrylate.
  • the cyanoacrylate adhesive was stored in the Al tubes at 80 ° C. After 12 days of storage, the adhesive was still readily usable in the Al tubes produced according to the invention. This corresponds to a storage time of approx. 2 years at room temperature. In contrast, the adhesive in the commonly treated Al tubes was polymerized after only about 4 to 7 days and was therefore unusable.
  • the usability of the stored cyanoacrylate adhesive was checked by checking curing times and adhesive strength.

Abstract

A lubricant containing a fatty acid amide and fatty acid for deforming Al semi-finished products is described. Using this, Al tubes can be manufactured without problems from round blanks by extrusion. They have a spot-free and bright appearance. A cyanoacrylate adhesive can be stored in these for a longer period than is the case when using the individual lubricant components on their own.

Description

Die Erfindung betrifft einen lagerstabilen Cyanoacrylat-Klebstoff in Al-Tuben, die Al-Tuben, das Al-Halbzeug und ein Schmierstoff für die Al-Umformung.The invention relates to a storage-stable cyanoacrylate adhesive in Al tubes, the Al tubes, the Al semi-finished product and a lubricant for Al forming.

Cyanoacrylat-Klebstoffe enthalten als wesentliche Komponente 2-Cyanoacrylsäureester. Deren Polymerisation wird sehr leicht und schnell durch Spuren von Anionen initiiert. Wegen dieser sekundenschnellen Reaktion kann die Lagerung von Cyanoacrylat-Klebstoff Schwierigkeiten bereiten. Das gilt insbesondere für die Lagerung in Al-Tuben. Füllt man nämlich in die Al-Tuben einen Cyanoacrylat-Klebstoff derselben Zusammensetzung wie für Kunststoff-Fläschchen, dann beobachtet man häufig bereits nach weniger als 6 Monaten bei 20 °C eine unerwünschte Polymerisation. Der Klebstoff ist damit unbrauchbar. Zur Vermeidung dieser vorzeitigen Polymerisation wird der Klebstoff mit 1 000 ppm an einer Säure (z.B. Phosphonsäure) überstabilisiert. Damit kann zwar die vorzeitige Polymerisation weitgehend vermieden werden, jedoch dauert dann die Verklebung wesentlich länger, z.B. 2 Minuten anstelle von 5 Sekunden.Cyanoacrylate adhesives contain 2-cyanoacrylic acid esters as an essential component. Their polymerization is initiated very easily and quickly by traces of anions. Because of this reaction in seconds, the storage of cyanoacrylate adhesive can be difficult. This applies in particular to storage in aluminum tubes. If you fill the Al tubes with a cyanoacrylate adhesive of the same composition as for plastic vials, you will often see an undesired polymerization after less than 6 months at 20 ° C. The adhesive is therefore unusable. To avoid this premature polymerization, the adhesive is overstabilized with 1,000 ppm of an acid (e.g. phosphonic acid). The premature polymerization can thus largely be avoided, but the bonding then takes considerably longer, e.g. 2 minutes instead of 5 seconds.

Die erfindungsgemäße Aufgabe besteht also darin, den Cyanoacrylat-Klebstoff in Al-Tuben zu stabilisieren, ohne den Nachteil einer verlängerten Reaktionszeit in Kauf zu nehmen.The object of the invention is therefore to stabilize the cyanoacrylate adhesive in Al tubes without accepting the disadvantage of an extended reaction time.

Die erfindungsgemäße Lösung ist den Patentansprüchen zu entnehmen. Sie beruht im wesentlichen auf der Erkenntnis, daß der Schmierstoff zur Herstellung der Al-Tuben für die Lagerstabilität von Bedeutung ist und daß er schwach sauer reagieren muß.The solution according to the invention can be found in the patent claims. It is essentially based on the knowledge that the lubricant for the production of the Al tubes is important for the storage stability and that it has to react weakly acidic.

