EP0233544A2 - Electrophotographical toner - Google Patents

Electrophotographical toner Download PDF

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Publication number
EP0233544A2
EP0233544A2 EP87101463A EP87101463A EP0233544A2 EP 0233544 A2 EP0233544 A2 EP 0233544A2 EP 87101463 A EP87101463 A EP 87101463A EP 87101463 A EP87101463 A EP 87101463A EP 0233544 A2 EP0233544 A2 EP 0233544A2
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EP
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Prior art keywords
alkyl
single bond
ethyl
benzyl
alkylene
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EP87101463A
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German (de)
French (fr)
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EP0233544A3 (en
EP0233544B1 (en
Inventor
Horst Dr. Harnisch
Roderich Dr. Raue
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Bayer AG
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Bayer AG
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/097Plasticisers; Charge controlling agents
    • G03G9/09733Organic compounds
    • G03G9/09741Organic compounds cationic

Definitions

  • R 1 and R 2 are preferably hydrogen.
  • C 1 -C 5 alkylene radicals A can be straight-chain or branched.
  • C 2 -C S -alkylene radicals and especially the n-propylene radical are preferred.
  • Preferred alkyl radicals R 3 are C 1 -C 16 alkyl radicals.
  • anions such as halides, for example 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 R 3 , that is to say choosing it in the range of C 5 -C 16 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 less than 3% by weight, in particular less than 1% by weight.
  • preferred anions are, in particular, aryl sulfonates, such as benzenesulfonates optionally substituted by C 1 -C 12 -alkyl or chlorine, C 5 -C 18 alkyl sulfates, salts of C 5 -C 18 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 image 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 sharpness of the image.
  • Another advantage is the much better pH stability, which 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 MFe 2 0 4 , 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.
  • punches contain: 4-dimethylaminobenzylidene-benzhydrazide, polyvinyl carbazole, 2-benzylidene-aminocarbazole, 2-nitrobenzylidene-p-bromoaniline, 2,4-diphenylehinazoline, 1,5-diphenyl-3-methyl-pyrazoline, 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).
  • the substance is practically pure by thin layer chromatography.
  • 1 shows fluorescence quenching on the fluorescent silica gel plate.
  • Rf value 0.3 (mobile solvent: 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).
  • the substance is practically pure by thin layer chromatography.
  • the substance is completely pure by thin layer chromatography. It melts at 220-221 ° C.
  • 408 g (98% of theory) of the compound of the formula are obtained 408 g (1 mol) of the compound obtained (35 A) 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.
  • 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)

Abstract

Positive geladene elektrophotographische Toner enthalten neben üblichen Harz- und Pigmentpartikeln ein die kationische Ladung verstärkendes Additiv der allgemeinen Formel <IMAGE> worin R¹ und R² je für Wasserstoff, Chlor, Brom, Hydroxy, C1-C4-Alkoxy, oder Carboxy, A für C1-C5-Alkylen oder -C6H4-CH2- (m oder p), m für 0 oder 1 n für 1 oder 2 <IMAGE> R³ für C1-C18-Alkyl, Carbamoyl-C1-C2-alkyl, C1-C4-Alkoxycarbonyl-C1-C2-alkyl, Benzyl, Cyclohexyl oder Allyl, R<4> für C1-C4-Alkyl oder eine an D anknüpfende Einfachbindung, R<5> für C1-C4-Alkyl, D für -CH2-, -CH2-CO-, -CH2-CO-NH- oder -CH2-CO-NH-CH2- <IMAGE> oder eine Einfachbindung und An<o> für ein Anion stehen.In addition to conventional resin and pigment particles, positively charged electrophotographic toners contain a cationic charge-increasing additive of the general formula <IMAGE> in which R¹ and R² each represent hydrogen, chlorine, bromine, hydroxyl, C1-C4-alkoxy, or carboxy, A for C1- C5-alkylene or -C6H4-CH2- (m or p), m for 0 or 1 n for 1 or 2 <IMAGE> R³ for C1-C18-alkyl, carbamoyl-C1-C2-alkyl, C1-C4-alkoxycarbonyl- C1-C2-alkyl, benzyl, cyclohexyl or allyl, R <4> for C1-C4-alkyl or a single bond linking to D, R <5> for C1-C4-alkyl, D for -CH2-, -CH2-CO -, -CH2-CO-NH- or -CH2-CO-NH-CH2- <IMAGE> or a single bond and An <o> stand for an anion.

