EP0628884B1 - Electrostatic toner, comprising a polyamine as charge control agent - Google Patents
Electrostatic toner, comprising a polyamine as charge control agent Download PDFInfo
- Publication number
- EP0628884B1 EP0628884B1 EP94107459A EP94107459A EP0628884B1 EP 0628884 B1 EP0628884 B1 EP 0628884B1 EP 94107459 A EP94107459 A EP 94107459A EP 94107459 A EP94107459 A EP 94107459A EP 0628884 B1 EP0628884 B1 EP 0628884B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyamine
- toner
- electrostatic
- charge
- nitrogen atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08768—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08766—Polyamides, e.g. polyesteramides
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09733—Organic compounds
- G03G9/09775—Organic compounds containing atoms other than carbon, hydrogen or oxygen
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08793—Crosslinked polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/001—Electric or magnetic imagery, e.g., xerography, electrography, magnetography, etc. Process, composition, or product
- Y10S430/105—Polymer in developer
Definitions
- the present invention relates to new electrostatic toners containing a polymeric binder and a polyamine as charge stabilizer, the average molecular weight of which is 150 to 15,000 and which has at least 3 nitrogen atoms, the nitrogen atoms being separated from one another by C 2 -C 4 -alkylene and having C 1 -C 13 alkyl, which is optionally substituted by phenyl, hydroxy or carboxyl, phenyl, C 1 -C 10 alkanoyl, benzoyl, C 1 -C 6 alkylcarbamoyl, phenylcarbamoyl or a radical of the formula CO-L-CO, where L is C 2 -C 8 -alkylene, where in the latter case a crosslinking of two polyamine units results, and the use of the above-mentioned polyamines as charge stabilizers in electrostatic toners.
- Latent electrostatic image recordings are developed that the toner is inductive on the electrostatic image is deposited.
- the charge stabilizers stabilize the electrostatic charge of the toner. This makes the picture more vivid and sharper contours.
- electrostatic toners contain amines or ammonium salts.
- EP-A-163 528 and JP-A-279 258/1989 describe electrostatic Toner with polyamines as charge stabilizers.
- the object of the present invention was therefore to develop new electrostatic Provide toners that have charge stabilizers have the advantageous application properties exhibit.
- All alkyl and alkylene residues occurring in the polyamines can be straight or branched.
- Suitable alkyl radicals are e.g. Methyl, ethyl, propyl, isopropyl, Butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, Hexyl, 2-methylpentyl, heptyl, 2-methylhexyl, octyl, Isooctyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, Dodecyl, tridecyl, isotridecyl, benzyl, 1- or 2-phenylethyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, 1-carboxylethyl or 2-carboxylpropyl.
- isooctyl, isononyl, Isodecyl and isotridecyl originate from those after oxosynthesis alcohols obtained - cf. also Ullmann's Encyclopedia der technical chemistry, 4th edition, volume 7, pages 215 to 217, and volume 11, pages 435 and 436).
- Suitable alkylene radicals are (CH 2 ) 2 , (CH 2 ) 3 , (CH 2 ) 4 , CH (CH 3 ) CH 2 , CH (CH 3 ) CH (CH 3 ), CH (C 6 H 5 ) CH 2 or CH (C 6 H 5 ) CH (C 6 H 5 ).
- Suitable alkanoyl residues are e.g. Formyl, acetyl, propionyl, Butyryl, isobutyryl, pentanoyl, isopentanoyl, hexanoyl, heptanoyl, Octanoyl, 2-ethylhexanoyl, nonanoyl or decanoyl.
- Suitable alkyl carbamoyl residues are e.g. Methylcarbamoyl, ethylcarbamoyl, Propylcarbamoyl, isopropylcarbamoyl, butylcarbamoyl, Isobutylcarbamoyl, pentylcarbamoyl, isopentylcarbamoyl, neopentylcarbmaoyl or hexylcarbamoyl.
- Electrostatic toners containing a polyamine are preferred. whose average molecular weight is 400 to 4,000.
- the polyamines in generally different proportions of primary, secondary and tertiary nitrogen atoms.
- Electrostatic toners which contain a polyamine in which the nitrogen atoms have C 1 -C 13 -alkyl as substituents are further preferred.
- Electrostatic toners containing a polyamine are particularly preferred contain, in which the nitrogen atoms by ethylene or 1,2- or 1,3-propylene, especially ethylene, separated from each other are.
- Electrostatic toners which contain a polyamine in which the nitrogen atoms have C 1 -C 6 -alkyl as substituents are also particularly preferred.
- polyamines mentioned above are generally known per se or can according to methods known per se, as in the US-A-3 705 200, DE-A-2 253 594 or DE-A-2 606 823, be preserved.
- alkylating substances all substances that are associated with the NH groups of Base body under exchange and enter into a reaction for this a substitutable group, e.g. Sulfate, halogen, hydroxy or Acetate.
- alkylating substances also consider such substances which contain an activated double bond, such as acrylic acid or styrene, or a reactive group, such as an oxirane ring, exhibit.
- acylating reagents like carboxylic acids, Carboxylic acid esters or isocyanates can be used for this purpose, since they also contain the primary and secondary nitrogen atoms of the Base body can substitute higher.
- reagents which are themselves substituted are particularly preferred Contain nitrogen atoms and easily with the nitrogen atoms of the base body can react and the largest Part of the primary and secondary amine functions in the main body in Convert tertiary amine functions.
- Particularly worth mentioning are Dialkylhydroxyalkylamines, whose alkyl groups have 1 to 13 carbon atoms contain linear, branched or cyclic with each other can be connected. They react with the polyamine body with leakage of water.