Bei den Cyanoacrylat-Klebstoffen handelt es sich um Klebstoffe auf der Basis von 2-Cyanoacrylsäureestern der allgemeinen Formel I



        H₂C=C(CN)-COOR   (I)



in der R eine Alkyl-, Alkenyl-, Cycloalkyl-, Aryl-, Alkoxyalkyl-, Aralkyl- oder Haloalkylgruppe bedeutet, insbesondere eine Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, iso-Butyl-, Pentyl-, Hexyl-, Allyl-, Methallyl-, Crotyl-, Propargyl-, Cyclohexyl-, Benzyl-, Phenyl-, Cresyl-, 2-Chlorethyl-, 3-Chlorpropyl-, 2-Chlorbutyl-, Trifluorethyl-, 2-Methoxyethyl-, 3-Methoxybutyl- und 2-Ethoxyethylgruppe ist. Die vorgenannten Cyanoacrylate sind dem Klebstoff-Fachmann bekannt, vgl. Ullmann's Encyclopaedia of Industrial Chemistry, Bd. Al, S. 240, Verlag Chemie Weinheim (1985) sowie US-PS 3 254 111 und US-PS 3 654 340.
Bevorzugte Monomere sind die Methoxyethyl-, Ethoxyethyl-, Methyl-, Ethyl-, Propyl- oder Butyl-Ester der 2-Cyanoacrylsäure.The cyanoacrylate adhesives are adhesives based on 2-cyanoacrylic acid esters of the general formula I



H₂C = C (CN) -COOR (I)



in which R denotes an alkyl, alkenyl, cycloalkyl, aryl, alkoxyalkyl, aralkyl or haloalkyl group, in particular a methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso- Butyl, pentyl, hexyl, allyl, methallyl, crotyl, propargyl, cyclohexyl, benzyl, phenyl, cresyl, 2-chloroethyl, 3-chloropropyl, 2-chlorobutyl, trifluoroethyl , 2-methoxyethyl, 3-methoxybutyl and 2-ethoxyethyl group. The above-mentioned cyanoacrylates are known to the person skilled in the adhesive, cf. Ullmann's Encyclopaedia of Industrial Chemistry, vol. Al, p. 240, Verlag Chemie Weinheim (1985) as well as US Pat. No. 3,254,111 and US Pat. No. 3,654,340.
Preferred monomers are the methoxyethyl, ethoxyethyl, methyl, ethyl, propyl or butyl esters of 2-cyanoacrylic acid.

Mit "Tuben" sind verschließbare Behälter zur Aufbewahrung von Cyanoacrylat-Klebstoff gemeint, unabhängig von ihrer Größe, ihrer Form oder der Art ihres Verschlusses. Hauptsächlich geht es aber um röhrenförmige, biegsame, an einem Ende flach aus laufende Behälter mit einem Schraubverschluß. Die Tuben sind aus "Aluminium" hergestellt. Damit ist Reinaluminium mit den verschiedenen Reinheitsgraden gemeint, vor allem aber Aluminiumlegierungen auf der Basis von Al/Mn, Al/Mg, Al/Mn/Mg, Al/Si/Mg, Al/Zn/Mg, Al/Zn/Mg/Cu und Al/Cu/Mg. Das Al-Halbzeug hat vorzugsweise eine Dicke von 2 bis 5 mm, insbesondere 4,0 bis 4,5 mm"Tubes" are closable containers for storing cyanoacrylate adhesive, regardless of their size, shape or type of closure. The main thing is tubular, flexible containers with a screw cap that run out flat at one end. The tubes are made of "aluminum". This means pure aluminum with the different degrees of purity, but above all aluminum alloys based on Al / Mn, Al / Mg, Al / Mn / Mg, Al / Si / Mg, Al / Zn / Mg, Al / Zn / Mg / Cu and Al / Cu / Mg. The Al semi-finished product preferably has a thickness of 2 to 5 mm, in particular 4.0 to 4.5 mm

Der Schmierstoff beeinflußt neben dem Halbzeug aus Aluminium, dem Werkzeug und den Maschinen entscheidend das Umformergebnis. Bei seiner Auswahl müssen folgende Gesichtspunkte berücksichtigt werden: Reibkraft, Werkzeugverschleiß, Druckbeständigkeit, Temperaturbeständigkeit, Oberflächenausbildung, Werkzeugverschmutzung, Aufbringen und Entfernen des Schmierstoffes, Werkzeugkorrosion, Wirtschaftlichkeit. Für das Aluminium-Halbzeug wie Bleche, Bänder, Folien und Ronden werden als Tiefziehmittel angegeben (s. Berichte zum Symposium der deutschen Gesellschaft für Metallkunde "Tiefziehen" (1975), S. 180 bis 197):

