EP0233544B1 - Electrophotographical toner - Google Patents

Electrophotographical toner Download PDF

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Publication number
EP0233544B1
EP0233544B1 EP87101463A EP87101463A EP0233544B1 EP 0233544 B1 EP0233544 B1 EP 0233544B1 EP 87101463 A EP87101463 A EP 87101463A EP 87101463 A EP87101463 A EP 87101463A EP 0233544 B1 EP0233544 B1 EP 0233544B1
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EP
European Patent Office
Prior art keywords
stands
alkyl
formula
single bond
methyl
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EP87101463A
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German (de)
French (fr)
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EP0233544A2 (en
EP0233544A3 (en
Inventor
Horst Dr. Harnisch
Roderich Dr. Raue
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Bayer AG
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Bayer AG
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    • 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
    • G03G9/09741—Organic compounds cationic

Definitions

  • EP-A 0 028 777 discloses naphthalimides which have an OR substituent in the naphthalene part and can be used as optical brighteners.
  • EP-A 0 154 740 discloses charge-enhancing phthalimides which have properties which need improvement.
  • C1-C5 alkylene radicals A can be straight-chain or branched.
  • C2-C5 alkylene radicals and especially the n-propylene radical are preferred.
  • Preferred alkyl radicals R3 are C1-C16 alkyl radicals.
  • halides e.g. Chloride, bromide and iodide. Tetrafluoroborates and anions of alkyl and aryl sulfonic acids, carboxylic acids, phosphoric acids and phosphonic acids are suitable.
  • Anions which lower the water solubility of the compounds (I) and at the same time increase the solubility in organic solvents such as dimethylformamide, acetone, chloroform or toluene are particularly suitable.
  • the water solubility can also be reduced by increasing the alkyl radical R3, that is to say approximately in the range of C5-C16-alkyl. In this case, more hydrophilic anions such as halides are also very suitable.
  • preferred water solubility of the compounds (I) at 20 ° C. is below 3% by weight, in particular below 1% by weight.
  • preferred anions are, in particular aryl sulfonates such as benzene sulfonates optionally substituted by C1-C12 alkyl or chlorine, C5-C18 alkyl sulfonates, salts of C5-C18 alkyl carboxylic acids and of condensation products of formaldehyde and aryl sulfonic acids and / or optionally sulfonated 4,4'-dihydroxydiphenyl sulfone.
  • the compounds of formula (I) can be prepared by known methods, e.g. according to the processes described in DE-A 35 35496.
  • the connections themselves are mostly known.
  • Charge-enhancing additives for electrophotographic toners also called charge control substances, are already known. They are described, for example, in U.S. Patent Nos. 3,893,935, 3,944,493, 4,007,293, 4,079,014, 4,298,672, 4,338,390, 4,394,430 and 4,493,883.
  • Latent electrostatic image recordings are developed by inductively depositing the toner on the electrostatic image.
  • the charge control substances increase the cationic charge of the toner. This makes the picture more vivid and sharper.
  • the substances (I) are very suitable as charge control substances in toners.
  • the compounds (I) result in a significant increase in the color depth of the developed image and an improvement in the image sharpness.
  • Another advantage is the much better pH Stability that makes both the production of the compounds and the toner preparations easier.
  • the resins contained in the toners are known, they are thermoplastic and have a softening point between 50 and 130 ° C, preferably between 65 and 115 ° C.
  • examples of such resins include polystyrene, copolymers of styrene with an acrylate or methacrylate, copolymers of styrene with butadiene and / or acrylonitrile, polyacrylates and 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 (U.S. Patent 3,590,000), epoxy resins, polyamides and polyurethanes.
  • the toners of the present invention contain coloring materials and magnetically attractable material in known amounts.
  • the magnetically attractable material can for example consist of iron, nickel, chromium oxide, iron oxide or a ferrite of the general formula MFe2O4, where M is a divalent metal such as iron, cobalt, zinc, nickel or manganese.
  • the toners containing the compounds (I) are prepared by customary processes, e.g. by melting the thermoplastic resin or a mixture of the thermoplastic resins, then finely dividing one or more charge control substances of formula (I), as well as the other additives, if used, into the melted resin using the mixing and kneading machinery known for this purpose Cooling the melt to a solid mass and finally grinding the solid mass into particles of the desired particle size. It is also possible to dissolve the thermoplastic resin and the compound (I) in a common solvent, to incorporate the other additives into the solution and then to spray-dry the liquid in a manner known per se or to evaporate off the solvent or solvents and to add the solid residue To grind particles of the desired particle size. According to a modification of this manufacturing process, the charge control substance of the formula (I) is not dissolved, but finely dispersed in the solution of the thermoplastic resin.
  • the toner preparation thus obtained is then used in a xerographic image recording system, for example analogously to US Pat. No. 4,265,990.
  • the photoreceptors used for this must have the ability to charge negatively. Examples are those also described in U.S. Patent 4,265,990.
  • You can use the following substances in the charge-conducting layer for example contain: 4-dimethylaminobenzylidene-benzhydrazide, polyvinylcarbazole, 2-benzylidene-aminocarbazole, 2-nitrobenzylidene-p-bromoaniline, 2,4-diphenylquinazollene, 1,5-diphenyl-3-methylpyrazoline, 1,3,5-triphenylpyrazoline, Charge transfer complex of polyvinyl carbazole and trinitrofluorenone, 2- (4'-dimethylaminophenyl) benzoxazole, selenium, tellurium and arsenic triselenide.
  • the photoreceptors used can also contain sensitizing dyes such as Bengal pink or Eosin G in the charge-generating layer.
  • the photoreceptors may contain diamines, as also specified in U.S. Patent 4,265,990.
  • the invention also relates to the compounds of the formula (II).
  • This toner formulation is incorporated into a xerographic imaging system as described in U.S. Patent 4,265,990.
  • the procedure for this is to provide a MYLAR® substrate with a charge-generating layer of polyvinylcarbazole, in which trigonal selenium is freely dispersed, and a transparent charge-transporting layer is applied over it, which acts as charge-transporting molecules N, N'-diphenyl -N, N'-bis- (3-methylphenyl) -1,1'-bisphenyl-4,4'-diamine, dispersed in a MAKROLON® polycarbonate composition.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Indole Compounds (AREA)

Description

Aus der EP-A 0 028 777 sind Naphthalimide bekannt, die im Naphthalinteil einen OR-Substituenten aufweisen und als optische Aufheller verwendet werden können Aus der EP-A 0 154 740 sind ladungsverstärkende Phthalimide bekannt, die verbesserungswürdige Eigenschaften aufweisen.EP-A 0 028 777 discloses naphthalimides which have an OR substituent in the naphthalene part and can be used as optical brighteners. EP-A 0 154 740 discloses charge-enhancing phthalimides which have properties which need improvement.