Description

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

  • R 1 und R2 je für Wasserstoff, Chlor, Brom, Hydroxy, C1-C4-Alkoxy, oder Carboxy,
  • A für C1-C5-Alkylen oder -C6H4-CH2- (m oder p), m für O oder 1
  • n für 1 oder 2
  • K für
    Figure imgb0002
  • R3 für C1-C18-Alkyl, Carbamoyl-C1-C2-alkylg C1-C4-Alkoxycarbonyl-C1-C2-alkyl, Benzyl, Cyclohexyl oder Allyl,
  • R4 für C1-C4-Alkyl oder eine an D anknüpfende Einfachbindung,
  • R 5 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
    Figure imgb0004
    -O-, -S-, -SO2-oder eine Einfachbindung und
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
  • R 1 and R 2 each represent hydrogen, chlorine, bromine, hydroxy, C 1 -C 4 alkoxy or carboxy,
  • A for C 1 -C 5 alkylene or -C 6 H 4 -CH 2 - (m or p), m for O or 1
  • n for 1 or 2
  • K for
    Figure imgb0002
  • R 3 is C 1 -C 18 alkyl, carbamoyl-C 1 -C 2 alkylg C 1 -C 4 alkoxycarbonyl-C 1 -C 2 alkyl, benzyl, cyclohexyl or allyl,
  • R 4 is C 1 -C 4 alkyl or a single bond linking to D,
  • R 5 is C 1 -C 4 alkyl,
  • D for -CH 2 -, -CH 2 -CO-, -CH 2 -CO-NH- or -CH 2 -CO-NH-CH 2 -
  • W for
    Figure imgb0003
    -CO-or a single bond,
  • Z for
    Figure imgb0004
    -O-, -S-, -SO 2 - or a single bond and

An(-) für ein Anion stehen,
die Verwendung der Verbindungen (I) in elektrographischen Tonern und neue Naphthalsäureimid-Derivate.
At (-) stand for an anion,
the use of the compounds (I) in electrographic toners and new naphthalimide derivatives.

Bevorzugt bedeuten R1 und R2 Wasserstoff.R 1 and R 2 are preferably hydrogen.

C1-C5-Alkylenreste A können geradkettig oder verzweigt sind. Dabei sind C2-CS-Alkylenreste und besonders der n-Propylenrest bevorzugt.C 1 -C 5 alkylene radicals A can be straight-chain or branched. C 2 -C S -alkylene radicals and especially the n-propylene radical are preferred.

Bevorzugte Alkylreste R3 sind C1-C16-Alkylreste.Preferred alkyl radicals R 3 are C 1 -C 16 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.The usual anions are anions, such as halides, for example 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 R 3 , that is to say choosing it in the range of C 5 -C 16 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.X, insbesondere unter 1 Gew.%. Bevorzugte Anionen sind außer Halogeniden und Tetrafluoroboraten insbesondere Arylsulfonate wie gegebenenfalls durch Ci-C12-Alkyl oder Chlor substituierte Benzolsulfonate, C5-C18-Alkylaulfcnate, Salze von C5-C18-Alkylcarbon- säuren 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 less than 3% by weight, in particular less than 1% by weight. In addition to halides and tetrafluoroborates, preferred anions are, in particular, aryl sulfonates, such as benzenesulfonates optionally substituted by C 1 -C 12 -alkyl or chlorine, C 5 -C 18 alkyl sulfates, salts of C 5 -C 18 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,
  • e
  • K1 für
    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
    Figure imgb0008
  • 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
  • A 1 for C 2 -C 5 alkylene,
  • e
  • K 1 for
    Figure imgb0006
  • R 6 is C 1 -C 16 alkyl, carbamoylmethyl or benzyl,
  • R 7 represents methyl or ethyl or a single bond linked to D,
  • R 8 represents methyl or ethyl,
  • W 1 for
    Figure imgb0007
  • Z 1 for
    Figure imgb0008
  • X stands 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 image more vivid and sharper.