- the corresponding polyamine base bodies can e.g. on itself known way by conventional condensation, addition or substitution reactions from ammonia or amines and the like Reactants, for example by reacting ammonia with ethylene dichloride or propylene dichloride. You can also be produced by partial acylation of the nitrogen atoms with appropriate carboxylic acids. Especially as a basic body those base bodies are preferred which e.g. through polymerization can be obtained from aziridine.
- the proportion of the polyamines specified above in the electrostatic Toner is usually 0.01 to 10 wt .-%, based on the weight of the toner.
- the polymers contained in the new electrostatic toners Binders are known per se. They are usually thermoplastic and have a softening point of 40 to 200 ° C, preferably 50 to 130 ° C and especially 65 to 115 ° C.
- Examples for polymeric binders are polystyrene, copolymers of styrene with an acrylate or methacrylate, copolymers of styrene with Butadiene and / or acrylonitrile, polyacrylates, polymethacrylates, Copolymers of an acrylate or methacrylate with vinyl chloride or Vinyl acetate, polyvinyl chloride, copolymers of vinyl chloride with Vinylidene chloride, copolymers of vinyl chloride with vinyl acetate, Polyester resins, epoxy resins, polyamides or polyurethanes.
- the toners according to the invention can be binders in known Amounts of colorant, magnetically attractable material, waxes and Contain plasticizers.
- the colorants can be organic dyes or pigments, such as Nigrosine, aniline blue, 2,9-dimethylquinacridone, C.I. Disperse Red 15 (C.I. 6010), C.I. Solvent Red 19 (C.I. 26 050), C.I. pigment Blue 15 (C.I. 74 160), C.I. Pigment Blue 22 (C.I. 69 810) or C.I. Solvent Yellow 16 (C.I. 12 700) or inorganic pigments, such as carbon black, red lead, yellow lead oxide or chrome yellow. Generally the amount of colorant present in the toner exceeds not 15% by weight based on the weight of the toner.
- the magnetically attractable material can be, for example, iron, nickel, chromium oxide, iron oxide or a ferrite of the formula MeFe 2 O 4 , in which Me is a divalent metal, for example iron, cobalt, zinc, nickel or manganese.
- the toners according to the invention are produced by customary methods Methods, e.g. by mixing the ingredients in a kneader and then pulverizing or melting the polymer Binder or a mixture of the polymeric binders, subsequent fine division of one or more of the polyamines specified above, and the other additives, if used, in the molten resin using the Mixing and kneading machines known for this purpose, subsequent Cooling of the melt to a solid mass and finally Grinding the solid mass to particles of the desired particle size (usually 0.1 to 50 ⁇ m). It is also possible that polymeric binder and the charge stabilizer in one Suspend solvent and the other additives in to give the suspension. The suspension can be used as a liquid toner be used.
- the liquid can also be prepared in a manner known per se spray dry, evaporate the solvents or the liquid freeze dry and the solid residue into particles of grind the desired particle size.
- the toner preparation thus obtained can then, for example according to US-A-4,265,990, in a xerographic imaging system.
- the polyamines described in more detail above are advantageous charge stabilizers. As a rule, they meet the requirements initially stated Application profile and are particularly characterized in that they when added to a toner preparation, this is a favorable electrostatic Give a charging profile, i.e. leave the toner charge yourself quickly and highly. Those to be used according to the invention Charge stabilizers also cause the charge to is kept constant at a high level.
- Examples H2 to H6 listed in Table 1 below were carried out analogously to Example H1.
- N N-Dibutyl-N- (2-hydroxyethyl) amine was used as the amine.
- the toner was almost completely removed from the carrier particles by means of a strong air flow (approx. 4,000 cm 3 / min) and simultaneous suction, the latter remaining in the measuring cell.
- the charge on the carrier was registered on the electrometer. It corresponded to the amount of charging of the toner particles, but with the opposite sign. The amount of q with the opposite sign was therefore used to calculate the q / m value.
- the mass of blown-off toner was determined by weighing the measuring cell back and the electrostatic charge q / m was calculated therefrom.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Developing Agents For Electrophotography (AREA)
Description
Die vorliegende Erfindung betrifft neue elektrostatische Toner, enthaltend ein polymeres Bindemittel und als Ladungsstabilisator ein Polyamin, dessen mittleres Molekulargewicht 150 bis 15.000 beträgt und das mindestens 3 Stickstoffatome aufweist, wobei die Stickstoffatome durch C2-C4-Alkylen voneinander getrennt sind und als Substituenten C1-C13-Alkyl, das gegebenenfalls durch Phenyl, Hydroxy oder Carboxyl substituiert ist, Phenyl, C1-C10-Alkanoyl, Benzoyl, C1-C6-Alkylcarbamoyl, Phenylcarbamoyl oder einen Rest der Formel CO-L-CO, worin L für C2-C8-Alkylen steht, aufweisen, wobei im letzten Fall eine Vernetzung von zwei Polyamineinheiten resultiert, sowie die Verwendung der obengenannten Polyamine als Ladungsstabilisatoren in elektrostatischen Tonern.The present invention relates to new electrostatic toners containing a polymeric binder and a polyamine as charge stabilizer, the average molecular weight of which is 150 to 15,000 and which has at least 3 nitrogen atoms, the nitrogen atoms being separated from one another by C 2 -C 4 -alkylene and having C 1 -C 13 alkyl, which is optionally substituted by phenyl, hydroxy or carboxyl, phenyl, C 1 -C 10 alkanoyl, benzoyl, C 1 -C 6 alkylcarbamoyl, phenylcarbamoyl or a radical of the formula CO-L-CO, where L is C 2 -C 8 -alkylene, where in the latter case a crosslinking of two polyamine units results, and the use of the above-mentioned polyamines as charge stabilizers in electrostatic toners.