  • a) Schmiermittel mit Schichtgitteraufbau bzw. lamellare Feststoffe wie Molybdändisulfid und Graphit,
  • b) Feste organische Metallseifen wie Zinkstearat sowie feste Fettsäuren, z.B. Palmitinsäure oder Stearinsäure, die in flüchtigen Kohlenwasserstoffen gelöst sind,
  • c) Mineralöle mit Zusätzen von Fettsäuren oder Mineralöle mit fetten Ölen sowie Zusätzen von Schwefel und Chloriden,
  • d) Emulsionen von c) mit Wasser und
  • e) Seifenlösungen mit Fettkomponenten.
In addition to the aluminum semi-finished product, the tool and the machine, the lubricant has a decisive influence on the forming result. The following aspects must be taken into account when selecting it: friction force, tool wear, pressure resistance, temperature resistance, surface formation, tool contamination, application and removal of the lubricant, tool corrosion, economy. For the aluminum semi-finished products such as sheets, strips, foils and round blanks are given as deep-drawing agents (see reports on the symposium of the German Society for Metallurgy "Deep-drawing" (1975), pp. 180 to 197):
  • a) lubricants with a layered grid structure or lamellar solids such as molybdenum disulfide and graphite,
  • b) solid organic metal soaps such as zinc stearate and solid fatty acids, for example palmitic acid or stearic acid, which are dissolved in volatile hydrocarbons,
  • c) mineral oils with additions of fatty acids or mineral oils with fatty oils and additions of sulfur and chlorides,
  • d) emulsions from c) with water and
  • e) Soap solutions with fat components.

Üblicherweise werden Stearate als Fließpreßmittel verwendet, vor allem Metallstearate und insbesondere Zinkstearat. Es wird auf die Ronden aufgepudert und nach dem fließpressen bei ca. 300 bis 400 °C ausgebrannt. Zurück bleibt ein unsichtbares Zinkoxid, welches normalerweise nicht für das Füllgut störend wirkt. Für Cyanacrylate wirken jedoch die Metalloxide bzw. Metallhydroxide polymerisationsauslösend.Usually stearates are used as extrusion agents, especially metal stearates and especially zinc stearate. It is powdered onto the blanks and burned out after extrusion at approx. 300 to 400 ° C. What remains is an invisible zinc oxide, which normally does not interfere with the contents. For cyanoacrylates, however, the metal oxides or metal hydroxides trigger the polymerization.

Man kann auch Stearinsäureamide als Fließpreßmittel für Al-Tuben für Cyanacrylate einsetzen. Es wird auf die Al-Ronden aufgetragen und nach dem Fließpressen bei Temperaturen oberhalb von 460 °C in mehr als 10 Minuten in Gegenwart von Luft zersetzt. Dabei bleiben deutlich sichtbar dunkelbraune Flecken auf der Al-Innenseite zurück. Je mehr davon vorhanden sind, um so geringer ist die Lagerfähigkeit des Cyanoacrylat-Klebstoffes. Ihre Häufigkeit ist von der Korngröße des Stearinsäureamids, der Dicke und Gleichmäßigkeit seines Auftrags, den Zersetzungsbedingungen usw. abhängig. In der großtechnischen Produktion lassen sich derartige Ungleichmäßigkeiten nicht vermeiden. Daher sind damit fließgepreßte Al-Tuben zum Befüllen mit üblichen Cyanoacrylat-Klebstoffen nicht geeignet. Es kommt zu einer vorzeitigen unerwünschten Polymerisation.Stearic acid amides can also be used as extrusion agents for Al tubes for cyanoacrylates. It is applied to the Al discs and, after extrusion at temperatures above 460 ° C, decomposes in more than 10 minutes in the presence of air. Dark brown spots remain clearly visible on the inside of the aluminum. The more of them there are, the less the cyanoacrylate adhesive can be stored. Their frequency depends on the grain size of the stearic acid amide, the thickness and uniformity of its application, the decomposition conditions, etc. Such irregularities cannot be avoided in large-scale production. Therefore, extruded Al tubes are not suitable for filling with conventional cyanoacrylate adhesives. An undesired polymerization occurs prematurely.

Überraschenderweise zeigte es sich nun, daß bei Verwendung eines Gemisches aus Fettsäureamid und Fettsäure als Schmierstoff die Aluminium-Tuben sehr gut zur Lagerung von Cyanoacrylat-Klebstoff geeignet sind.Surprisingly, it has now been found that when a mixture of fatty acid amide and fatty acid is used as the lubricant, the aluminum tubes are very suitable for storing cyanoacrylate adhesive.

