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EP0371360B1 - Electrophotographic toners - Google Patents

Electrophotographic toners Download PDF

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Publication number
EP0371360B1
EP0371360B1 EP89121373A EP89121373A EP0371360B1 EP 0371360 B1 EP0371360 B1 EP 0371360B1 EP 89121373 A EP89121373 A EP 89121373A EP 89121373 A EP89121373 A EP 89121373A EP 0371360 B1 EP0371360 B1 EP 0371360B1
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EP
European Patent Office
Prior art keywords
alkyl
formula
phenyl
electrophotographic toners
compounds
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EP89121373A
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German (de)
French (fr)
Other versions
EP0371360A3 (en
EP0371360A2 (en
Inventor
Horst Dr. Harnisch
Roderich Dr. Raue
Klaus Dr. Wunderlich
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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
    • G03G9/09758—Organic compounds comprising a heterocyclic ring

Definitions

  • Preferred substituents on alkyl radicals are hydroxy, C1-C4-alkoxy, chlorine, cyano, carbamoyl or C1-C2-alkoxycarbonyl.
  • Suitable anions are conventional anions such as halides, for example chloride, bromide and iodide, tetrafluoroborates and anions of alkyl and arylsulfonic acids, carboxylic acids, phosphoric acids and phosphonic acids.
  • Anions which reduce the water solubility of the compounds (I) are particularly suitable. However, the reduction in water solubility can also be achieved by increasing the alkyl radical R1, that is to say in the range of C8-C22-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 benzenesulfonates optionally substituted by C1-C12 alkyl or chlorine, C5-C18 alkyl sulfonates, salts of C5-C18 alkyl carboxylic acids and condensation products of formaldehyde and aryl sulfonic acids and / or optionally sulfonated 4,4'-dihydroxydiphenyl sulfone and anions of heteropolyacids based on tungsten and / or molybdenum with phosphorus or silicon, in particular phosphorus tungsten molybdate.
  • the compounds of the formula (I) can be prepared by methods known per se in that compounds of the formula or a tautomer of (III), wherein R1 and R2 have the meaning given above, with compounds of the formula HX, wherein X represents a group forming an anion, implemented and then possibly exchanged the anion.
  • the reaction is expediently carried out in an inert organic solvent in the temperature range from 10-200 ° C., preferably at 20-140 ° C.
  • the reaction product (I) generally crystallizes out of the reaction solution and can be isolated therefrom by filtration. However, the solution can also be evaporated in a paddle dryer and (I) obtained in this way as a crystalline powder.
  • the starting compounds with R 1 not equal to H can be prepared by using a compound of the formula where R2 has the meaning given above, with a primary amine of the formula R1-NH2 (V) condensed with elimination of ammonia.
  • This reaction is also advantageously carried out in an inert solvent in the temperature range from 50-150 ° C., preferably at 70-130 ° C.
  • This reaction is advantageously carried out under the same or the same conditions as the reaction of (IV) and (V).
  • Suitable inert solvents are, for example, sulfolane, aromatics such as toluene, chlorobenzene, o-dichlorobenzene, trichlorobenzenes and xylene, alkanols such as ethanol, propanol, isopropanol, n-butanol, 2-methoxyethanol, 2-ethoxyethanol, alkanediols such as ethylene glycol, dialkoxyalkanes such as ethylene glycol dimethyl ether such as acetonitrile, chlorinated aliphatics such as methylene chloride or chloroform, and dipolar aprotic solvents such as dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide.
  • aromatics such as toluene, chlorobenzene, o-dichlorobenzene, trichlorobenzenes and xylene
  • alkanols such as ethanol, propano
  • the compounds of formula (I) are mostly colorless or only slightly colored.
  • Compounds of formula (I) in which R1 and R2 are phenyl have a yellowish intrinsic color.
  • Charge enhancing additives for electrophotographic toners also called charge control substances, are already known. They are described, for example, in DE-A 36 04 827 and 37 38 948, in EP-A 2 33 544, in US-A 3 893 935, 3 944 493, 4 007 293, 4 079 014, 4 265 990, 4,298,672, 4,338,390, 4,394,430, 4,493,883, and in JA-A 61-156144.
  • 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 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.
  • the toners according to the invention contain coloring materials and, if appropriate, 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, for example by mixing the constituents in a kneader and then pulverizing or by melting the thermoplastic resin or a mixture of the thermoplastic resins, followed by fine division of one or more charge control substances of the formula (I ), as well as the other additives, if used, in the molten resin using the mixing and kneading machines known for this purpose, then 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 suspend the thermoplastic resin and the compound (I) in a common solvent and to incorporate the other additives into the suspension. The suspension can thus be used as a liquid toner.
  • the liquid can also be spray-dried in a manner known per se or the solvents evaporated and the solid residue ground into particles of the desired particle size.
  • 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 substances of the formula (I) have a further improvement in image sharpness, an even lower sensitivity to high atmospheric humidity and an even longer life of the toner (more than 70,000 copies) compared to the previously known cationic compounds.
  • the solution is mixed in small portions with a total of 171 g of p-toluenesulfonic acid monohydrate (0.9 mol), briefly heated to 85 ° C, cooled to room temperature and 5 h at 20 ° C and 1 h stirred at 5 ° C.
  • the colorless crystalline precipitate is filtered off, washed with ice-cold isopropanol and dried at 50 ° C in a vacuum. 283 g, corresponding to 84% of the theory, of the compound of the formula are obtained as a colorless crystal powder with a melting point of 235-237 ° C (from isopropanol).
  • Example 1 is repeated, but 1.6 mol of benzylamine is used instead of cyclohexylamine. 286 g (82% of theory) of the compound of the formula are obtained as colorless crystals with a melting point of 217-218 ° C.
  • 1,290 g of water are introduced and 8.5 g of sodium hydroxide (0.2 mol) are added.
  • the solution is heated to 90 ° C. 416.4 g of ammonium tungstate solution (50% WO3, corresponding to 230.7 g, 100%, corresponding to 1 mol), 28.5 g of molybdenum 6-oxide (approx. 0.2 mol ), 35.7 g disodium hydrogenphosphate dihydrate, 27.9 g hydrochloric acid crude (32%, corresponding to 0.24 mol) and 53.6 g sodium bisulfite solution 40% (0.2 mol), the solution is heated for 30 min to boiling (approx. 102 ° C), cools it down to 30 ° C and adjusts the pH to 4 with approx. 6.2 ml hydrochloric acid (approx. 32%).
  • styrene-n-butyl methacrylate copolymer mol: 50,000
  • 5 g of the phosphorus tungsten molybdate mentioned in Example 16 are mixed uniformly in a kneader. After cooling, the resin is pulverized in a jet mill to an average grain size of 12 ⁇ . 5 g of this toner powder are charged with 95 g of a carrier material made of iron with a polymer coating by rotation and the charge is determined by the blow-off method. It is 20.2 ⁇ C / g and is still high after 70,000 copies.
  • the procedure for this is to provide a MYLAR R substrate with a polyvinyl carbazole charge-generating layer upon exposure, 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-methyl-phenyl) -1,1, -bisphenyl-4,4'-diamine, dispersed in a MAKROLON R polycarbonate composition.