Latente elektrostatische Bildaufzeichnungen werden dadurch entwickelt, daß der Toner auf dem elektrostatischen Bild induktiv abgeschieden wird. Die Ladungsstabilisatoren stabilisieren die elektrostatische Ladung des Toners. Dadurch wird das Bild kräftiger und konturenschärfer.Latent electrostatic image recordings are developed that the toner is inductive on the electrostatic image is deposited. The charge stabilizers stabilize the electrostatic charge of the toner. This makes the picture more vivid and sharper contours.
Die verwendeten Ladungsstabilisatoren müssen dabei vielseitige Anforderungen erfüllen:
- Fähigkeit zur Entwicklung des latenten elektrostatischen Bildes zu einem farbstarken sichtbaren Bild.
- Leichte Verteilbarkeit in der Tonerzubereitung, um ein störungsfreies, konturenscharfes, gleichförmiges Bild zu erzeugen.
- Unempfindlichkeit gegen Feuchtigkeit.
- Hohe Thermostabilität.
- Ability to develop the latent electrostatic image into a highly visible color image.
- Easily distributable in the toner preparation in order to produce a trouble-free, contour-sharp, uniform image.
- Insensitivity to moisture.
- High thermal stability.
Aus der EP-A-242 420 sind elektrostatische Toner bekannt, die als Ladungsstabilisatoren Amine oder Ammoniumsalze enthalten.From EP-A-242 420 electrostatic toners are known which are known as Charge stabilizers contain amines or ammonium salts.
Die EP-A-163 528 sowie die JP-A-279 258/1989 beschreiben elektrostatische Toner mit Polyaminen als Ladungsstabilisatoren.EP-A-163 528 and JP-A-279 258/1989 describe electrostatic Toner with polyamines as charge stabilizers.
Es hat sich jedoch gezeigt, daß die Ladungsstabilisatoren des Standes der Technik häufig Mängel in ihrem Anforderungsprofil aufweisen. However, it has been shown that the charge stabilizers of State of the art often deficiencies in their requirement profile exhibit.
Aufgabe der vorliegenden Erfindung war es daher, neue elektrostatische Toner bereitzustellen, die über Ladungsstabilisatoren verfügen, die vorteilhafte anwendungstechnische Eigenschaften aufweisen.The object of the present invention was therefore to develop new electrostatic Provide toners that have charge stabilizers have the advantageous application properties exhibit.
Demgemäß wurden die eingangs näher bezeichneten elektrostatischen Toner gefunden.Accordingly, the electrostatic specified in the beginning Toner found.
Alle in den Polyaminen auftretenden Alkyl- und Alkylenreste können sowohl geradkettig als auch verzweigt sein.All alkyl and alkylene residues occurring in the polyamines can be straight or branched.
Geeignete Alkylreste sind z.B. Methyl, Ethyl, Propyl, Isopropyl, Butyl, Isobutyl, sec-Butyl, Pentyl, Isopentyl, Neopentyl, tert-Pentyl, Hexyl, 2-Methylpentyl, Heptyl, 2-Methylhexyl, Octyl, Isooctyl, 2-Ethylhexyl, Nonyl, Isononyl, Decyl, Isodecyl, Undecyl, Dodecyl, Tridecyl, Isotridecyl, Benzyl, 1- oder 2-Phenylethyl, 2-Hydroxyethyl, 2- oder 3-Hydroxypropyl, 1-Carboxylethyl oder 2-Carboxylpropyl. (Die obigen Bezeichnungen Isooctyl, Isononyl, Isodecyl und Isotridecyl stammen von den nach der Oxosynthese erhaltenen Alkoholen - vgl. dazu Ullmanns Encyclopädie der technischen Chemie, 4. Auflage, Band 7, Seiten 215 bis 217, sowie Band 11, Seiten 435 und 436).Suitable alkyl radicals are e.g. Methyl, ethyl, propyl, isopropyl, Butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, Hexyl, 2-methylpentyl, heptyl, 2-methylhexyl, octyl, Isooctyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, Dodecyl, tridecyl, isotridecyl, benzyl, 1- or 2-phenylethyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, 1-carboxylethyl or 2-carboxylpropyl. (The terms isooctyl, isononyl, Isodecyl and isotridecyl originate from those after oxosynthesis alcohols obtained - cf. also Ullmann's Encyclopedia der technical chemistry, 4th edition, volume 7, pages 215 to 217, and volume 11, pages 435 and 436).
Geeignete Alkylenreste sind (CH2)2, (CH2)3, (CH2)4, CH(CH3)CH2, CH(CH3)CH(CH3), CH(C6H5)CH2 oder CH (C6H5)CH (C6H5).Suitable alkylene radicals are (CH 2 ) 2 , (CH 2 ) 3 , (CH 2 ) 4 , CH (CH 3 ) CH 2 , CH (CH 3 ) CH (CH 3 ), CH (C 6 H 5 ) CH 2 or CH (C 6 H 5 ) CH (C 6 H 5 ).
Geeignete Alkanoylreste sind z.B. Formyl, Acetyl, Propionyl, Butyryl, Isobutyryl, Pentanoyl, Isopentanoyl, Hexanoyl, Heptanoyl, Octanoyl, 2-Ethylhexanoyl, Nonanoyl oder Decanoyl.Suitable alkanoyl residues are e.g. Formyl, acetyl, propionyl, Butyryl, isobutyryl, pentanoyl, isopentanoyl, hexanoyl, heptanoyl, Octanoyl, 2-ethylhexanoyl, nonanoyl or decanoyl.