Gegenstand der Erfindung sind positiv geladene elektrophotographische Toner, die neben üblichen Harz- und Pigmentpartikeln ein die kationische Ladung verstärkendes Additiv der allgemeinen Formel

Figure imgb0001

enthalten,
worin

A
für C₁-C₅-Alkylen oder -C₆H₄-CH₂- (m oder p),
m
für O oder 1
n
für 1 oder 2
Figure imgb0002
R³
für C₁-C₁₈-Alkyl, Carbamoyl-C₁-C₂-alkyl, C₁-C₄-Alkoxycarbonyl-C₁-C₂-alkyl, Benzyl, Cyclohexyl oder Allyl,
R⁴
für C₁-C₄-Alkyl oder eine an D anknüpfende Einfachbindung,
R⁵
für C₁-C₄-Alkyl,
D
für -CH₂-, -CH₂-CO-, -CH₂-CO-NH- oder -CH₂-CO-NH-CH₂-
W
für
Figure imgb0003
 -CO-oder eine Einfachbindung,
Z
für -CH₂-,
Figure imgb0004
 -O-, -S-, -SO₂-oder eine Einfachbindung und
An(-)
für ein Anion stehen,
die Verwendung der Verbindungen (I) in elektrographischen Tonern und neue Naphthalsäureimid-Derivate.The invention relates to positively charged electrophotographic toners which, in addition to conventional resin and pigment particles, contain an additive of the general formula which increases the cationic charge
Figure imgb0001
contain,
wherein
A
for C₁-C₅ alkylene or -C₆H₄-CH₂- (m or p),
m
for O or 1
n
for 1 or 2
Figure imgb0002
R³
for C₁-C₁₈-alkyl, carbamoyl-C₁-C₂-alkyl, C₁-C₄-alkoxycarbonyl-C₁-C₂-alkyl, benzyl, cyclohexyl or allyl,
R⁴
for C₁-C₄-alkyl or a single bond linking to D,
R⁵
for C₁-C₄ alkyl,
D
for -CH₂-, -CH₂-CO-, -CH₂-CO-NH- or -CH₂-CO-NH-CH₂-
W
For
Figure imgb0003
 -CO-or a single bond,
Z
for -CH₂-,
Figure imgb0004
 -O-, -S-, -SO₂- or a single bond and
To (-)
stand for an anion,
the use of the compounds (I) in electrographic toners and new naphthalimide derivatives.

C₁-C₅-Alkylenreste A können geradkettig oder verzweigt sind. Dabei sind C₂-C₅-Alkylenreste und besonders der n-Propylenrest bevorzugt.C₁-C₅ alkylene radicals A can be straight-chain or branched. C₂-C₅ alkylene radicals and especially the n-propylene radical are preferred.

Bevorzugte Alkylreste R³ sind C₁-C₁₆-Alkylreste.Preferred alkyl radicals R³ are C₁-C₁₆ alkyl radicals.

Als Anionen sind übliche Anionen wie Halogenide, z.B. Chlorid, Bromid und Jodid. Tetrafluoroborate und Anionen von Alkyl- und Aryl-sulfonsäuren, -carbonsäuren, -phosphorsäuren und -phosphonsäuren geeignet. Besonders geeignet sind solche Anionen, die die Wasserlöslichkeit der Verbindungen (I) erniedrigen und gleichzeitig die Löslichkeit in organischen Lösungsmitteln wie Dimethylformamid, Aceton, Chloroform oder Toluol erhöhen. Die Verminderung der Wasserlöslichkeit kann aber auch dadurch erfolgen, daß man den Alkylrest R³ vergrößert, also etwa im Bereich von C₅-C₁₆-Alkyl wählt. In diesem Falle sind auch hydrophilere Anionen wie Halogenide bestens geeignet.Common anions such as halides, e.g. Chloride, bromide and iodide. Tetrafluoroborates and anions of alkyl and aryl sulfonic acids, carboxylic acids, phosphoric acids and phosphonic acids are suitable. Anions which lower the water solubility of the compounds (I) and at the same time increase the solubility in organic solvents such as dimethylformamide, acetone, chloroform or toluene are particularly suitable. However, the water solubility can also be reduced by increasing the alkyl radical R³, that is to say approximately in the range of C₅-C₁₆-alkyl. In this case, more hydrophilic anions such as halides are also very suitable.

Die bevorzugte Wasserlöslichkeit der Verbindungen (I) bei 20°C liegt bei unter 3 Gew.%, insbesondere unter 1 Gew.%. Bevorzugte Anionen sind außer Halogeniden und Tetrafluoroboraten, insbesondere Arylsulfonate wie gegebenenfalls durch C₁-C₁₂-Alkyl oder Chlor substituierte Benzolsulfonate, C₅-C₁₈-Alkylsulfonate, Salze von C₅-C₁₈-Alkylcarbonsäuren und von Kondensationsprodukten aus Formaldehyd und Arylsulfonsäuren und/oder gegebenenfalls sulfoniertem 4,4'-Dihydroxydiphenylsulfon.The preferred water solubility of the compounds (I) at 20 ° C. is below 3% by weight, in particular below 1% by weight. In addition to halides and tetrafluoroborates, preferred anions are, in particular aryl sulfonates such as benzene sulfonates optionally substituted by C₁-C₁₂ alkyl or chlorine, C₅-C₁₈ alkyl sulfonates, salts of C₅-C₁₈ alkyl carboxylic acids and of condensation products of formaldehyde and aryl sulfonic acids and / or optionally sulfonated 4,4'-dihydroxydiphenyl sulfone.