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

Description

Verbindungen der Formel (I) (siehe unten) sind bereits bekannt.Compounds of formula (I) (see below) are already known.

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

Figure imgb0001

enthalten, worin

R¹ und R²
unabhängig voneinander für H, C₁-C₂₂-Alkyl, Allyl, Cyclohexyl, Phenyl-C₁-C₂-alkyl oder Phenyl stehen und
An⁻
ein Anion bedeutet,
worin der Ring A und die cyclischen und acyclischen Reste 1-2 nichtionogene Substituenten tragen können, und worin der an der Klammer stehende Wasserstoff an einem Stickstoffatom sitzt.The invention relates to positively charged electrophotographic toners which, in addition to conventional resin and pigment particles, an additive of the general formula which increases the cationic charge
Figure imgb0001
included in what
R1 and R2
independently represent H, C₁-C₂₂-alkyl, allyl, cyclohexyl, phenyl-C₁-C₂-alkyl or phenyl and
An⁻
an anion means
wherein the ring A and the cyclic and acyclic radicals can carry 1-2 nonionic substituents, and where the hydrogen on the bracket sits on a nitrogen atom.

Von besonderem technischen Wert sind Verbindungen der Formel (I), in denen

R₁ und R₂
unabhängig voneinander für Wasserstoff, unsubstituiertes C₄-C₁₈-Alkyl, Benzyl oder Cyclohexyl stehen und
die nichtionogenen Substituenten C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Hydroxy, Halogen wie Chlor und Brom, Cyan, einen Carbamoyl- oder Sulfamoylrest, der durch 1-2 C₁-C₄-Alkylreste substituiert sein kann, C₁-C₄-Alkoxycarbonyl oder Phenyl bedeuten.Of particular technical value are compounds of formula (I) in which
R₁ and R₂
independently represent hydrogen, unsubstituted C₄-C₁₈ alkyl, benzyl or cyclohexyl and
the nonionic substituents C₁-C₄-alkyl, C₁-C₄-alkoxy, hydroxy, halogen such as chlorine and bromine, cyano, a carbamoyl or sulfamoyl radical, which can be substituted by 1-2 C₁-C₄-alkyl radicals, C₁-C₄-alkoxycarbonyl or phenyl.

Bevorzugte Substituenten an Alkylresten sind Hydroxy, C₁-C₄-Alkoxy, Chlor, Cyan, Carbamoyl oder C₁-C₂-Alkoxycarbonyl.Preferred substituents on alkyl radicals are hydroxy, C₁-C₄-alkoxy, chlorine, cyano, carbamoyl or C₁-C₂-alkoxycarbonyl.