Geeignete Alkylcarbamoylreste sind z.B. Methylcarbamoyl, Ethylcarbamoyl, Propylcarbamoyl, Isopropylcarbamoyl, Butylcarbamoyl, Isobutylcarbamoyl, Pentylcarbamoyl, Isopentylcarbamoyl, Neopentylcarbmaoyl oder Hexylcarbamoyl.Suitable alkyl carbamoyl residues are e.g. Methylcarbamoyl, ethylcarbamoyl, Propylcarbamoyl, isopropylcarbamoyl, butylcarbamoyl, Isobutylcarbamoyl, pentylcarbamoyl, isopentylcarbamoyl, neopentylcarbmaoyl or hexylcarbamoyl.
Bevorzugt sind elektrostatische Toner, die ein Polyamin enthalten, dessen mittleres Molekulargewicht 400 bis 4.000 beträgt.Electrostatic toners containing a polyamine are preferred. whose average molecular weight is 400 to 4,000.
In den elektrostatischen Tonern, die ein Polyamin enthalten, das mindestens 3 Stickstoffatome aufweist, weisen die Polyamine im allgemeinen unterschiedliche Anteile an primären, sekundären und tertiären Stickstoffatomen auf. In the electrostatic toners containing a polyamine that has at least 3 nitrogen atoms, the polyamines in generally different proportions of primary, secondary and tertiary nitrogen atoms.
Weiterhin bevorzugt sind elektrostaische Toner, die ein Polyamin enthalten, in dem die Stickstoffatome C1-C13-Alkyl als Substituenten aufweisen.Electrostatic toners which contain a polyamine in which the nitrogen atoms have C 1 -C 13 -alkyl as substituents are further preferred.
Besonders bevorzugt sind elektrostatische Toner, die ein Polyamin enthalten, in dem die Stickstoffatome durch Ethylen oder 1,2- oder 1,3-Propylen, insbesondere Ethylen, voneinander getrennt sind.Electrostatic toners containing a polyamine are particularly preferred contain, in which the nitrogen atoms by ethylene or 1,2- or 1,3-propylene, especially ethylene, separated from each other are.
Besonders bevorzugt sind weiterhin elektrostatische Toner, die ein Polyamin enthalten, in dem die Stickstoffatome C1-C6-Alkyl als Substituenten aufweisen.Electrostatic toners which contain a polyamine in which the nitrogen atoms have C 1 -C 6 -alkyl as substituents are also particularly preferred.
Die obengenannten Polyamine sind in der Regel an sich bekannt oder können nach an sich bekannten Methoden, wie in der US-A-3 705 200, DE-A-2 253 594 oder DE-A-2 606 823 beschrieben, erhalten werden.The polyamines mentioned above are generally known per se or can according to methods known per se, as in the US-A-3 705 200, DE-A-2 253 594 or DE-A-2 606 823, be preserved.
Sie können beispielsweise erhalten werden, indem man Polyamin-Grundkörper mit alkylierenden oder acylierenden Substanzen umsetzt, die die primären und sekundären Stickstoffatome des Grundkörpers höher substituieren. Als alkylierende Substanzen kommen dabei alle Substanzen in Betracht, die mit den NH-Gruppen des Grundkörpers unter Austausch eine Reaktion eingehen und hierfür eine substituierbare Gruppe, z.B. Sulfat, Halogen, Hydroxy oder Acetat, enthalten. Es kommen z.B. auch solche Substanzen in Betracht, die eine aktivierte Doppelbindung enthalten, wie Acrylsäure oder Styrol, oder die eine reaktive Gruppe, wie einen Oxiranring, aufweisen. Auch acylierende Reagenzien wie Carbonsäuren, Carbonsäureester oder Isocyanate können hierzu Verwendung finden, da sie ebenfalls die primären und sekundären Stickstoffatome des Grundkörpers höher substituieren können.They can be obtained, for example, by using polyamine bases reacted with alkylating or acylating substances, which are the primary and secondary nitrogen atoms of the main body substitute higher. Come as alkylating substances all substances that are associated with the NH groups of Base body under exchange and enter into a reaction for this a substitutable group, e.g. Sulfate, halogen, hydroxy or Acetate. E.g. also consider such substances which contain an activated double bond, such as acrylic acid or styrene, or a reactive group, such as an oxirane ring, exhibit. Also acylating reagents like carboxylic acids, Carboxylic acid esters or isocyanates can be used for this purpose, since they also contain the primary and secondary nitrogen atoms of the Base body can substitute higher.
Besonders bevorzugt sind solche Reagenzien, die selbst substituierte Stickstoffatome enthalten und leicht mit den Stickstoffatomen des Grundkörpers reagieren können und dabei den größten Teil der primären und sekundären Aminfunktionen im Grundkörper in tertiäre Aminfunktionen umwandeln. Besonders zu nennen sind z.B. Dialkylhydroxyalkylamine, deren Alkylgruppen 1 bis 13 Kohlenstoffatome enthalten, die linear, verzweigt oder cyclisch miteinander verbunden sein können. Sie reagieren mit den Polyamin-Grundkörpern unter Austritt von Wasser. Those reagents which are themselves substituted are particularly preferred Contain nitrogen atoms and easily with the nitrogen atoms of the base body can react and the largest Part of the primary and secondary amine functions in the main body in Convert tertiary amine functions. Particularly worth mentioning are Dialkylhydroxyalkylamines, whose alkyl groups have 1 to 13 carbon atoms contain linear, branched or cyclic with each other can be connected. They react with the polyamine body with leakage of water.