Unter "Fettsäureamide" werden Amide der allgemeinen Formel R₃-CO-NR₁R₂ verstanden, bei denen R₃ für einen Alkylrest mit mehr als 9 C-Atomen steht, insbesondere mit 11 bis 21 C-Atomen. Die Fettsäureamide können auch am Stickstoffatom Alkyl-Substituenten mit 1 bis 6 C-Atomen tragen. In der Regel handelt es sich bei den Fettsäureamiden um Gemische. Bevorzugt wird das Stearinsäureamid."Fatty acid amides" are understood to mean amides of the general formula R₃-CO-NR₁R₂, in which R₃ represents an alkyl radical with more than 9 carbon atoms, in particular with 11 to 21 carbon atoms. The fatty acid amides can also carry alkyl substituents with 1 to 6 carbon atoms on the nitrogen atom. The fatty acid amides are usually mixtures. The stearic acid amide is preferred.

Zweckmäßigerweise werden langkettige Fettsäuren der allgemeinen Formel CH₃-(CH₂)n-COOH eingesetzt, wobei n > 10 und vorzugsweise 16 ist. Auch hierbei handelt es sich in der Regel um Gemische verschiedener Fettsäuren wie Undecan-, Laurin-, Tridecan-, Myristin-, Pentadecan-, Palmitin-, Margarin-, Stearin-, Nonadecan-, Arachin- und Behen-Säure.Long-chain fatty acids of the general formula CH₃- (CH₂) n -COOH are expediently used, where n is> 10 and preferably 16. These are also usually mixtures of different fatty acids such as undecane, lauric, tridecane, myristic, Pentadecane, palmitic, margarine, stearic, nonadecane, arachinic and behenic acid.

Um sowohl eine ausreichende Lagerstabilität als auch eine ausreichende Schmierwirkung zu erzielen, muß die Fettsäure in einer bestimmten Konzentration in dem Fettsäureamid vorliegen. Im allgemeinen kommen auf 100 Gew.-Teile Fettsäureamid 10 bis 70 Gew.-Teile Fettsäure, vorzugsweise 20 bis 50 Gew.-Teile. Die genauen Grenzen hängen jedoch noch von den konkret eingesetzten Fettsäureamiden und Fettsäuren ab, insbesondere von der Menge der verunreinigenden Basen in dem Fettsäureamid.In order to achieve both a sufficient storage stability and a sufficient lubricating effect, the fatty acid must be present in the fatty acid amide in a certain concentration. In general, there are 10 to 70 parts by weight of fatty acid, preferably 20 to 50 parts by weight, per 100 parts by weight of fatty acid amide. However, the exact limits still depend on the fatty acid amides and fatty acids used, in particular on the amount of the contaminating bases in the fatty acid amide.

Das Fettsäureamid und die Fettsäure werden gemischt, indem beide Stoffe in pulverförmigem Zustand in einer Mischtrommel vermischt werden.The fatty acid amide and the fatty acid are mixed by mixing both substances in powder form in a mixing drum.

Das erfindungsgemäße Fließpreßmittel wird auf die Al-Ronde aufgetragen, indem das Fließpreßmittel in einer Mischtrommel auf die Al-Ronden aufgepudert wird.The extrusion agent according to the invention is applied to the Al circular blank by powdering the extrusion agent onto the Al circular blanks in a mixing drum.

Die Ronde mit dem aufgetragenen Fließpreßmittel wird fließgepreßt, indem ein Stempel auf die Ronde trifft und das Aluminium sich zwischen Stempel und Außenwand der Form legt.The round blank with the extrusion agent applied is extruded, in that a stamp hits the round blank and the aluminum lies between the stamp and the outer wall of the mold.

Die fließgepreßte Al-Ronde wird zu einer Tube weiterverarbeitet, indem die Hinterkanten beschnitten und auf dem Vorderteil ein Gewinde aufgebracht wird.The extruded aluminum blank is further processed into a tube by trimming the rear edges and applying a thread to the front part.

Vorzugsweise schließt sich an das Fließpressen eine Erwärmung in Gegenwart von Luft auf ca. 300 °C für mindestens 10 Minuten an.Extrusion is preferably followed by heating in the presence of air to about 300 ° C. for at least 10 minutes.