Derartige Ladungskontrollsubstanzen müssen vielseitige Anforderungen erfüllen.Such charge control substances have to meet diverse requirements.

  • 1. Fähigkeit zur Entwicklung des latenten elektrostatischen Bildes zu einem farbstarken sichtbaren Bild.1. Ability to develop the latent electrostatic image into a highly visible color image.
  • 2. Leichte Verteilbarkeit in der Tonerzubereitung und gleichmäßige Verteilung auf der Bildoberfläche, um ein störungsfreies, konturenacharfes, gleichförmiges Bild zu erzeugen.2. Easily distributable in the toner preparation and evenly distributed on the image surface in order to produce a trouble-free, contour-accurate, uniform image.
  • 3. Unempfindlichkeit gegen Feuchtigkeit.3. Insensitivity to moisture.
  • 4. Hohe Thermostabilitat.4. High thermal stability.
  • 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.5. Resistance to the hot mixture of lead oxide and a vinylidene fluoride-hexafluoropropylene copolymer resin (e.g. 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. Ungiftigkeit.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 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, the compounds (I) result in a significant increase in the color depth of the developed image and an improvement in the sharpness of the image. Another advantage is the much better pH stability, which 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.X 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, CI Disperse Red 15 (= CI 60 710), CI Solvent Red 19 (= CI 26 050), CI Pigment Blue 15 (= C .I. 74 160), CI Pigment Blue 22 (= CI 69 810) and CI Solvent Yellow 16 (= CI 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 der allgemeinen Formel MFe204, 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 MFe 2 0 4 , 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 Ladungskontrollsubslanzen 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 ladungserzeugenden Schicht beispielsweise folgende Substanzen enthalten: 4-Dimethylaminobenzyliden-benzhydrazid, Polyvinylcarbazol, 2-Benzyliden-aminocarbazol, 2-Nitrobenzyliden-p-bromanilin, 2,4-Diphenylehinazolin, 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 sub in the charge generating layer, for example punches contain: 4-dimethylaminobenzylidene-benzhydrazide, polyvinyl carbazole, 2-benzylidene-aminocarbazole, 2-nitrobenzylidene-p-bromoaniline, 2,4-diphenylehinazoline, 1,5-diphenyl-3-methyl-pyrazoline, 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).

Bcispiel 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 (durchsehn. 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
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 (see Mol. 4 00) heated to 100 ° C for 3 h, initially forming a clear viscous solution, 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

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).The substance is practically pure by thin layer chromatography. 1 shows fluorescence quenching on the fluorescent silica gel plate. Rf value: 0.3 (mobile solvent: 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 her- gestellt:

Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Ebenfalls in analoger Weise werden die folgenden Verbindungen hergestellt:
Figure imgb0014
Analogously, the following compounds are he h - asked:
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
The following connections are also made in an analogous manner:
Figure imgb0014

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 with suction, washed with 800 ml of ethanol and dried at 60 ° C. in vacuo.

Man erhält 366 g Verbindung der Formel

Figure imgb0015
Figure imgb0016
366 g of compound of the formula are obtained
Figure imgb0015
Figure imgb0016

Schmelzpunkt 186-188° CMelting point 186-188 ° C

Die Substanz ist dünnschichtchromatographisch praktisch rein.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 verrUhrt. Der farblose kristalline Niederschlag wird abgesaugt, mit 150 ml Isopropanol gewaschen und bei 40°C im Vakuum getrocknet. Man erhält 87 g (93X der Theorie) Verbindung der Formel56.5 g (0.2 mol) of naphthalic acid N- (3-dimethylaminopropyl) imide are suspended in 700 ml of toluene, 56 g of methyl p-toluenesulfonic acid 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 (93X of theory) of the compound of the formula are obtained