Die entsprechenden Polyamin-Grundkörper können z.B. auf an sich bekanntem Wege durch übliche Kondensations-, Additions- oder Substitutionsreaktionen aus Ammoniak oder Aminen und entsprechenden Reaktanden, beispielsweise durch Umsetzung von Ammoniak mit Ethylendichlorid oder Propylendichlorid hergestellt werden. Sie können auch hergestellt werden durch teilweise Acylierung der Stickstoffatome mit entsprechenden Carbonsäuren. Als Grundkörper besonders bevorzugt sind solche Grundkörper, die z.B. durch Polymerisation von Aziridin erhalten werden.The corresponding polyamine base bodies can e.g. on itself known way by conventional condensation, addition or substitution reactions from ammonia or amines and the like Reactants, for example by reacting ammonia with ethylene dichloride or propylene dichloride. You can also be produced by partial acylation of the nitrogen atoms with appropriate carboxylic acids. Especially as a basic body those base bodies are preferred which e.g. through polymerization can be obtained from aziridine.
Der Anteil der oben näher bezeichneten Polyamine im elektrostatischen Toner beträgt in der Regel 0,01 bis 10 Gew.-%, bezogen auf das Gewicht des Toners.The proportion of the polyamines specified above in the electrostatic Toner is usually 0.01 to 10 wt .-%, based on the weight of the toner.
Die in den neuen elektrostatischen Tonern enthaltenen polymeren Bindemittel sind an sich bekannt. Sie sind in der Regel thermoplastisch und haben einen Erweichungspunkt von 40 bis 200°C, vorzugsweise 50 bis 130°C und insbesondere 65 bis 115°C. Beispiele für polymere Bindemittel sind Polystyrol, Copolymere von Styrol mit einem Acrylat oder Methacrylat, Copolymere von Styrol mit Butadien und/oder Acrylnitril, Polyacrylate, Polymethacrylate, Copolymere eines Acrylats oder Methacrylats mit Vinylchlorid oder Vinylacetat, Polyvinylchlorid, Copolymere von Vinylchlorid mit Vinylidenchlorid, Copolymere von Vinylchlorid mit Vinylacetat, Polyesterharze, Epoxyharze, Polyamide oder Polyurethane.The polymers contained in the new electrostatic toners Binders are known per se. They are usually thermoplastic and have a softening point of 40 to 200 ° C, preferably 50 to 130 ° C and especially 65 to 115 ° C. Examples for polymeric binders are polystyrene, copolymers of styrene with an acrylate or methacrylate, copolymers of styrene with Butadiene and / or acrylonitrile, polyacrylates, polymethacrylates, Copolymers of an acrylate or methacrylate with vinyl chloride or Vinyl acetate, polyvinyl chloride, copolymers of vinyl chloride with Vinylidene chloride, copolymers of vinyl chloride with vinyl acetate, Polyester resins, epoxy resins, polyamides or polyurethanes.
Zusätzlich zu den obengenannten Polyaminen und den polymeren Bindemitteln können die erfindungsgemäßen Toner in bekannten Mengen Farbmittel, magnetisch anziehbares Material, Wachse und Fließmittel enthalten.In addition to the above polyamines and polymers The toners according to the invention can be binders in known Amounts of colorant, magnetically attractable material, waxes and Contain plasticizers.
Die Farbmittel können organische Farbstoffe oder Pigmente, wie Nigrosin, Anilinblau, 2,9-Dimethylchinacridon, C.I. Disperse Red 15 (C.I. 6010), C.I. Solvent Red 19 (C.I. 26 050), C.I. Pigment Blue 15 (C.I. 74 160), C.I. Pigment Blue 22 (C.I. 69 810) oder C.I. Solvent Yellow 16 (C.I. 12 700) oder anorganische Pigmente, wie Ruß, Rotblei, gelbes Bleioxid oder Chromgelb, sein. Allgemein überschreitet die Menge des im Toner vorhandenen Farbmittels nicht 15 Gew.-%, bezogen auf das Gewicht des Toners.The colorants can be organic dyes or pigments, such as Nigrosine, aniline blue, 2,9-dimethylquinacridone, C.I. Disperse Red 15 (C.I. 6010), C.I. Solvent Red 19 (C.I. 26 050), C.I. pigment Blue 15 (C.I. 74 160), C.I. Pigment Blue 22 (C.I. 69 810) or C.I. Solvent Yellow 16 (C.I. 12 700) or inorganic pigments, such as carbon black, red lead, yellow lead oxide or chrome yellow. Generally the amount of colorant present in the toner exceeds not 15% by weight based on the weight of the toner.
Das magnetisch anziehbare Material kann beispielsweise Eisen, Nickel, Chromoxid, Eisenoxid oder ein Ferrit der Formel MeFe2O4, worin Me ein zweiwertiges Metall, z.B. Eisen, Kobalt, Zink, Nickel oder Mangan, darstellt, sein. The magnetically attractable material can be, for example, iron, nickel, chromium oxide, iron oxide or a ferrite of the formula MeFe 2 O 4 , in which Me is a divalent metal, for example iron, cobalt, zinc, nickel or manganese.
Die Herstellung der erfindungsgemäßen Toner erfolgt nach üblichen Verfahren, z.B. durch Vermischen der Bestandteile in einem Kneter und anschließendes Pulverisieren oder durch Schmelzen des polymeren Bindemittels oder eines Gemisches der polymeren Bindemittel, anschließende feine Zerteilung eines oder mehrerer der oben näher bezeichneten Polyamine, sowie der anderen Zusätze, falls verwendet, in dem geschmolzenen Harz unter Anwendung der für diesen Zweck bekannten Misch- und Knetmaschinen, anschließende Abkühlung der Schmelze zu einer festen Masse und schließlich Vermahlen der festen Masse zu Teilchen der gewünschten Teilchengröße (in der Regel 0,1 bis 50 µm). Es ist auch möglich, das polymere Bindemittel und den Ladungsstabilisator in einem gemeinsamen Lösungsmittel zu suspendieren und die anderen Zusätze in die Suspension zu geben. Die Suspension kann so als Flüssigtoner verwendet werden.The toners according to the invention are produced by customary methods Methods, e.g. by mixing the ingredients in a kneader and then pulverizing or melting the polymer Binder or a mixture of the polymeric binders, subsequent fine division of one or more of the polyamines specified above, and the other additives, if used, in the molten resin using the Mixing and kneading machines known for this purpose, subsequent Cooling of the melt to a solid mass and finally Grinding the solid mass to particles of the desired particle size (usually 0.1 to 50 µm). It is also possible that polymeric binder and the charge stabilizer in one Suspend solvent and the other additives in to give the suspension. The suspension can be used as a liquid toner be used.