Bevorzugte Verbindungen der Formel (I) entsprechen der Formel

Figure imgb0005

A¹
für C₂-C₅-Alkylen,
Figure imgb0006
R⁶
für C₁-C₁₆-Alkyl, Carbamoylmethyl oder Benzyl,
R⁷
für Methyl oder Ethyl oder eine an D anknüpfende Einfachbindung,
R⁸
für Methyl oder Ethyl,
W¹
für
Figure imgb0007
Z¹
für -CH₂-,
Figure imgb0008
 -O- oder -SO₂- und
X⊖
für ein Anion stehen, und
D, m und n
die gleiche Bedeutung wie in Formel (I) besitzen.
Preferred compounds of formula (I) correspond to the formula
Figure imgb0005
A¹
for C₂-C₅ alkylene,
Figure imgb0006
R⁶
for C₁-C₁₆ alkyl, carbamoylmethyl or benzyl,
R⁷
for methyl or ethyl or a single bond linked to D,
R⁸
for methyl or ethyl,
W¹
For
Figure imgb0007
Z¹
for -CH₂-,
Figure imgb0008
 -O- or -SO₂- and
X ⊖
stand for an anion, and
D, m and n
have the same meaning as in formula (I).

Die Verbindungen der Formel (I) können nach bekannten Methoden, z.B. nach den in DE-A 35 35496 beschriebenen Verfahren, hergestellt werden. Die Verbindungen selbst sind größtenteils bekannt.The compounds of formula (I) can be prepared by known methods, e.g. according to the processes described in DE-A 35 35496. The connections themselves are mostly known.

Ladungsverstärkende Additive für elektrophotographische Toner, auch Ladungskontroll-Substanzen genannt, sind bereits bekannt. Sie werden beispielsweise in der US-PS 3 893 935, 3 944 493, 4 007 293, 4 079 014, 4 298 672, 4 338 390, 4 394 430 und 4 493 883 beschrieben.Charge-enhancing additives for electrophotographic toners, also called charge control substances, are already known. They are described, for example, in U.S. Patent Nos. 3,893,935, 3,944,493, 4,007,293, 4,079,014, 4,298,672, 4,338,390, 4,394,430 and 4,493,883.

Latente elektrostatische Bildaufzeichnungen werden dadurch entwickelt, daß der Toner auf dem elektrostatischen Bild induktiv abgeschieden wird. Die Ladungskontrollsubstanzen verstärken die kationische Ladung des Toners. Dadurch wird das Bild kräftiger und konturenschärfer.Latent electrostatic image recordings are developed by inductively depositing the toner on the electrostatic image. The charge control substances increase the cationic charge of the toner. This makes the picture more vivid and sharper.

Derartige Ladungskontrollsubstanzen müssen vielseitige Anforderungen erfüllen.

  • 1. Fähigkeit zur Entwicklung des latenten elektrostatischen Bildes zu einem farbstarken sichtbaren Bild.
  • 2. Leichte Verteilbarkeit in der Tonerzubereitung und gleichmäßige Verteilung auf der Bildoberfläche, um ein störungsfreies, konturenscharfes, gleichförmiges Bild zu erzeugen.
  • 3. Unempfindlichkeit gegen Feuchtigkeit.
  • 4. Hohe Thermostabilität.
  • 5. Beständigkeit gegenüber der heißen Mischung aus Bleioxid und einem Vinylidenfluorid-Hexafluoropropylen-Copolymerisat-Harz (z.B. VITON®E-430 von Dupont), mit der das Bild mit Hilfe einer heißen Walze fixiert werden kann. Die Beschichtungsmasse darf sich nicht durch Zersetzungsprodukte schwarz färben.
  • 6. Ungiftigkeit.
Such charge control substances have to meet diverse requirements.
  • 1. Ability to develop the latent electrostatic image into a highly visible color image.
  • 2. Easily distributable in the toner preparation and evenly distributed on the image surface in order to produce a trouble-free, contour-sharp, uniform image.
  • 3. Insensitivity to moisture.
  • 4. High thermal stability.
  • 5. Resistance to the hot mixture of lead oxide and a vinylidene fluoride-hexafluoropropylene copolymer resin (eg VITON®E-430 from Dupont), with which the image can be fixed with the help of a hot roller. The coating material must not turn black due to decomposition products.
  • 6. Non-toxicity.

Die aus den obengenannten US-Patentschriften bekannten Ladungskontrollsubstanzen erfüllen bei weitem nicht alle diese Anforderungen.The charge control substances known from the above-mentioned US patents do not meet all of these requirements by far.

Überraschenderweise zeigte sich nun, daß sich die Substanzen (I) sehr gut als Ladungskontrollsubstanzen in Tonern eignen. Gegenüber den aus der US-PS 4 493 883 (= EP-A 0 154 740) bekannten kationischen Phthalimidoverbindungen ergeben die Verbindungen (I) eine deutliche Steigerung der Farbtiefe des entwickelten Bildes und eine Verbesserung der Bildschärfe Ein weiterer Vorteil ist die wesentlich bessere pH-Stabilität, die sowohl die Herstellung der Verbindungen als auch der Toner-Zubereitungen problemloser gestaltet.Surprisingly, it has now been shown that the substances (I) are very suitable as charge control substances in toners. Compared to the cationic phthalimido compounds known from US Pat. No. 4,493,883 (= EP-A 0 154 740), the compounds (I) result in a significant increase in the color depth of the developed image and an improvement in the image sharpness. Another advantage is the much better pH Stability that makes both the production of the compounds and the toner preparations easier.