Als Anionen sind übliche Anionen wie Halogenide, z.B. Chlorid, Bromid und Jodid, Tetrafluoroborate und Anionen von Alkyl- und Arylsulfonsäuren, -carbonsäuren, -phosphorsäuren und -phosphonsäuren geeignet. Besonders geeignet sind solche Anionen, die die Wasserloslichkeit der Verbindungen (I) erniedrigen. Die Verminderung der Wasserloslichkeit kann aber auch dadurch erfolgen, daß man den Alkylrest R¹ vergrößert, also etwa im Bereich von C₈-C₂₂-Alkyl wählt. In diesem Falle sind auch hydrophilere Anionen wie Halogenide bestens geeignet.Suitable anions are conventional anions such as halides, for example chloride, bromide and iodide, tetrafluoroborates and anions of alkyl and arylsulfonic acids, carboxylic acids, phosphoric acids and phosphonic acids. Anions which reduce the water solubility of the compounds (I) are particularly suitable. However, the reduction in water solubility can also be achieved by increasing the alkyl radical R¹, that is to say in the range of C₈-C₂₂-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 ggf. 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 ggf. sulfoniertem 4,4'-Dihydroxydiphenylsulfon sowie Anionen von Heteropolysäuren auf Basis Wolfram und/oder Molybdän mit Phosphor oder Silicium, insbesondere Phosphorwolframmolybdate.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 benzenesulfonates optionally substituted by C₁-C₁₂ alkyl or chlorine, C₅-C₁₈ alkyl sulfonates, salts of C₅-C₁₈ alkyl carboxylic acids and condensation products of formaldehyde and aryl sulfonic acids and / or optionally sulfonated 4,4'-dihydroxydiphenyl sulfone and anions of heteropolyacids based on tungsten and / or molybdenum with phosphorus or silicon, in particular phosphorus tungsten molybdate.

Von besonderem technischen Wert sind solche Verbindungen der Formel (I), worin R² = R¹ ist.Of particular technical value are those compounds of formula (I) in which R² = R¹.

Die Verbindungen der Formel (I) können nach an sich bekannten Methoden dadurch hergestellt werden, daß man Verbindungen der Formel

Figure imgb0002

oder ein Tautomeres von (III), worin
R¹ und R² die oben angegebene Bedeutung besitzen,
mit Verbindungen der Formel HX, worin
X für eine ein Anion bildende Gruppe steht,
umsetzt und anschließend ggf. das Anion austauscht.The compounds of the formula (I) can be prepared by methods known per se in that compounds of the formula
Figure imgb0002
or a tautomer of (III), wherein
R¹ and R² have the meaning given above,
with compounds of the formula HX, wherein
X represents a group forming an anion,
implemented and then possibly exchanged the anion.

Die Reaktion wird zweckmäßig in einem inerten organischen Lösungsmittel im Temperaturbereich von 10-200°C, vorzugsweise bei 20-140°C durchgeführt.
Das Reaktionsprodukt (I) kristallisiert in der Regel aus der Reaktionslösung aus und kann daraus durch Abfiltrieren isoliert werden. Man kann die Lösung aber auch im Schaufeltrockner eindampfen und (I) auf diese Weise als kristallines Pulver gewinnen.The reaction is expediently carried out in an inert organic solvent in the temperature range from 10-200 ° C., preferably at 20-140 ° C.
The reaction product (I) generally crystallizes out of the reaction solution and can be isolated therefrom by filtration. However, the solution can also be evaporated in a paddle dryer and (I) obtained in this way as a crystalline powder.

Die Ausgangsverbindungen mit R¹ ungleich H können dadurch hergestellt werden, daß man eine Verbindung der Formel

Figure imgb0003

worin R² die oben angegebene Bedeutung besitzt,
mit einem primären Amin der Formel



        R¹-NH₂   (V)



unter Abspaltung von Ammoniak kondensiert.The starting compounds with R 1 not equal to H can be prepared by using a compound of the formula
Figure imgb0003
where R² has the meaning given above,
with a primary amine of the formula



R¹-NH₂ (V)



condensed with elimination of ammonia.

Auch diese Reaktion wird zweckmäßig in einem inerten Lösungsmittel im Temperaturbereich von 50-150°C, vorzugsweise bei 70-130°C durchgeführt.This reaction is also advantageously carried out in an inert solvent in the temperature range from 50-150 ° C., preferably at 70-130 ° C.

Verbindungen der Formel (IV) oder Tautomere von (IV) werden dadurch hergestellt, daß man eine Verbindung der Formel

Figure imgb0004

mit einem primären Amin der Formel



        R²-NH₂   (VII),



worin R² die oben angegebene Bedeutung besitzt,
unter Abspaltung von Ammoniak kondensiert.Compounds of formula (IV) or tautomers of (IV) are prepared by using a compound of formula
Figure imgb0004
with a primary amine of the formula



R²-NH₂ (VII),



where R² has the meaning given above,
condensed with elimination of ammonia.