Man kann die Flüssigkeit aber auch in an sich bekannter Weise sprühtrocknen, die Lösungsmittel abdampfen oder die Flüssigkeit gefriertrocknen und den festen Rückstand zu Teilchen der gewünschten Teilchengröße vermahlen.However, the liquid can also be prepared in a manner known per se spray dry, evaporate the solvents or the liquid freeze dry and the solid residue into particles of grind the desired particle size.
Es ist weiterhin möglich, die als Ladungstabilisatoren verwendeten Polyamine nicht zu lösen, sondern fein in der Lösung des polymeren Bindemittels zu dispergieren. Die so erhaltene Tonerzubereitung kann dann, beispielsweise gemäß der US-A-4 265 990, in einem xerographischen Bildaufzeichnungssystem verwendet werden.It is also possible to use the charge stabilizers Not to dissolve polyamines, but fine in the solution of the disperse polymeric binder. The toner preparation thus obtained can then, for example according to US-A-4,265,990, in a xerographic imaging system.
Die oben näher bezeichneten Polyamine sind vorteilhafte Ladungsstabilisatoren. Sie genügen in der Regel dem eingangs geforderten Anwendungsprofil und zeichnen sich besonders dadurch aus, daß sie bei Zusatz zu einer Tonerpräparation dieser ein günstiges elektrostatisches Aufladungsprofil verleihen, d.h. die Toner lassen sich schnell und hoch aufladen. Die erfindungsgemäß anzuwendenden Ladungsstabilisatoren bewirken weiterhin, daß die Ladung auf einem hohen Niveau konstant gehalten wird.The polyamines described in more detail above are advantageous charge stabilizers. As a rule, they meet the requirements initially stated Application profile and are particularly characterized in that they when added to a toner preparation, this is a favorable electrostatic Give a charging profile, i.e. leave the toner charge yourself quickly and highly. Those to be used according to the invention Charge stabilizers also cause the charge to is kept constant at a high level.
Die folgenden Beispiele sollen die Erfindung näher erläutern.The following examples are intended to explain the invention in more detail.
277,3 g (1,6 mol) N,N-Dibutyl-N-(2-hydroxyethyl)amin wurden bei Raumtemperatur mit 69,6 g (1,28 mol) Polyethylenamin (mittleres Molgewicht: 430) unter Zugabe von 5 g 50 gew.-%iger wäßriger unterphosphoriger Säure vermischt. Unter Rühren und Stickstoffatmosphäre wurde die Mischung bis auf 230°C erwärmt. Hierbei destillierten insgesamt 26,9 g Wasser und 15,1 g N,N-Dibutyl-N-(2-hydroxyethyl)amin ab. Der Rückstand (ein viskoses Öl) wurde nach Erkalten in den Toner eingearbeitet.277.3 g (1.6 mol) of N, N-dibutyl-N- (2-hydroxyethyl) amine were added Room temperature with 69.6 g (1.28 mol) of polyethylene amine (medium Molecular weight: 430) with the addition of 5 g of 50 wt .-% aqueous hypophosphorous acid mixed. With stirring and nitrogen atmosphere the mixture was heated to 230 ° C. Here distilled a total of 26.9 g of water and 15.1 g of N, N-dibutyl-N- (2-hydroxyethyl) amine from. The residue (a viscous oil) was incorporated into the toner after cooling.
Analog Beispiel H1 wurden die in der folgenden Tabelle 1 aufgeführten
Beispiele H2 bis H6 durchgeführt. Als Amin wurde jeweils
N,N-Dibutyl-N-(2-hydroxyethyl)amin verwendet.
Die Anwendungsbeispiele wurden mit farbmittelfreien Tonermodellen, bestehend aus Harz und den erfindungsgemäßen Ladungsstabilisatoren, durchgeführt.The application examples were made with colorant-free toner models, consisting of resin and the charge stabilizers according to the invention, carried out.
In eine Lösung von 10 g eines nicht vernetzten Styrol/Butylacrylatharzes in 100 ml Xylol wurden bei Raumtemperatur 0,2 g des Polyamins aus Beispiel H 1 eingetragen und anschließend gefriergetrocknet.In a solution of 10 g of an uncrosslinked styrene / butyl acrylate resin 0.2 g of the were in 100 ml of xylene at room temperature Polyamine from Example H 1 entered and then freeze-dried.
In einem Mixer wurden 10 g eines nicht vernetzten Styrol/Butylacrylatharzes und 0,2 g des Polyamins aus Beispiel H 1 intensiv gemischt, bei 120°C geknetet, extrudiert und gemahlen. Es wurden durch Sichtung Tonerteilchen einer mittleren Partikelgröße von 50 µm erzeugt. 10 g of a non-crosslinked styrene / butyl acrylate resin were placed in a mixer and 0.2 g of the polyamine from Example H 1 intensive mixed, kneaded at 120 ° C, extruded and ground. There were by sighting toner particles with an average particle size of 50 µm generated.