Figure imgb0017
Die Substanz ist dünnschichtchromatographisch vollkommen rein. Sie schmilzt bei 220-221°C.
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
In an analogous manner, the following substances of the formula
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 1 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 1 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 X 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 1 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 1 Wasser gelöst und tropfenweise unter Rühren mit 1 1 einer 40 Xigen 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
Qe = 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 obtained (35 A) 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 e = equivalent of an anion obtained by condensing 4,4'-dihydrodiphenylsulfone, sulfuric acid and formaldehyde in a molar ratio of 1: 1: 0.67.

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 5p 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 5p is.

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 ladüngstransportierende 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, Beispiel 1, hergestellten in der Konturenschärfe noch überlegen sind.Razor-sharp image recordings are obtained which are still superior in contour definition to those produced according to US Pat. No. 4,493,883, Example 1.

Claims (5)

1. Elektrophotographische Toner, die ein die kationische Ladung verstärkendes Additiv der allgemeinen Formel
Figure imgb0026
enthalten,
worin R1 und R2 je für Wasserstoff, Chlor, Brom, Hydroxy, C1-C4-Alkoxy, oder Carboxy, A für C1-C5-Alkylen oder -C6H4-CH2- (m oder p), m für O oder 1 n für 1 oder 2 K für
Figure imgb0027
R3 für C1-C18-Alkyl, Carbamoyl-Cl-C2-alkyl, Cl-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 imgb0028
oder eine Einfachbindung,
Z für
Figure imgb0029
oder eine Einfachbindung und
An⊖ für ein Anion stehen.
1. Electrophotographic toners, which are a cationic charge enhancing additive of the general formula
Figure imgb0026
contain,
wherein R 1 and R 2 each represent hydrogen, chlorine, bromine, hydroxy, C 1 -C 4 alkoxy or carboxy, A for C 1 -C 5 alkylene or -C 6 H 4 -CH 2 - (m or p), m for O or 1 n for 1 or 2 K for
Figure imgb0027
R 3 is C 1 -C 18 -alkyl, carbamoyl-C 1 -C 2 -alkyl, C 1 -C 4 -alkoxycarbonyl-C 1 -C 2 -alkyl, benzyl, cyclohexyl or allyl, R 4 is C 1 -C 4 alkyl or a single bond linking to D, R5 for C 1 -C 4 alkyl, D for -CH 2 -, -CH 2 -CO-, -CH 2 -CO-NH- or -CH 2 -CO-NH-CH 2 - W for
Figure imgb0028
or a single bond,
Z for
Figure imgb0029
or a single bond and
An⊖ stand for an anion.
2. Elektrophotographische Toner nach Anspruch 1, dadurch gekennzeichnet, daß sie ein die kationische Ladung verstärkendes Additiv der allgemeinen Formel
Figure imgb0030
enthalten, worin A1 für C2-C5-AlKylen, K1 für
Figure imgb0031
R6 für C1-C16-Alkyl, Carbamoylmethyl oder Benzyl, R1 für Methyl oder Ethyl oder eine an D anknüpfende Einfachbindung, R8 für Methyl oder Ethyl, W1 für
Figure imgb0032
OS
Z1 für
Figure imgb0033
und
X⊖ für ein Anion stehen, und D, m und h die in Ansprüch 1 angegebene Bedeutung haben.
2. Electrophotographic toner according to claim 1, characterized in that it is a cationic charge-increasing additive of the general formula
Figure imgb0030
included in what A 1 for C 2 -C 5 alkylene, K 1 for
Figure imgb0031
R 6 is C 1 -C 16 alkyl, carbamoylmethyl or benzyl, R 1 represents methyl or ethyl or a single bond linked to D, R 8 represents methyl or ethyl, W 1 for