Die in den Tonern enthaltenen Harze sind bekannt, Sie sind thermoplastisch und haben einen Erweichungspunkt zwischen 50 und 130°C, vorzugsweise zwischen 65 und 115°C. Beispiele für derartige Harze umfassen Polystyrol, Copolymere von Styrol mit einem Acrylat oder Methacrylat, Copolymere von Styrol mit Butadien und/oder Acrylnitril, Polyacrylate und Polymethacrylate, Copolymere eines Acrylates oder Methacrylats mit Vinylchlorid oder Vinylacetat, Polyvinylchlorid, Copolymere von Vinylchlorid mit Vinylidenchlorid, Copolymere von Vinylchlorid mit Vinylacetat, Polyesterharze (US-PS 3 590 000), Epoxyharze, Polyamide und Polyurethane.The resins contained in the toners are known, they are thermoplastic and have a softening point between 50 and 130 ° C, preferably between 65 and 115 ° C. Examples of such resins include polystyrene, copolymers of styrene with an acrylate or methacrylate, copolymers of styrene with butadiene and / or acrylonitrile, polyacrylates and 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 (U.S. Patent 3,590,000), epoxy resins, polyamides and polyurethanes.

Zusätzlich zu den Verbindungen (I) und den thermoplastischen Harzen enthalten die erfindungsgemäßen Toner in bekannten Mengen Färbungsmaterialien und magnetisch anziehbares Material. Das Färbungsmaterial kann aus einem organischen Farbstoff wie Nigrosin, Anilinblau, 2,9-Dimethylchinacridon, C.I. Disperse Red 15 (=C.I. 60 710), 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) und C.I. Solvent Yellow 16 (=C.I. 12 700), oder einem anorganischen Pigment, wie Ruß, Rotblei, gelbem Bleioxid oder Chromgelb bestehen. Allgemein überschreitet die Menge des in den Tonern vorhandenen Färbungsmaterials etwa 15 Gew.% nicht.In addition to the compounds (I) and the thermoplastic resins, the toners of the present invention contain coloring materials and magnetically attractable material in known amounts. The coloring material can be made from an organic dye such as nigrosine, aniline blue, 2,9-dimethylquinacridone, C.I. Disperse Red 15 (= C.I. 60 710), 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) and C.I. Solvent Yellow 16 (= C.I. 12 700), or an inorganic pigment such as carbon black, red lead, yellow lead oxide or chrome yellow. Generally the amount of the coloring material present in the toners does not exceed about 15% by weight.

Das magnetisch anziehbare Material kann beispielsweise aus Eisen, Nickel, Chromoxid, Eisenoxid oder einem Ferrit dar allgemeinen Formel MFe₂O₄, worin M ein zweiwertiges Metall, wie Eisen, Kobalt, Zink, Nickel oder Mangan darstellt, bestehen.The magnetically attractable material can for example consist of iron, nickel, chromium oxide, iron oxide or a ferrite of the general formula MFe₂O₄, where M is a divalent metal such as iron, cobalt, zinc, nickel or manganese.

Die Herstellung der die Verbindungen (I) enthaltenden Toner erfolgt nach üblichen Verfahren, z.B. durch Schmelzen des thermoplastischen Harzes oder eines Gemisches der thermoplastischen Harze, anschließend feiner Zerteilung einer oder mehrerer Ladungskontrollsubstanzen der Formel (I), sowie der anderen Zusätze, falls verwendet, in dem geschmolzenen Harz unter Anwendung der für diesen Zweck bekannten Misch- und Knetmaschinerie, anschließende Abkühlung der Schmelze zu einer festen Masse und schließlich Vermahlen der festen Masse zu Teilchen der gewünschten Teilchengröße. Es ist auch möglich, das thermoplastische Harz und die Verbindung (I) in einem gemeinsamen Lösungsmittel zu lösen, die anderen Zusätze in die Lösung einzuverleiben und anschließend die Flüssigkeit in an sich bekannter Weise sprühzutrocknen oder das Lösungsmittel oder die Lösungsmittel abzudampfen und den festen Rückstand zu Teilchen der gewünschten Teilchengröße zu vermahlen. Entsprechend einer Abänderung dieses Herstellungsverfahrens wird die Ladungskontrollsubstanz der Formel (I) nicht gelöst, sondern fein in der Lösung des thermoplastischen Harzes dispergiert.The toners containing the compounds (I) are prepared by customary processes, e.g. by melting the thermoplastic resin or a mixture of the thermoplastic resins, then finely dividing one or more charge control substances of formula (I), as well as the other additives, if used, into the melted resin using the mixing and kneading machinery known for this purpose Cooling the melt to a solid mass and finally grinding the solid mass into particles of the desired particle size. It is also possible to dissolve the thermoplastic resin and the compound (I) in a common solvent, to incorporate the other additives into the solution and then to spray-dry the liquid in a manner known per se or to evaporate off the solvent or solvents and to add the solid residue To grind particles of the desired particle size. According to a modification of this manufacturing process, the charge control substance of the formula (I) is not dissolved, but finely dispersed in the solution of the thermoplastic resin.

Die so erhaltene Tonerzubereitung wird dann, beispielsweise analog US-PS 4 265 990, in einem xerographischen Bildaufzeichnungssystem eingesetzt. Die dafür eingesetzten Photorezeptoren müssen die Fähigkeit haben, sich negativ aufzuladen. Beispiele sind solche, wie sie ebenfalls in US-PS 4 265 990 beschrieben sind. Sie können in der ladungsleitenden Schicht beispielsweise folgende Substanzen enthalten: 4-Dimethylaminobenzyliden-benzhydrazid, Polyvinylcarbazol, 2-Benzyliden-aminocarbazol, 2-Nitrobenzyliden-p-bromanilin, 2,4-Diphenylchinazolln, 1,5-Diphenyl-3-methyl-pyrazolin, 1,3,5-Triphenylpyrazolin, Charge-Transfer-Komplex aus Polyvinylcarbazol und Trinitrofluorenon, 2-(4'-Dimethylaminophenyl)-benzoxazol, Selen, Tellur und Arsentriselenid.The toner preparation thus obtained is then used in a xerographic image recording system, for example analogously to US Pat. No. 4,265,990. The photoreceptors used for this must have the ability to charge negatively. Examples are those also described in U.S. Patent 4,265,990. You can use the following substances in the charge-conducting layer, for example contain: 4-dimethylaminobenzylidene-benzhydrazide, polyvinylcarbazole, 2-benzylidene-aminocarbazole, 2-nitrobenzylidene-p-bromoaniline, 2,4-diphenylquinazollene, 1,5-diphenyl-3-methylpyrazoline, 1,3,5-triphenylpyrazoline, Charge transfer complex of polyvinyl carbazole and trinitrofluorenone, 2- (4'-dimethylaminophenyl) benzoxazole, selenium, tellurium and arsenic triselenide.