Diese Reaktion wird zweckmäßig unter gleichartigen oder gleichen Bedingungen durchgeführt wie die Umsetzung von (IV) und (V).This reaction is advantageously carried out under the same or the same conditions as the reaction of (IV) and (V).

Liegt der bevorzugte Fall vor, daß R¹ = R² ist, so kondensiert man (VI) zweckmäßig mit 2 Äquivalenten R¹-NH₂.If the preferred case is that R¹ = R², then (VI) is appropriately condensed with 2 equivalents of R¹-NH₂.

Eine bevorzugte Ausfuhrungsform des Verfahrens zur Herstellung von (I) mit R² = R¹ besteht darin, daß man zunachst (VI) mit 2 Äquivalenten R¹-NH₂ kondensiert und die so erhaltene Verbindung (III) ohne Zwischenisolierung im gleichen Reaktionsmedium mit HX weiter umsetzt und anschließend gewünschtenfalls das Anion, z.B. analog DE-A 37 38 948, austauscht.A preferred embodiment of the process for the preparation of (I) with R² = R¹ is that first (VI) is condensed with 2 equivalents of R¹-NH₂ and the compound (III) thus obtained is reacted with HX without intermediate isolation in the same reaction medium and then if desired, the anion, for example analogous to DE-A 37 38 948.

Geeignete inerte Lösungsmittel sind beispielsweise Sulfolan, Aromaten wie Toluol, Chlorbenzol, o-Dichlorbenzol, Trichlorbenzole und Xylol, Alkanole wie Ethanol, Propanol, Isopropanol, n-Butanol, 2-Methoxyethanol, 2-Ethoxyethanol, Alkandiole wie Ethylenglykol, Dialkoxyalkane wie Ethylenglykoldimethylether, Nitrile wie Acetonitril, chlorierte Aliphaten wie Methylenchlorid oder Chloroform, und dipolar aprotische Lösungsmittel wie Dimethylformamid, N-Methylpyrrolidon oder Dimethylsulfoxid.Suitable inert solvents are, for example, sulfolane, aromatics such as toluene, chlorobenzene, o-dichlorobenzene, trichlorobenzenes and xylene, alkanols such as ethanol, propanol, isopropanol, n-butanol, 2-methoxyethanol, 2-ethoxyethanol, alkanediols such as ethylene glycol, dialkoxyalkanes such as ethylene glycol dimethyl ether such as acetonitrile, chlorinated aliphatics such as methylene chloride or chloroform, and dipolar aprotic solvents such as dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide.

Die Verbindungen der Formel (I) sind zumeist farblos oder nur schwach gefärbt. Verbindungen der Formel (I), in denen R¹ und R² für Phenyl stehen, haben eine gelbliche Eigenfarbe.The compounds of formula (I) are mostly colorless or only slightly colored. Compounds of formula (I) in which R¹ and R² are phenyl have a yellowish intrinsic color.

Ladungsverstärkende Additive für elektrophotographische Toner, auch Ladungskontrollsubstanzen genannt, sind bereits bekannt. Sie werden beispielsweise in der DE-A 36 04 827 und 37 38 948, in der EP-A 2 33 544, in den US-A 3 893 935, 3 944 493, 4 007 293, 4 079 014, 4 265 990, 4 298 672, 4 338 390, 4 394 430, 4 493 883, und in der JA-A 61-156 144 beschrieben.Charge enhancing additives for electrophotographic toners, also called charge control substances, are already known. They are described, for example, in DE-A 36 04 827 and 37 38 948, in EP-A 2 33 544, in US-A 3 893 935, 3 944 493, 4 007 293, 4 079 014, 4 265 990, 4,298,672, 4,338,390, 4,394,430, 4,493,883, and in JA-A 61-156144.

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.

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 Methacrylates 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. Zusätzlich zu den Verbindungen (I) und den thermoplastischen Harzen enthalten die erfindungsgemäßen Toner in bekannten Mengen Färbungsmaterialien und ggf. magnetisch anziehbares Material. Das Farbungsmaterial kann aus einem organischen Farbstoff wie Nigrosin, Anilinblau, 2,9-Dimethylchinacridon, C.I. Disperse Red 15 (= C.I. 60 10), 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 Bleidioxid oder Chromgelb bestehen. Allgemein überschreitet die Menge des in dem Toner vorhandenen Färbungsmaterials etwa 15 Gew.% nicht.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. In addition to the compounds (I) and the thermoplastic resins, the toners according to the invention contain coloring materials and, if appropriate, magnetically attractable material in known amounts. The coloring material can consist of an organic dye such as nigrosine, aniline blue, 2,9-dimethylquinacridone, CI Disperse Red 15 (= CI 60 10), CI Solvent Red 19 (= CI 26 050), CI Pigment Blue 15 (= CI 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 dioxide or chrome yellow. Generally, the amount of the coloring material present in the toner does not exceed about 15% by weight.