Figure imgb0032
OS
Z 1 for
Figure imgb0033
and
X⊖ stand for an anion, and D, m and h have the meaning given in claims 1.
3. Elektrophotographische Toner nach Anspruch 1, dadurch gekennzeichnet, daß sie außer dem die kationische Ladung verstärkenden Additiv Harz- und Pigmentpartikel enthalten.3. Electrophotographic toner according to claim 1, characterized in that they contain resin and pigment particles in addition to the additive which increases the cationic charge. 4. Verwendung von Verbindungen der Formel des Anspruchs 1 als die positive Ladung verstärkende Additive in elektrophotographischen Tonern.4. Use of compounds of the formula of claim 1 as positive charge enhancing additives in electrophotographic toners. 5. Naphthalsäureimide der allgemeinen Formel
Figure imgb0034
worin Al für C2-C5-Alkylen, K1 für
Figure imgb0035
R 6 für C1-C16-Alkyl, Carbamoylmethyl oder Benzyl, R 7 für Methyl oder Ethyl oder eine an D anknüpfende Einfachbindung, R 8 für Methyl oder Ethyl, W1 für
Figure imgb0036
Z 1 für
Figure imgb0037
und
X⊖ für ein gegebenenfalls durch C1 oder C1-C12-Alkyl substituiertes Benzolsulfonat, C5-C18-Alkyl-sulfonat oder ein Salz einer C5-C18-Alkylcarbonsäure oder ein Salz eines Kondensationsproduktes aus Formaldehyd und Arylsulfonsäuren und/oder gegebenenfalls sulfoniertem 4,4'-Dihydroxydiphenylsulfon stehen, und D, m und n die in Anspruch 1 angegebene Bedeutung haben.
5. Naphthalic imides of the general formula
Figure imgb0034
wherein A l for C 2 -C 5 alkylene, K 1 for
Figure imgb0035
R 6 is C 1 -C 16 alkyl, carbamoylmethyl or benzyl, R 7 represents methyl or ethyl or a single bond linked to D, R 8 represents methyl or ethyl, W 1 for
Figure imgb0036
Z 1 for
Figure imgb0037
and
X⊖ for an optionally substituted by C1 or C 1 -C 12 alkyl benzenesulfonate, C 5 -C 18 alkyl sulfonate or a salt of a C 5 -C 18 alkyl carboxylic acid or a salt of a condensation product of formaldehyde and aryl sulfonic acids and / or optionally sulfonated 4,4'-dihydroxydiphenyl sulfone, and D, m and n have the meaning given in claim 1.
EP87101463A 1986-02-15 1987-02-03 Electrophotographical toner Expired - Lifetime EP0233544B1 (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
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EP0355006A2 (en) * 1988-08-19 1990-02-21 Bayer Ag Electrophotographical toner
EP0355006A3 (en) * 1988-08-19 1990-03-28 Bayer Ag Electrophotographical toner electrophotographical toner
EP0501249A1 (en) * 1991-02-27 1992-09-02 Bayer Ag Naphthalimides, toners containing them and their use as additive for toners
US5292881A (en) * 1991-02-27 1994-03-08 Bayer Aktiengesellschaft New naphthalimides, toners containing these and the use of the new naphthalimides as additives for toners
WO1993002399A1 (en) * 1991-07-18 1993-02-04 Eastman Kodak Company Toners and developers containing amide-containing quaternary ammonium salts as charge control agents
WO1994011789A1 (en) * 1992-11-07 1994-05-26 Basf Aktiengesellschaft Electrostatic toners containing amphiphilic liquid crystals
US10835453B2 (en) 2016-12-21 2020-11-17 Voco Gmbh Storage-stable resin-modified glass ionomer cement

Also Published As

Publication number Publication date
EP0233544A3 (en) 1990-04-04
EP0233544B1 (en) 1993-09-08
JPH0431584B2 (en) 1992-05-26
US4812379A (en) 1989-03-14
US4841052A (en) 1989-06-20
DE3787297D1 (en) 1993-10-14
DE3604827A1 (en) 1987-08-20
JPS62192755A (en) 1987-08-24

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