Die eingesetzten Photorezeptoren können in der ladungserzeugenden Schicht auch zusätzlich Sensibilisierungsfarbstoffe wie beispielsweise Bengal Rosa oder Eosin G enthalten. In der ladungstransportierenden Schicht können die Photorezeptoren Diamine enthalten, wie sie ebenfalls in US-PS 4 265 990 angegeben sind.The photoreceptors used can also contain sensitizing dyes such as Bengal pink or Eosin G in the charge-generating layer. In the charge transport layer, the photoreceptors may contain diamines, as also specified in U.S. Patent 4,265,990.

Gegenstand der Erfindung sind auch die Verbindungen der Formel (II).The invention also relates to the compounds of the formula (II).

Beispiel 1example 1

282 g Naphthalsäure-N-(3-dimethylaminopropyl)-imid (1 Mol) und 175,5 g 4,4'-Bis-(chloracetamidophenyl)-methan (0,5 Mol) werden in 1330 g Polyglykol (durchschn. Molgew. 400) 3 h auf 100°C erhitzt, wobei sich zunächst eine klare viskose Lösung bildet, aus der sich anschließend ein farbloser kristalliner Niederschlag abscheidet. Nach dem Abkühlen auf Raumtemperatur verdünnt man die Reaktionsmischung unter Rühren mit 3,3 1 Isopropanol, saugt den kristallinen Niederschlag ab, wäscht ihn mit Isopropanol bis zum farblosen Ablauf und trocknet ihn bei 60°C im Vakuum. Man erhält 444 g (97% der Theorie) Verbindung der Formel

Figure imgb0009

Die Substanz ist dünnschichtchromatographisch praktisch rein. 1 zeigt auf der fluoreszierenden Kieselgelplatte Fluoreszenzlöschung. Rf-Wert: 0,3 (Laufmittel: 45 Vol-% Essigsäurebutylester, 33 Vol-% Eisessig, 9 Vol-% Ameisensäure und 13 Vol-% Wasser).282 g of naphthalic acid N- (3-dimethylaminopropyl) imide (1 mol) and 175.5 g of 4,4'-bis (chloroacetamidophenyl) methane (0.5 mol) are dissolved in 1330 g of polyglycol (average mol. 400) heated to 100 ° C. for 3 h, a clear viscous solution initially forming, from which a colorless crystalline precipitate is then deposited. After cooling to room temperature, the reaction mixture is diluted with 3.3 l of isopropanol with stirring, the crystalline precipitate is filtered off with suction, washed with isopropanol until it is colorless and dried at 60 ° C. in vacuo. 444 g (97% of theory) of the compound of the formula are obtained
Figure imgb0009
The substance is practically pure by thin layer chromatography. 1 shows fluorescence quenching on the fluorescent silica gel plate. Rf value: 0.3 (mobile phase: 45% by volume of butyl acetate, 33% by volume of glacial acetic acid, 9% by volume of formic acid and 13% by volume of water).

In analoger Weise werden die folgenden Verbindungen hergestellt:

Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
 The following connections are made in an analogous manner:
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013

Ebenfalls in analoger Weise werden die folgenden Verbindungen hergestellt:

Figure imgb0014
Figure imgb0015
 The following connections are also made in an analogous manner:
Figure imgb0014
Figure imgb0015

Beispiel 21Example 21

Man setzt in gleicher Weise, wie im Beispiel 1 beschrieben, 282 g Naphthalsäure -N-(3-dimethylaminopropyl)-imid und 175,5 g 4,4'-Bis(chloracetamidophenyl)-methan in 1330 Polyglykol 3h bei 100°C um, setzt 600 ml Ethanol und 225 g p-Toluolsulfonsäure hinzu, erhitzt die Mischung 2 h unter Rückfluß zum Sieden, saugt den farblosen kristallinen Niederschlag ab, wäscht ihn mit 800 ml Ethanol und trocknet ihn bei 60°C im Vakuum.In the same way as described in Example 1, 282 g of naphthalic acid -N- (3-dimethylaminopropyl) imide and 175.5 g of 4,4'-bis (chloroacetamidophenyl) methane are reacted in 1330 polyglycol at 100 ° C. for 3 hours , 600 ml of ethanol and 225 g of p-toluenesulfonic acid are added, the mixture is heated to boiling under reflux for 2 hours, the colorless crystalline precipitate is filtered off, washed with 800 ml of ethanol and dried at 60 ° C. in vacuo.

Man erhält 366 g Verbindung der Formel

Figure imgb0016

Die Substanz ist dünnschichtchromatographisch praktisch rein.366 g of compound of the formula are obtained
Figure imgb0016
The substance is practically pure by thin layer chromatography.

In analoger Weise werden auch die p-Toluol- und Benzolsulfonate der Verbindungen 2 bis 20 hergestellt.The p-toluene and benzenesulfonates of compounds 2 to 20 are also prepared in an analogous manner.