Das magnetisch anziehbare Material kann beispielsweise aus Eisen, Nickel, Chromoxid, Eisenoxid oder einem Ferrit der 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 Vermischen der Bestandteile in einem Kneter und anschließendes Pulverisieren oder durch Schmelzen des thermoplastischen Harzes oder eines Gemisches der thermoplastischen Harze, anschließende feine 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 Knetmaschinen, anschließende Abkuhlung 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 suspendieren und die anderen Zusätze in die Suspension einzuverleiben. Die Suspension kann so als Flüssigtoner verwendet werden.The toners containing the compounds (I) are prepared by customary processes, for example by mixing the constituents in a kneader and then pulverizing or by melting the thermoplastic resin or a mixture of the thermoplastic resins, followed by fine division of one or more charge control substances of the formula (I ), as well as the other additives, if used, in the molten resin using the mixing and kneading machines known for this purpose, then 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 suspend the thermoplastic resin and the compound (I) in a common solvent and to incorporate the other additives into the suspension. The suspension can thus be used as a liquid toner.

Man kann die Flüssigkeit aber auch in an sich bekannter Weise sprühtrocknen oder die Lösungsmittel abdampfen und den festen Rückstand zu Teilchen der gewünschten Teilchengröße vermahlen.However, the liquid can also be spray-dried in a manner known per se or the solvents evaporated and the solid residue ground into particles of the desired particle size.

Entsprechend einer Abänderung dieses Herstellungsverfahrens wird die Ladungskontrollsubstanz der Formel (I) nicht gelöst, sondern fein in der Lösung des thermoplastischen Harzes dispergiert.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 Tonerzübereitung wird dann, beispielsweise analog US-PS 4 265 990, in einem xerographischen Bildaufzeichnungssystem eingesetzt.The toner preparation thus obtained is then used in a xerographic image recording system, for example analogously to US Pat. No. 4,265,990.

Die verwendeten Ladungskontrollsubstanzen müssen vielseitige Anforderungen erfüllen.

  • 1. Fähigkeit zur Entwicklung des latenten elektrostatischen Bildes zu einem farbstarken sichtbaren Bild.
  • 2. Leichte Verteilbarkeit in der Tonerzübereitung und gleichmäige 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 Blei dioxid und einem Vinylidenfluorid-Hexafluoropropylen-Copolymerisat-Harz (z.B. VITONRE430 von Dupont), mit der das Bild mit Hilfe einer heißen Walze fixiert werden kann. Die Beschichtungsmasse darf sich nicht durch Zersetzungsprodukte schwarz färben.
The charge control substances used must meet diverse requirements.
  • 1. Ability to develop the latent electrostatic image into a highly visible color image.
  • 2. Easily distributable in the ore preparation and even distribution 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 dioxide and a vinylidene fluoride-hexafluoropropylene copolymer resin (eg VITON R E430 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.

Die aus den oben genannten Patent- und Offenlegungsschriften bekannten Ladungskontrollsubstanzen erfullen nicht alle diese Anforderungen.The charge control substances known from the above-mentioned patent and published documents do not meet all of these requirements.

Überraschenderweise zeigte sich nun, daß die Substanzen der Formel (I) gegenüber den genannten, bisher bekannten kationischen Verbindungen eine weitere Verbesserung der Bildschärfe, eine noch geringere Empfindlichkeit gegenüber hoher Luftfeuchtigkeit und eine noch höhere Lebensdauer des Toners (mehr als 70 000 Kopien) aufweisen.Surprisingly, it has now been found that the substances of the formula (I) have a further improvement in image sharpness, an even lower sensitivity to high atmospheric humidity and an even longer life of the toner (more than 70,000 copies) compared to the previously known cationic compounds.

Beispiel 1example 1

110 g 3-Amino-1-imino-isoindolenin 92%ig (0,7 mol) werden in 700 ml Isopropanol mit 160 g Cyclohexylamin (ca. 1,6 mol) 16 h unter Rückfluß zum Sieden erhitzt, wobei Ammoniak entweicht und eine klare, leicht grünliche Lösung entsteht. Ein Dünnschichtchromatogramm einer 5%igen methanolischen Lösung in einem Laufmittelgemisch von 350 ml Butylacetat, 100 ml Wasser, 250 ml Eisessig und 100 ml Ameisensäure zeigt eine praktisch einheitliche Umsetzung zu der Verbindung der Formel