Das erfindungsgemäße Fließpreßmittel ermöglicht nicht nur die Herstellung von Al-Tuben ohne Probleme beim Fließpressen, sondern vor allem auch die Lagerung von Cyanoacrylat-Klebstoffen über einen sehr langen Zeitraum von mehr als 12 Monaten bei Raumtemperatur und ermöglicht gleichzeitig eine sehr schnelle Reaktion innerhalb von ca. 3 Sekunden beim Verkleben. Weitere Vorteile sind, daß man Tuben erhält, die optisch fleckenfrei, blank und absolut rückstandsfrei sind. Dies wird auch in der Pharmaindustrie gefordert.The extrusion agent according to the invention not only enables the production of Al tubes without problems during extrusion, but above all also the storage of cyanoacrylate adhesives over a very long period of more than 12 months at room temperature and at the same time enables a very fast reaction within approx. 3 seconds when gluing. Further advantages are that you get tubes that are optically stain-free, bare and absolutely residue-free. This is also required in the pharmaceutical industry.

Die Erfindung wird anhand von folgendem Beispiel näher erläutert.The invention is illustrated by the following example.

Beispielexample

100 Gew.-Teile von Stearinsäureamid mit dem Handelsnamen COSMIC-WAX 84 der Firma Abril Industrial Waxes Ltd. werden mit A) 50 Gew.-Teilen und B) 25 Gew.-Teilen einer Stearinsäure gemischt, indem beide Stoffe im pulverförmigen Zustand in einer Mischtrommel vermischt werden.100 parts by weight of stearic acid amide with the trade name COSMIC-WAX 84 from Abril Industrial Waxes Ltd. are mixed with A) 50 parts by weight and B) 25 parts by weight of a stearic acid by mixing both substances in the pulverulent state in a mixing drum.

25 g der erfindungsgemäßen Fließpreßmittel A und B sowie des Fließpreßmittels Stearinsäureamid (ohne weiteren Zusatz an Stearinsäure) wurden auf 1 kg Al-Ronden mit einer Dicke von ca. 5 mm und einem Durchmesser von 13 mm aufgetragen, indem das Fließpreßmittel in einer Mischtrommel auf die Al-Ronden aufgepudert wird.25 g of the extrusion agents A and B according to the invention and of the extrusion agent stearic acid amide (without further addition of stearic acid) were applied to 1 kg of Al discs with a thickness of approx. 5 mm and a diameter of 13 mm, by the extrusion agent in a mixing drum on the Al-blanks is powdered.

Aus den so präparierten Al-Ronden wurden ca. 3 Mill. Tuben hergestellt mit einem Füllvolumen von 3 ml.Approx. 3 million tubes with a filling volume of 3 ml were produced from the Al blanks prepared in this way.

Die Al-Tuben wurden bei 460 °C ca. 10 Minuten lang an Luft erwärmt. Die erfindungsgemäßen Fließpreßmittel führten zu blanken hochglänzenden fleckenfreien Oberflächen, das Stearinsäureamid dagegen zu Tuben mit braunen Flecken.The Al tubes were heated in air at 460 ° C for about 10 minutes. The extrusion agents according to the invention led to bright, high-gloss, spot-free surfaces, the stearic acid amide, on the other hand, to tubes with brown spots.

Die Al-Tuben wurden mit Cyanoacrylat-Klebstoff folgender Zusammensetzung gefüllt: 95 Cyanacrylat, 5 % Polymethylmethacrylat.The Al tubes were filled with cyanoacrylate adhesive of the following composition: 95 cyanoacrylate, 5% polymethyl methacrylate.

Der Cyanoacrylat-Klebstoff wurde in den Al-Tuben bei 80 °C gelagert. Nach 12 Tagen Lagerung war der Klebstoff in den erfindungsgemäß hergestellten Al-Tuben noch ohne weiteres brauchbar. Das entspricht einer Lagerzeit von ca. 2 Jahren bei Raumtemperatur. Der Klebstoff in den üblich behandelten Al-Tuben war dagegen schon nach ca. 4 bis 7 Tagen polymerisiert und damit unbrauchbar.The cyanoacrylate adhesive was stored in the Al tubes at 80 ° C. After 12 days of storage, the adhesive was still readily usable in the Al tubes produced according to the invention. This corresponds to a storage time of approx. 2 years at room temperature. In contrast, the adhesive in the commonly treated Al tubes was polymerized after only about 4 to 7 days and was therefore unusable.