Beispiel 22Example 22

56,5 g (0,2 Mol) Naphthalsäure-N-(3-dimethylaminopropyl)-imid werden in 700 ml Toluol suspendiert, unter Rühren mit 56 g p-Toluolsulfonsäure-methylester versetzt und 1 h bei 60°C verrührt. Der farblose kristalline Niederschlag wird abgesaugt, mit 150 ml Isopropanol gewaschen und bei 40°C im Vakuum getrocknet. Man erhält 87 g (93% der Theorie) Verbindung der Formel

Figure imgb0017

Die Substanz ist dünnschichtchromatographisch vollkommen rein. Sie schmilzt bei 220-221°C.56.5 g (0.2 mol) of naphthalic acid N- (3-dimethylaminopropyl) imide are suspended in 700 ml of toluene, 56 g of p-toluenesulfonic acid methyl ester are added with stirring and the mixture is stirred at 60 ° C. for 1 h. The colorless crystalline precipitate is filtered off, washed with 150 ml of isopropanol and dried at 40 ° C in a vacuum. 87 g (93% of theory) of the compound of the formula are obtained
Figure imgb0017
The substance is completely pure by thin layer chromatography. It melts at 220-221 ° C.

In analoger Weise werden die folgenden Substanzen der Formel

Figure imgb0018

hergestellt.
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
 The following substances of the formula are used in an analogous manner
Figure imgb0018
produced.
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022

Beispiel 34Example 34

282 g (1 Mol) Naphthalsäure-N-(3-dimethylaminopropyl)-imid werden in 2 l Acetonitril suspendiert, unter Rühren mit 307 g (1 Mol) 1-Bromhexadecan versetzt und 15 Stunden unter Rückfluß zum Sieden erhitzt. Die Lösung wird 35°C warm von geringen ungelösten Anteilen filtriert. Das Filtrat wird mit 2,5 l Aceton verrührt und auf -5°C abgekühlt. Der kristalline Niederschlag wird abgesaugt, zuerst mit Aceton, dann mit Petrolether gewaschen und bei 30°C im Vakuum getrocknet. Man erhält 540 g (92 % der Theorie) Verbindung der Formel

Figure imgb0023
282 g (1 mol) of naphthalic acid N- (3-dimethylaminopropyl) imide are suspended in 2 l of acetonitrile, 307 g (1 mol) of 1-bromohexadecane are added with stirring and the mixture is heated to boiling under reflux for 15 hours. The solution is filtered 35 ° C warm from small undissolved portions. The filtrate is stirred with 2.5 l of acetone and cooled to -5 ° C. The crystalline precipitate is filtered off, washed first with acetone, then with petroleum ether and dried at 30 ° C in a vacuum. 540 g (92% of theory) of the compound of the formula are obtained
Figure imgb0023

Beispiel 35Example 35

289 g (1,02 Mol) Naphthalsäure-N-(3-dimethylaminopropyl)-imid werden in 6,1 l Toluol suspendiert, bei 60 bis 65°C unter Rühren tropfenweise mit 138 g (1,09 Mol) Dimethylsulfat versetzt und 6 Stunden bei 60 bis 65°C verrührt. Nach dem Kühlen auf Raumtemperatur wird der kristalline Niederschlag abgesaugt, mit Toluol gewaschen und bei 50°C im Vakuum getrocknet. Man erhält 408 g (98 % der Theorie) Verbindung der Formel

Figure imgb0024

408 g (1 Mol) der erhaltenen Verbindung (35 A) werden bei Raumtemperatur in 4 l Wasser gelöst und tropfenweise unter Rühren mit 1 l einer 40 %igen wäßrigen Lösung eines Polykondensationsproduktes von sulfoniertem 4,4'-Dihydroxydiphenylsulfon und Formaldehyd versetzt. Der kristalline Niederschlag wird abgesaugt, mit Wasser gewaschen und bei 50°C im Vakuum getrocknet. Man erhält 685 g Verbindung der Formel
Figure imgb0025

Q⊖ =
Äquivalent eines Anions, das durch Kondensation von 4,4'-Dihydrodiphenylsulfon, Schwefelsäure und Formaldehyd im Molverhältnis 1:1:0,67 erhalten wird.
289 g (1.02 mol) of naphthalic acid N- (3-dimethylaminopropyl) imide are suspended in 6.1 l of toluene, 138 g (1.09 mol) of dimethyl sulfate are added dropwise at 60 to 65 ° C. while stirring, and 6 Stirred at 60 to 65 ° C for hours. After cooling to room temperature, the crystalline precipitate is filtered off, washed with toluene and dried at 50 ° C in a vacuum. 408 g (98% of theory) of the compound of the formula are obtained
Figure imgb0024
408 g (1 mol) of the compound (35 A) obtained are dissolved in 4 l of water at room temperature and 1 l of a 40% aqueous solution of a polycondensation product of sulfonated 4,4'-dihydroxydiphenyl sulfone and formaldehyde is added dropwise while stirring. The crystalline precipitate is filtered off, washed with water and dried at 50 ° C in a vacuum. 685 g of compound of the formula are obtained
Figure imgb0025
Q ⊖ =
Equivalent to an anion obtained by condensing 4,4'-dihydrodiphenyl sulfone, sulfuric acid and formaldehyde in a 1: 1: 0.67 molar ratio.

AnwendungsbeispielApplication example

2 Gewichtsprozent Verbindung des Beispiels 22, 6 Gewichtsprozent Ruß und 92 Gewichtsprozent eines Styrol-Butadien-Harzes, welches 89 Gewichtsprozent Styrol und 11 Gewichtsprozent Butadien enthält werden im Extruder bei 100°C verschmolzen und verknetet, dann zerkleinert und gemahlen, bis der Partikeldurchmesser kleiner als 5µ ist.2 percent by weight of the compound of Example 22, 6 percent by weight of carbon black and 92 percent by weight of a styrene-butadiene resin which contains 89 percent by weight of styrene and 11 percent by weight of butadiene are melted and kneaded in the extruder at 100 ° C., then comminuted and ground until the particle diameter is less than Is 5µ.