Figure imgb0005

C₂₀H₂₅N₃ (307,44) m/e = 307 (M⁺).
Die Lösung wird, bei 40°C beginnend, in kleinen Portionen mit insgesamt 171 g p-Toluolsulfonsäure-monohydrat (0,9 mol) versetzt, kurz auf 85°C erhitzt, abgekühlt auf Raumtemperatur und 5 h bei 20°C sowie 1 h bei 5°C verrührt. Der farblose kristalline Niederschlag wird abgesaugt, mit eiskaltem Isopropanol gewaschen und bei 50°C im Vakuum getrocknet. Man erhält 283 g, entspr. 84 % der Theorie Verbindung der Formel
Figure imgb0006
als farbloses Kristallpulver vom Schmelzpunkt 235-237°C (aus Isopropanol).110 g of 3-amino-1-imino-isoindolenine 92% (0.7 mol) are refluxed in 700 ml of isopropanol with 160 g of cyclohexylamine (approx. 1.6 mol) for 16 hours, ammonia escaping and a clear, slightly greenish solution is created. A thin layer chromatogram of a 5% methanolic solution in a mobile phase mixture of 350 ml of butyl acetate, 100 ml of water, 250 ml of glacial acetic acid and 100 ml of formic acid shows a practically uniform conversion to the compound of the formula
Figure imgb0005
C₂₀H₂₅N₃ (307.44) m / e = 307 (M⁺).
Starting at 40 ° C, the solution is mixed in small portions with a total of 171 g of p-toluenesulfonic acid monohydrate (0.9 mol), briefly heated to 85 ° C, cooled to room temperature and 5 h at 20 ° C and 1 h stirred at 5 ° C. The colorless crystalline precipitate is filtered off, washed with ice-cold isopropanol and dried at 50 ° C in a vacuum. 283 g, corresponding to 84% of the theory, of the compound of the formula are obtained
Figure imgb0006
as a colorless crystal powder with a melting point of 235-237 ° C (from isopropanol).

Beispiel 2Example 2

Man wiederholt Beispiel 1, setzt aber anstelle von Cyclohexylamin 1,6 mol Benzylamin ein. Man erhält 286 g (82 % der Theorie) Verbindung der Formel

Figure imgb0007

als farblose Kristalle vom Schmelzpunkt 217-218°C.Example 1 is repeated, but 1.6 mol of benzylamine is used instead of cyclohexylamine. 286 g (82% of theory) of the compound of the formula are obtained
Figure imgb0007
as colorless crystals with a melting point of 217-218 ° C.

Beispiel 3Example 3

Man verfährt wie in Beipsiel 1, setzt aber anstelle von Cyclohexylamin 1,6 mol Hexadecylamin ein. Man erhält 424 g (79 % der Theorie) Verbindung der Formel

Figure imgb0008

als farblose Kristalle vom Schmelzpunkt 81-83°C.The procedure is as in Example 1, but using 1.6 mol of hexadecylamine instead of cyclohexylamine. 424 g (79% of theory) of the compound of the formula are obtained
Figure imgb0008
as colorless crystals with a melting point of 81-83 ° C.

Analog Beispiel I werden auch folgende Verbindungen der Formel

Figure imgb0009

hergestellt.
Figure imgb0010
Figure imgb0011
 Analogous to Example I, the following compounds of the formula
Figure imgb0009
produced.
Figure imgb0010
Figure imgb0011

Beispiel 16Example 16 a) Herstellung einer Phosphorwolframmolybdatlösung:a) Preparation of a Phosphotungsten Molybdate Solution:

1 290 g Wasser werden vorgelegt und mit 8,5 g Natriumhydroxid (0,2 mol) versetzt. Die Lösung wird auf 90°C erwärmt. Anschließend trägt man in der angegebenen Reihenfolge 416,4 g Ammoniumwolframatlösung (50 % WO₃, entspr. 230,7 g, 100%ig, entspr. 1 mol), 28,5 g Molybdän-6-oxid (ca. 0,2 mol), 35,7 g Dinatriumhydrogenphosphat-dihydrat, 27,9 g Salzsäure roh (32%ig, entspr. 0,24 mol) und 53,6 g Natriumbisulfitlösung 40%ig (0,2 mol) ein, erwärmt die Lösung 30 min zum Sieden (ca. 102°C), kühlt sie auf 30°C ab und stellt den pH-Wert mit ca. 6,2 ml Salzsäure (ca. 32%ig) auf 4.1,290 g of water are introduced and 8.5 g of sodium hydroxide (0.2 mol) are added. The solution is heated to 90 ° C. 416.4 g of ammonium tungstate solution (50% WO₃, corresponding to 230.7 g, 100%, corresponding to 1 mol), 28.5 g of molybdenum 6-oxide (approx. 0.2 mol ), 35.7 g disodium hydrogenphosphate dihydrate, 27.9 g hydrochloric acid crude (32%, corresponding to 0.24 mol) and 53.6 g sodium bisulfite solution 40% (0.2 mol), the solution is heated for 30 min to boiling (approx. 102 ° C), cools it down to 30 ° C and adjusts the pH to 4 with approx. 6.2 ml hydrochloric acid (approx. 32%).