Die Temperaturbehandlung kann bei den erfindungsgemäßen Fließpreßmitteln auch bei niedrigeren Temperaturen stattfinden, unter Umständen sogar ganz entfallen:

  • Eine Verringerung der Temperatur von 460 °C auf 350 °C führte praktisch zu den gleichen Ergebnissen.
  • In Al-Tuben ohne jegliche Wärmebehandlung konnte der Cyanoacrylat-Klebstoff 8 bis 10 Tage bei 80 °C ohne Polymerisation gelagert werden. Die mit dem bekannten Tiefziehmittel hergestellten Al-Tuben führte dagegen zu einer Polymerisation in weniger als einem Tag.
The heat treatment in the extrusion molding agents according to the invention can also take place at lower temperatures, in some cases even completely omitted:
  • Reducing the temperature from 460 ° C to 350 ° C practically gave the same results.
  • In Al tubes without any heat treatment, the cyanoacrylate adhesive could be stored at 80 ° C for 8 to 10 days without polymerization. The Al tubes produced with the well-known thermoforming agent, on the other hand, led to polymerization in less than a day.

Die Brauchbarkeit des gelagerten Cyanoacrylat-Klebstoffs wurde geprüft, indem man Aushärtzeiten und Klebkraft überprüft.The usability of the stored cyanoacrylate adhesive was checked by checking curing times and adhesive strength.

Claims (8)

Lagerstabiler Cyanoacrylat-Klebstoff in Al-Tuben, dadurch gekennzeichnet, daß bei der Herstellung der Al-Tube ein Schmierstoff verwendet wird, der ein Fettsäureamid und eine Fettsäure enthält.Storage-stable cyanoacrylate adhesive in Al tubes, characterized in that a lubricant which contains a fatty acid amide and a fatty acid is used in the manufacture of the Al tube. Lagerstabiler Cyanoacrylat-Klebstoff nach Anspruch 1, gekennzeichnet durch ein Fettsäureamid der allgemeinen Formel R₃-CO-NR₁R₂, wobei R₁ und R₂ unabhängig voneinander H oder eine Alkylgruppe mit 1 bis 6 C-Atomen, insbesondere in beiden Fällen gleichzeitig H sind, und wobei R₃ eine Alkylgruppe mit mehr als 9, insbesondere 11 bis 21, C-Atomen ist.Storage-stable cyanoacrylate adhesive according to claim 1, characterized by a fatty acid amide of the general formula R₃-CO-NR₁R₂, where R₁ and R₂ are independently H or an alkyl group with 1 to 6 C atoms, in particular in both cases simultaneously H, and wherein R₃ is an alkyl group with more than 9, in particular 11 to 21, carbon atoms. Lagerstabiler Cyanoacrylat-Klebstoff nach Anspruch 1, gekennzeichnet durch eine Fettsäure der allgemeinen Formel CH₃-(CH₂)n-COOH, wobei n > 10 ist, vorzugsweise 16.Storage-stable cyanoacrylate adhesive according to claim 1, characterized by a fatty acid of the general formula CH₃- (CH₂) n -COOH, where n is> 10, preferably 16. Lagerstabiler Cyanoacrylat-Klebstoff nach Anspruch 1, gekennzeichnet durch einen Gehalt an Fettsäure von 10 bis 70 Gew.-%, bezogen auf das Fettsäureamid, vorzugsweise 20 bis 50 Gew.-%.Storage-stable cyanoacrylate adhesive according to claim 1, characterized by a fatty acid content of 10 to 70% by weight, based on the fatty acid amide, preferably 20 to 50% by weight. Lagerstabiler Cyanoacrylat-Klebstoff nach Anspruch 1, gekennzeichnet durch die Verfahrensschritte: a) Auftrag des Schmierstoffes auf das Al-Halbzeug und b) Umformen des Al-Halbzeugs, wobei sich vorzugsweise folgender Schritt anschließt: c) Erwärmen auf mehr als 300 °C für mindestens 10 Minuten. Storage-stable cyanoacrylate adhesive according to claim 1, characterized by the process steps: a) application of the lubricant to the Al semi-finished product and b) reshaping of the Al semi-finished product, preferably followed by the following step: c) Heating to more than 300 ° C for at least 10 minutes. Al-Tuben, hergestellt nach mindestens einem der Ansprüche 1 bis 5.Al tubes produced according to at least one of claims 1 to 5. Al-Halbzeug mit einem Schmierstoff nach mindestens einem der Ansprüche 1 bis 4.Al semi-finished product with a lubricant according to at least one of claims 1 to 4. Schmierstoff zum Umformen von Al-Halbzeug nach mindestens einem der Ansprüche 1 bis 4, insbesondere zum Fließpressen.Lubricant for forming Al semi-finished products according to at least one of Claims 1 to 4, in particular for extrusion.
EP92117603A 1991-10-24 1992-10-15 Storage stable cyanoacrylate adhesive in aluminum tubes Expired - Lifetime EP0538734B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4135116 1991-10-24
DE4135116A DE4135116A1 (en) 1991-10-24 1991-10-24 STORAGE CYANOACRYLATE ADHESIVE IN AL TUBES