Diese Toner-Zubereitung wird in ein xerographisches Bildaufzeichnungssystem, wie es in US-PS 4 265 990 beschrieben ist, eingearbeitet. Dazu geht man in der Weise vor, daß man ein MYLAR®-Substrat mit einer bei Belichtung ladungserzeugenden Schicht aus Polyvinylcarbazol versieht, in das trigonales Selen frei dispergiert ist, darüber eine transparente ladungstransportierende Schicht aufbringt, die als ladungstransportierende Moleküle N,N'-Diphenyl-N,N'-bis-(3-Methylphenyl)-1,1'-bisphenyl-4,4'-diamin, dispergiert in eine MAKROLON®-Polycarbonatmasse, enthält.This toner formulation is incorporated into a xerographic imaging system as described in U.S. Patent 4,265,990. The procedure for this is to provide a MYLAR® substrate with a charge-generating layer of polyvinylcarbazole, in which trigonal selenium is freely dispersed, and a transparent charge-transporting layer is applied over it, which acts as charge-transporting molecules N, N'-diphenyl -N, N'-bis- (3-methylphenyl) -1,1'-bisphenyl-4,4'-diamine, dispersed in a MAKROLON® polycarbonate composition.

Man erhält gestochen scharfe Bildaufzeichnungen, die denen nach US-PS 4 493 883 (= EP-A 0 154 740), Beispiel 1, hergestellten in der Konturenschärfe noch überlegen sind.Pin-sharp image recordings are obtained which are still superior in contour definition to those produced according to US Pat. No. 4,493,883 (= EP-A 0 154 740), Example 1.

Claims (5)

  1. Electrophotographic toners containing an additive corresponding to the following general formula which reinforces the cationic charge:
    Figure imgb0038
     in which formula,
    A   stands for C₁-C₅-alkylene or C₆H₄-CH₂ (m or p),
    m   stands for 0 or 1,
    n   stands for 1 or 2,
    Figure imgb0039
    R³   stands for C₁-C₁₈-alkyl, carbamoyl-C₁-C₂-alkyl, C₁-C₄-alkoxycarbonyl-C₁-C₂-alkyl, benzyl, cyclohexyl or allyl,
    R⁴   stands for C₁-C₄-alkyl or a single bond attached to D,
    R⁵   stands for C₁-C₄-alkyl,
    D   stands for CH₂, CH₂-CO, CH₂-CO-NH or CH₂-CO-NH-CH₂,
    W   stands for
    Figure imgb0040
     -CO-
    or a single bond,
    Z   stands for CH₂,
    Figure imgb0041
     -O-, -S-,
    -SO₂- or a -single bond and
    An⊖   for an anion.
  2. Electrophotographic toners according to Claim 1, characterised in that they contain an additive corresponding to the following general formula which reinforces the cationic charge:
    Figure imgb0042
     in which formula,
    A¹   stands for C₂-C₅-alkylene,
    Figure imgb0043
    R⁶   stands for C₁-C₁₆-alkyl, carbamoylmethyl or benzyl,
    R⁷   stands for methyl or ethyl or a single bond attached to D,
    R⁸   stands for methyl or ethyl,
    W¹   stands for
    Figure imgb0044
    Z¹   stands for CH₂,
    Figure imgb0045
     O or SO₂ and
    X⊖   stands for an anion and
    D, m and n   have the meanings indicated in Claim 1.
  3. Electrophotographic toner according to Claim 1, characterised in that they contain resin and pigment particles in addition to the additive which reinforces the cationic charge.
  4. Use of compounds corresponding to the formula of Claim 1 as additives reinforcing the positive charge in electrophotographic toners.
  5. Naphthalic acid imides corresponding to the following general formula
    Figure imgb0046
     wherein
    A¹   stands for C₂-C₅-alkylene,
    Figure imgb0047
    R⁶   stands for C₁-C₁₆-alkyl, carbamoylmethyl or benzyl,
    R⁷   stands for methyl or ethyl or a single bond attached to D,
    R⁸   stands for methyl or ethyl,
    W¹   stands for
    Figure imgb0048
    Z¹   stands for CH₂,
    Figure imgb0049
     O or SO₂ and
    X⊖   stands for a benzene sulphonate optionally substituted by Cl or by C₁-C₁₂-alkyl or it stands for C₅-C₁₈-alkylsulphonate or for a salt of a C₅-C₁₈-alkylcarboxylic acid or a salt of a condensation product of formaldehyde and arylsulphonic acids and/or optionally sulphonated 4,4'-dihydroxydiphenylsulphone and
    D, m and n   have the meanings indicated in Claim 1.
EP87101463A 1986-02-15 1987-02-03 Electrophotographical toner Expired - Lifetime EP0233544B1 (en)

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DE3604827 1986-02-15
DE19863604827 DE3604827A1 (en) 1986-02-15 1986-02-15 ELECTROPHOTOGRAPHIC TONER