b) Fällungb) Precipitation

148 g 3-Amino-1-imino-isoindolenin 98%ig (1 mol) werden in 2 l Wasser bei 60°C gelöst. In die so hergestellte Lösung läßt man unter Rühren bei 50-55°C innerhalb von 30-60 min 1 600 ml der unter a) hergestellten Lösung einlaufen. Das Umsetzungsprodukt kristallisiert aus und der pH-Wert steigt auf >4 an. Durch Zutropfen von ca. 5,7 ml Salzsäure stellt man den pH-Wert auf 3,3 und rührt die Suspension 30 min bei 50-55°C nach. Der kristalline Niederschlag wird bei 30°C abgesaugt, in 5 Portionen mit insgesamt 1000 ml Wasser gewaschen und bei 80°C im Vakuum getrocknet.
Ausbeute: 183 g Verbindung der Formel

Figure imgb0012
148 g of 3-amino-1-imino-isoindolenine 98% (1 mol) are dissolved in 2 l of water at 60 ° C. 600 ml of the solution prepared under a) are run into the solution thus prepared with stirring at 50-55 ° C. within 30-60 min. The reaction product crystallizes out and the pH rises to> 4. By dropping approx. 5.7 ml of hydrochloric acid, the pH is adjusted to 3.3 and the suspension is stirred at 50-55 ° C. for 30 minutes. The crystalline precipitate is filtered off at 30 ° C, washed in 5 portions with a total of 1000 ml of water and dried at 80 ° C in a vacuum.
Yield: 183 g of compound of the formula
Figure imgb0012

Beispiel 17Example 17

165,2 g wasserfreie p-Toluolsulfonsaure werden in 200 ml Dimethylformamid eingetragen und bei 80°C mit einer bei 70°C hergestellten Lösung von 116,0 g 3-Amino-1-iminoisoindolenin in 800 ml Dimethylformamid versetzt. Nach Verdünnen mit 400 ml Dimethylformamid wird nach 1/2 h Rühren bei 80°C auf Raumtemperatur abgekühlt. Nach weiteren 3,5 h Rühren wird abgesaugt, mit 200 ml Dimethylformamid und anschließend mit Aceton gewaschen. Nach Trocknung bei 70°C werden 190,0 g der Verbindung der Formel

Figure imgb0013

erhalten. Elementaranalyse: C H N O S ber. 56,8 4,7 13,3 15,1 10,1 % gef. 54,3 5,0 12,4 16,4 10,9 % 165.2 g of anhydrous p-toluenesulfonic acid are introduced into 200 ml of dimethylformamide and a solution of 116.0 g of 3-amino-1-iminoisoindolenine in 800 ml of dimethylformamide prepared at 70 ° C. is added at 80 ° C. After dilution with 400 ml of dimethylformamide, the mixture is cooled to room temperature after stirring for 1/2 h at 80 ° C. After stirring for a further 3.5 h, the product is filtered off with suction, washed with 200 ml of dimethylformamide and then with acetone. After drying at 70 ° C 190.0 g of the compound of formula
Figure imgb0013
receive. Elemental analysis: C. H N O S about. 56.8 4.7 13.3 15.1 10.1% found 54.3 5.0 12.4 16.4 10.9%

Beispiel 18Example 18

23,3 g Amidosulfonsäure werden in 75 ml Dimethylformamid gelöst und anschließend mit einer bei 80°C bereiteten Lösung von 29,0 g 3-Amino-1-imino-isoindolenin in 200 ml Dimethylformamid versetzt. Nach 3 h Ruhren bei 65°C wird auf Raumtemperatur abgekühlt. Es wird mit 250 ml Aceton verdunnt und nach 1/4 h Ruhren abgesaugt. Nach dem Waschen mit 100 ml Aceton und Trocknen bei 60°C werden 32,7 g der Verbindung der Formel

Figure imgb0014

erhalten. Elementaranalyse: C H N O S ber. 39,7 4,1 23,1 19,8 13,2 % gef. 39,4 4,0 23,1 19,9 13,2 % 23.3 g of amidosulfonic acid are dissolved in 75 ml of dimethylformamide and then a solution of 29.0 g of 3-amino-1-imino-isoindolenine in 200 ml of dimethylformamide prepared at 80 ° C. is added. After 3 hours of stirring at 65 ° C., the mixture is cooled to room temperature. It is diluted with 250 ml of acetone and suction filtered after 1/4 h stirring. After washing with 100 ml of acetone and drying at 60 ° C, 32.7 g of the compound of formula
Figure imgb0014
receive. Elemental analysis: C. H N O S about. 39.7 4.1 23.1 19.8 13.2% found 39.4 4.0 23.1 19.9 13.2%

Anwendungsbeispiel AExample of use A

100 g Styrol-n-butylmethacrylat-Copolymer (Mol: 50 000) und 5 g des in Beispiel 16 genannten Phosphorwolframmolybdats werden in einem Kneter gleichmäßig vermischt. Nach dem Abkühlen pulverisiert man das Harz in einer Strahlmühle auf eine mittlere Kornfeinheit von 12 µ. 5 g dieses Tonerpulvers werden mit 95 g eines Carriermaterials aus Eisen mit Polymerbeschichtung durch Rotation aufgeladen und die Ladung nach der Blow-off-Methode bestimmt. Sie beträgt 20,2 µC/g und ist nach 70 000 Kopien noch unverändert hoch.100 g of styrene-n-butyl methacrylate copolymer (mol: 50,000) and 5 g of the phosphorus tungsten molybdate mentioned in Example 16 are mixed uniformly in a kneader. After cooling, the resin is pulverized in a jet mill to an average grain size of 12 µ. 5 g of this toner powder are charged with 95 g of a carrier material made of iron with a polymer coating by rotation and the charge is determined by the blow-off method. It is 20.2 µC / g and is still high after 70,000 copies.