Zur Herstellung eines Developers wurden 99 Gew.-% eines Stahlcarriers, der eine mittlere Teilchengröße von 100 µm aufwies, mit 1 Gew.-% des Toners genau eingewogen und über einen unten näher bestimmten Zeitraum hinweg auf einem Rollenbock aktiviert. Danach wurde die elektrostatische Aufladung des Developers bestimmt. Etwa 5 g des aktivierten Developers wurden in einem handelsüblichen q/m-Meter (Firma Epping GmbH, Neufahrn) in eine hard-blow-off-Zelle, die mit einem Elektrometer elektrisch verbunden war, eingefüllt. Die Maschenweiten der in der Meßzelle eingesetzten Siebe betrug 80 µm.99% by weight of a steel carrier, which had an average particle size of 100 microns with 1% by weight of the toner weighed in exactly and more closely below activated for a certain period of time on a roller block. After that the electrostatic charge of the developer was determined. About 5 g of the activated developer were in a commercially available q / m meter (Epping GmbH, Neufahrn) in a hard-blow-off cell, that was electrically connected to an electrometer, filled. The mesh sizes of those used in the measuring cell Sieves were 80 µm.
Damit war gewährleistet, daß der Toner möglichst vollständig ausgeblasen wurde, der Carrier aber in der Meßzelle verblieb. Durch einen kräftigen Luftstrom (ca. 4 000 cm3/min) und gleichzeitigem Absaugen wurde der Toner nahezu vollständig von den Carrierteilchen entfernt, wobei letztere in der Meßzelle verblieben. Die Aufladung des Carriers wurde am Elektrometer registriert. Sie entsprach dem Betrag der Aufladung der Tonerteilchen, nur mit umgekehrten Vorzeichen. Zur Berechnung des q/m-Wertes wurde deshalb der Betrag von q mit den umgekehrten Vorzeichen verwendet. Durch Zurückwiegen der Meßzelle wurde die Masse an ausgeblasenem Toner bestimmt und daraus die elektrostatische Aufladung q/m berechnet.This ensured that the toner was blown out as completely as possible, but the carrier remained in the measuring cell. The toner was almost completely removed from the carrier particles by means of a strong air flow (approx. 4,000 cm 3 / min) and simultaneous suction, the latter remaining in the measuring cell. The charge on the carrier was registered on the electrometer. It corresponded to the amount of charging of the toner particles, but with the opposite sign. The amount of q with the opposite sign was therefore used to calculate the q / m value. The mass of blown-off toner was determined by weighing the measuring cell back and the electrostatic charge q / m was calculated therefrom.
Die an den Tonern bestimmte Aufladung ist in der folgenden
Tabelle 2 zusammengefaßt.
Claims (4)
- Electrostatic toners comprising a polymeric binder and a charge stabilizer that is a polyamine whose average molecular weight is from 150 to 15,000 and which has at least three nitrogen atoms, wherein the nitrogen atoms are separated from each other by C2-C4-alkylene, and are substituted by C1-C13-alkyl, which may be phenyl-, hydroxyl- or carboxyl-substituted, phenyl, C1-C10-alkanoyl, benzoyl, C1-C6-alkylcarbamoyl, phenylcarbamoyl or a radical of the formula CO-L-CO, where L is C2-C8-alkylene, the last case resulting in the crosslinking of two polyamine units.
- Electrostatic toners as claimed in claim 1 comprising a polyamine whose average molecular weight is from 400 to 4,000.
- Electrostatic toners as claimed in claim 1 comprising a polyamine in which the nitrogen atoms are substituted by C1-C13-alkyl.
- The use of the amines of claim 1 as charge stabilizers in electrostatic toners.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4317059A DE4317059A1 (en) | 1993-05-21 | 1993-05-21 | Electrostatic toners containing polyamines as charge stabilisers |
DE4317059 | 1993-05-21 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0628884A1 EP0628884A1 (en) | 1994-12-14 |
EP0628884B1 true EP0628884B1 (en) | 1998-12-23 |
Family
ID=6488665
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94107459A Expired - Lifetime EP0628884B1 (en) | 1993-05-21 | 1994-05-13 | Electrostatic toner, comprising a polyamine as charge control agent |
Country Status (4)
Country | Link |
---|---|
US (1) | US5491043A (en) |
EP (1) | EP0628884B1 (en) |
JP (1) | JPH06348061A (en) |
DE (2) | DE4317059A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1205812B1 (en) | 2000-10-30 | 2006-05-17 | Dainippon Ink And Chemicals, Inc. | Charge-controlling agent and toner using the same |
DE102008002989A1 (en) * | 2007-08-16 | 2009-02-19 | Basf Se | Electrically conductive, magnetic composite material, process for its preparation and its use |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3705200A (en) * | 1970-10-30 | 1972-12-05 | Exxon Research Engineering Co | Process for telomerizing conjugated diolefins with aromatics and olefins |
US3758580A (en) * | 1971-11-26 | 1973-09-11 | Exxon Research Engineering Co | Separation of tertiary chelating polyamines |
JPS5111492B2 (en) * | 1973-02-19 | 1976-04-12 | ||
JPS5313284B2 (en) * | 1974-07-12 | 1978-05-09 | ||
US4068058A (en) * | 1975-03-05 | 1978-01-10 | Exxon Research And Engineering Company | Aminated polymeric additives for fuel and lubricants |
GB1538350A (en) * | 1975-03-05 | 1979-01-17 | Exxon Research Engineering Co | Aminated polymeric additives for fuels and lubricants |
US4265990A (en) * | 1977-05-04 | 1981-05-05 | Xerox Corporation | Imaging system with a diamine charge transport material in a polycarbonate resin |
DE2931087C2 (en) * | 1978-08-01 | 1986-07-03 | Fujitsu Ltd., Kawasaki, Kanagawa | Electrostatographic developer material |
JPS5941184B2 (en) * | 1982-04-01 | 1984-10-05 | 株式会社 巴川製紙所 | Color toner for electrophotography |
JPS59116662A (en) * | 1982-12-23 | 1984-07-05 | Tomoegawa Paper Co Ltd | Electrophotographic sensitive body |