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Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3738948A1 (en) * 1987-11-17 1989-05-24 Bayer Ag COLORLESS SALTS OF HETEROPOLYSAURS AND CATIONIC AROMATIC IMIDES AS CHARGE CONTROL SUBSTANCES IN TONERS
JPH0814721B2 (en) * 1988-02-09 1996-02-14 株式会社巴川製紙所 Positively chargeable color toner
DE3828193A1 (en) * 1988-08-19 1990-02-22 Bayer Ag ELECTROPHOTOGRAPHIC TONER
EP0388535B1 (en) * 1989-03-24 1994-05-18 Agfa-Gevaert N.V. Particulate toner material
US5086059A (en) * 1990-06-07 1992-02-04 Du Pont Merck Pharmaceutical Company Bis-naphthalimides as anticancer agents
DE4106122A1 (en) * 1991-02-27 1992-09-03 Bayer Ag NEW NAPHTHALIMIDES, THESE CONTAINING TONERS AND THE USE OF THE NEW NAPHTHALIMIDES AS ADDITIVES FOR TONER
US5206250A (en) * 1991-03-27 1993-04-27 Du Pont Merck Pharmaceutical Company Bis-naphthalimides containing amide and thioamide linkers as anticancer agents
US5329048A (en) * 1991-03-27 1994-07-12 The Dupont Merck Pharmaceutical Company Process of preparing tetraamino intermediates
US5162188A (en) * 1991-07-18 1992-11-10 Eastman Kodak Company Toners and developers containing amide-containing quaternary ammonium salts as charge control agents
JPH07501822A (en) * 1991-12-11 1995-02-23 デュポン・ファーマシュウティカルズ・カンパニー Highly water-soluble bis-naphthalimide useful as an anticancer agent
US5376664A (en) * 1992-07-27 1994-12-27 The Du Pont Merck Pharmaceutical Company Unsymmetrical mono-3-nitro bis-naphthalimides as anticancer agents
DE4232739A1 (en) * 1992-09-30 1994-03-31 Knoll Ag New asymmetrically substituted bis-naphthalimides
DE4237661A1 (en) * 1992-11-07 1994-05-11 Basf Ag Electrostatic toners containing amphiphilic liquid crystals
US5359070A (en) * 1993-02-11 1994-10-25 The Du Pont Merck Pharmaceutical Company Unsymmetrical bis-imides as anticancer agents
US5416089A (en) * 1993-06-24 1995-05-16 The Du Pont Merck Pharmaceutical Company Polycyclic and heterocyclic chromophores for bis-imide tumoricidals
US5358817A (en) * 1993-08-31 1994-10-25 Eastman Kodak Company Toner compositions containing as a negative charge-controlling agent the calcium salt of ortho-benzoic sulfimide
US5358815A (en) * 1993-08-31 1994-10-25 Eastman Kodak Company Toner compositions containing negative charge-controlling additive
US5358818A (en) * 1993-08-31 1994-10-25 Eastman Kodak Company Ortho-benzoic sulfimide as charge-controlling agent
US5358814A (en) * 1993-08-31 1994-10-25 Eastman Kodak Company Toner compositions containing as a negative charge-controlling agent a mixture of ortho-benzoic sulfimide and para-anisic acid
US5332637A (en) * 1993-08-31 1994-07-26 Eastman Kodak Company Electrostatographic dry toner and developer compositions with hydroxyphthalimide
US5358816A (en) * 1993-08-31 1994-10-25 Eastman Kodak Company Zinc salt of ortho-benzoic sulfimide as negative charge-controlling additive for toner and developer compositions
US5604095A (en) * 1994-07-22 1997-02-18 Cancer Therapy & Research Center Unsymmetrically linked bisnaphthalimides as antitumor agents
US5561042A (en) * 1994-07-22 1996-10-01 Cancer Therapy And Research Center Diamine platinum naphthalimide complexes as antitumor agents
US5641782A (en) * 1995-02-16 1997-06-24 The Dupont Merck Pharmaceutical Company 3-aromatic and 3-heteroaromatic substituted bisnaphthalimides
EP3338756B1 (en) 2016-12-21 2020-02-26 VOCO GmbH Storage-stable resin-modified glass ionomer cement

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2140087B1 (en) * 1971-06-03 1978-03-17 Basf Ag
CH560235A5 (en) * 1972-02-18 1975-03-27 Ciba Geigy Ag
US3953451A (en) * 1972-06-28 1976-04-27 Basf Aktiengesellschaft Compounds of the naphthalimide series
US3940398A (en) * 1975-01-23 1976-02-24 E. R. Squibb & Sons, Inc. 2-[[4-(Azine or diazine or triazine)-1-piperazinyl]alkyl]-1H-benz[de]isoquinoline-1,3(2H)-diones
US4007191A (en) * 1975-10-14 1977-02-08 E. R. Squibb & Sons, Inc. 2-(Piperidinyl or tetrahydropyridinyl)-alkyl)-2,3-dihydro-3-hydroxy-1H-benz(DE)isoquinolin-1-ones
US4139532A (en) * 1976-05-14 1979-02-13 Basf Aktiengesellschaft N-Acylaminonaphthalimides
ES459497A1 (en) * 1977-06-04 1978-04-16 Made Labor Sa N(Aminoalkyl)-naphthalimides and their derivatives
DE2753152A1 (en) * 1977-11-29 1979-06-07 Basf Ag NAPHTHALIMIDE DERIVATIVES
DE2944867A1 (en) * 1979-11-07 1981-05-27 Hoechst Ag, 6000 Frankfurt CATIONIC COMPOUNDS OF THE NAPHTHALIMIDE SERIES, METHOD FOR THE PRODUCTION AND USE THEREOF
US4508900A (en) * 1980-11-03 1985-04-02 Hoechst Aktiengesellschaft Cationic compounds of the naphthalimide series, process for their preparation and their use
JPS59114546A (en) * 1982-12-22 1984-07-02 Nippon Kayaku Co Ltd Electrophotographic printing toner
US4499266A (en) * 1983-04-01 1985-02-12 Warner-Lambert Company 3,6-Dinitro-1,8-naphthalimides
US4614820A (en) * 1983-04-01 1986-09-30 Warner-Lambert Co. 3,6-disubstituted-1,8-naphthalimides
DE3413833A1 (en) * 1983-04-12 1984-10-18 Canon K.K., Tokio/Tokyo DEVELOPMENT PROCESS AND DEVELOPER THEREFOR
JPH0625874B2 (en) * 1983-04-23 1994-04-06 キヤノン株式会社 Triboelectric toner for developing electrostatic image
US4493883A (en) * 1984-02-21 1985-01-15 Xerox Corporation Electrophotographic toner compositions containing novel imide charge control _additives
US4665071A (en) * 1984-02-21 1987-05-12 Warner-Lambert Company 3,6-disubstituted-1,8-naphthalimides and methods for their production and use
DE3535496A1 (en) * 1985-10-04 1987-04-16 Bayer Ag METHOD FOR FLUORESCENT EXTINGUISHING AND NEW CATIONIC NAPHTHALINE PERI DICARBONIC ACID IMID DERIVATIVES
US4686166A (en) * 1985-10-07 1987-08-11 Hitachi Chemical Co. Electrophoto toner comprising imido group monomer unit in polymer
US4782064A (en) * 1986-07-21 1988-11-01 American Cyanamid Co. 2-heteroaryl-alkyl-1H-benz[de]-isoquinoline-1,3(2H)-diones

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DE3787297D1 (en) 1993-10-14
US4841052A (en) 1989-06-20
EP0233544A3 (en) 1990-04-04
JPS62192755A (en) 1987-08-24

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