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EP0538734A1 true EP0538734A1 (en) 1993-04-28
EP0538734B1 EP0538734B1 (en) 1995-12-06

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AT (1) ATE131204T1 (en)
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DK (1) DK0538734T3 (en)
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GR (1) GR3019218T3 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999025774A1 (en) * 1997-11-17 1999-05-27 Henkel Kommanditgesellschaft Auf Aktien Stabilised cyanoacrylate adhesives

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3505844A (en) * 1966-08-22 1970-04-14 Reynolds Metals Co Rolling lubrication
US3523895A (en) * 1969-04-21 1970-08-11 Mobil Oil Corp Metal working lubricant
US3523628A (en) * 1968-01-18 1970-08-11 Lee B Colvin Container for cyanoacrylate adhesive
BE890553A (en) * 1981-09-30 1982-03-30 Loctite Corp STABILIZED CYANO-ACRYLATE COMPOSITIONS
EP0192329A1 (en) * 1985-01-29 1986-08-27 Alcan International Limited Metal-forming lubricant
EP0276568A1 (en) * 1986-12-29 1988-08-03 Alcan International Limited Lubricant emulsion
US4980086A (en) * 1985-10-16 1990-12-25 Toagosei Chemical Industry, Co., Ltd. Curable composition
DE4109105A1 (en) * 1991-03-20 1992-09-24 Henkel Kgaa Stabilising cyanoacrylate ester(s) - by adding acid, e.g. p-toluenesulphonic or citric acid etc., to moulded plastics used in prodn., storage or use of ester(s)

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3505844A (en) * 1966-08-22 1970-04-14 Reynolds Metals Co Rolling lubrication
US3523628A (en) * 1968-01-18 1970-08-11 Lee B Colvin Container for cyanoacrylate adhesive
US3523895A (en) * 1969-04-21 1970-08-11 Mobil Oil Corp Metal working lubricant
BE890553A (en) * 1981-09-30 1982-03-30 Loctite Corp STABILIZED CYANO-ACRYLATE COMPOSITIONS
EP0192329A1 (en) * 1985-01-29 1986-08-27 Alcan International Limited Metal-forming lubricant
US4980086A (en) * 1985-10-16 1990-12-25 Toagosei Chemical Industry, Co., Ltd. Curable composition
EP0276568A1 (en) * 1986-12-29 1988-08-03 Alcan International Limited Lubricant emulsion
DE4109105A1 (en) * 1991-03-20 1992-09-24 Henkel Kgaa Stabilising cyanoacrylate ester(s) - by adding acid, e.g. p-toluenesulphonic or citric acid etc., to moulded plastics used in prodn., storage or use of ester(s)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPIL Week 9045, Derwent Publications Ltd., London, GB; AN 90-338154 & JP-A-2 242 897 (ORIENTAL SANGYO) 27. September 1990 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999025774A1 (en) * 1997-11-17 1999-05-27 Henkel Kommanditgesellschaft Auf Aktien Stabilised cyanoacrylate adhesives
US6642337B1 (en) 1997-11-17 2003-11-04 Henkel Kommanditgesellschaft Auf Aktien Stabilized cyanoacrylate adhesives

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DE4135116A1 (en) 1993-04-29
ES2081024T3 (en) 1996-02-16
ATE131204T1 (en) 1995-12-15
EP0538734B1 (en) 1995-12-06
DK0538734T3 (en) 1996-04-29
DE59204592D1 (en) 1996-01-18
GR3019218T3 (en) 1996-06-30

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