JPS60188958A (en) * | 1984-03-08 | 1985-09-26 | Sumitomo Chem Co Ltd | Electrostatic charge image developing toner |
EP0163528A3 (en) * | 1984-05-29 | 1987-05-06 | Konica Corporation | Toner for developing electrostatic latent image |
US4749638A (en) * | 1985-05-08 | 1988-06-07 | Kao Corporation | Electrophotographic toner composition |
JPH0661006B2 (en) * | 1985-07-11 | 1994-08-10 | 三田工業株式会社 | Image forming method using photoconductive toner |
JPS6294856A (en) * | 1985-10-21 | 1987-05-01 | Orient Chem Ind Ltd | Toner for developing electrostatic charge image |
JPH01279258A (en) * | 1988-05-02 | 1989-11-09 | Canon Inc | Toner for developing electrostatic charge image |
US5009979A (en) * | 1989-10-23 | 1991-04-23 | Olin Hunt Specialty Products Inc. | Electrostatographic particulate toner and developer compositions |
US5334470A (en) * | 1991-09-02 | 1994-08-02 | Ricoh Company, Ltd. | Electrophotographic element with M-phenylenediamine derivatives therein |
EP0534514B1 (en) * | 1991-09-24 | 1996-11-20 | Agfa-Gevaert N.V. | Electrophotographic recording material |
US5256516A (en) * | 1992-07-31 | 1993-10-26 | Xerox Corporation | Toner compositions with dendrimer charge enhancing additives |
-
1993
- 1993-05-21 DE DE4317059A patent/DE4317059A1/en not_active Withdrawn
-
1994
- 1994-05-13 EP EP94107459A patent/EP0628884B1/en not_active Expired - Lifetime
- 1994-05-13 DE DE59407514T patent/DE59407514D1/en not_active Expired - Fee Related
- 1994-05-18 US US08/245,559 patent/US5491043A/en not_active Expired - Fee Related
- 1994-05-20 JP JP6106617A patent/JPH06348061A/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
JPH06348061A (en) | 1994-12-22 |
DE4317059A1 (en) | 1994-11-24 |
EP0628884A1 (en) | 1994-12-14 |
US5491043A (en) | 1996-02-13 |
DE59407514D1 (en) | 1999-02-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE3885567T3 (en) | Dispersant. | |
EP0270126B1 (en) | Addition compounds suitable as dispersants or as dispersion stabilizers, process for their preparation, their use and the solids coated therewith | |
DE69509088T2 (en) | POLYETHERPHOSPHATE | |
DE69301706T2 (en) | Urea-modified copolymer dispersant for pigments in coating compositions | |
DE1719427C3 (en) | Use of a polymeric amphiphilic compound as a stabilizer in dispersing particulate solids in a lipophilic or hydrophilic liquid | |
EP1061419A1 (en) | Use of cyan pigments in electrophotographic toners, developers, powder lacquers and ink-jet-inks | |
EP0548826B1 (en) | Diallyl ammonium-compounds, method for their preparation and their application | |
DE102006062441A1 (en) | Comb polymer is useful as a wetting agent and dispersant comprises styrene units and derivatized maleic anhydride units with phosphate or quaternary ammonium functions | |
DE19712765A1 (en) | Powder coating composition with improved screening properties | |
DE3405206A1 (en) | MICROCAPSLE SHAPED TONER | |
WO2006040284A1 (en) | Aqueous effect pigment paste, method for producing the same and the use thereof | |
EP0656131B1 (en) | Electrostatic toner containing a metal complex colorant as charge stabiliser | |
DE3586731T2 (en) | RESIN COLORS AND RESIN DYE. | |
EP0476647B1 (en) | Polymeric ammonium compounds as charge directors | |
EP0628884B1 (en) | Electrostatic toner, comprising a polyamine as charge control agent | |
DE3120542C2 (en) | Positively chargeable toner | |
EP0377553A2 (en) | Toner composition comprising rosin modified styrene acrylic resin | |
EP0609718A2 (en) | Ammonium salts of cyclic diallylpolysulfones | |
DE3422564C2 (en) | ||
DE4232524A1 (en) | Benzimidazoles and their application as charge stabilizers | |
EP0750652B1 (en) | Levelling agents for powdered paints | |
EP0680627B1 (en) | Electrostatic toners containing aminodiacetic acid derivatives | |
US4448916A (en) | Resin antistatic and strengthening composition | |
DE3738948A1 (en) | COLORLESS SALTS OF HETEROPOLYSAURS AND CATIONIC AROMATIC IMIDES AS CHARGE CONTROL SUBSTANCES IN TONERS | |
DE69611446T2 (en) | POWDER COMPOSITIONS FOR USE AS TONER |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE CH DE ES FR GB IE IT LI NL |
|
17P | Request for examination filed |
Effective date: 19941117 |
|
17Q | First examination report despatched |
Effective date: 19970225 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE CH DE ES FR GB IE IT LI NL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 19981223 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 19981223 Ref country code: ES Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY Effective date: 19981223 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REF | Corresponds to: |
Ref document number: 59407514 Country of ref document: DE Date of ref document: 19990204 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19990115 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: GERMAN |
|
ET | Fr: translation filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990531 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990531 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990531 |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990820 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FD4D |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
BERE | Be: lapsed |
Owner name: BASF A.G. Effective date: 19990531 |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19991223 Year of fee payment: 7 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20000413 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20000505 Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010513 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010517 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20010513 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020131 |