Setzt man anstelle von Verbindung des Beispiels 16 eine in den übrigen Beispielen beschriebene Verbindung ein, so erhält man ähnlich gute Aufladungseffekte.If, instead of the compound from Example 16, a compound described in the other examples is used, similarly good charging effects are obtained.

Anwendungsbeispiel BExample of use B

2 Gewichtsprozent Verbindung des Beispiels 1, 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 5 µ ist.
Diese Toner-Zubereitung wird in ein xerographisches Bildaufzeichnungssystem, wie es in US-A 4 265 990 beschrieben ist, eingearbeitet. Dazu geht man in der Weise vor, daß man ein MYLARR-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-methyl-phenyl)-1,1,-bisphenyl-4,4′-diamin, dispergiert in einer MAKROLONR-Polycarbonatmasse enthält.2 percent by weight of the compound of Example 1, 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 smaller than 5 µ.
This toner preparation is incorporated into a xerographic imaging system as described in US-A 4,265,990. The procedure for this is to provide a MYLAR R substrate with a polyvinyl carbazole charge-generating layer upon exposure, 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-methyl-phenyl) -1,1, -bisphenyl-4,4'-diamine, dispersed in a MAKROLON R polycarbonate composition.

Man erhält gestochen scharfe Bildaufzeichnungen.You get pin sharp image recordings.

Claims (4)

  1. Electrophotographic toners which contain an additive which intensifies the cationic charge, of the general formula
    Figure imgb0016
     wherein
    R¹ and R²   independently of one another represent H, C₁-C₂₂-alkyl, allyl, cyclohexyl, phenyl-C₁-C₂-alkyl or phenyl and
    An⁻   denotes an anion,
    wherein the ring A and the cyclic and acyclic radicals can carry 1-2 nonionic substituents, and wherein the hydrogen on the bracket is located on a nitrogen atom.
  2. Electrophotographic toners according to Claim 1, characterized in that
    R¹ and R² independently of one another represent hydrogen, unsubstituted C₄-C₁₈-alkyl, benzyl or cyclohexyl and
    the nonionic substituents denote C₁-C₄-alkyl, C₁-C₄-alkoxy, hydroxyl, halogen, such as chlorine and bromine, cyano, a carbamoyl or sulphamoyl radical, which can be substituted by 1-2 C₁-C₄-alkyl radicals, C₁-C₄-alkoxycarbonyl or phenyl.
  3. Electrophotographic toners according to Claim 1, characterized in that
    R¹ = R².
  4. Electrophotographic toners according to Claim 1, characterized in that, in addition to the additive which intensifies the cationic charge, they contain resin and pigment particles.
EP89121373A 1988-12-01 1989-11-18 Electrophotographic toners Expired - Lifetime EP0371360B1 (en)

Applications Claiming Priority (2)

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DE3840488 1988-12-01
DE3840488A DE3840488A1 (en) 1988-12-01 1988-12-01 ELECTROPHOTOGRAPHIC TONER

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EP0371360A2 EP0371360A2 (en) 1990-06-06
EP0371360A3 EP0371360A3 (en) 1990-11-07
EP0371360B1 true EP0371360B1 (en) 1993-03-31

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3935858A1 (en) * 1989-10-27 1991-05-02 Bayer Ag METHOD FOR PRODUCING ISOINDOL-BASED PIGMENTS
JPH05289407A (en) * 1992-04-09 1993-11-05 Tomoegawa Paper Co Ltd Positive charge color developer
US5559247A (en) * 1994-04-26 1996-09-24 Mitsui Toatsu Chemicals, Inc. Carboxylate and heat-sensitive recording material using same
JP3720092B2 (en) * 1995-09-06 2005-11-24 保土谷化学工業株式会社 Toner for electrostatic image development
WO1998031667A1 (en) * 1997-01-16 1998-07-23 Ciba Specialty Chemicals Holding Inc. Amino-iminoisoindolenine benzene sulfonate, and process for the preparation of nitrate and benzene sulfonate salts of amino-aminoisoindolenine derivatives

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Publication number Priority date Publication date Assignee Title
NL102119C (en) * 1949-08-25 1900-01-01
US2752346A (en) * 1949-08-25 1956-06-26 Bayer Ag Process for production of isoindolenine derivatives
DD207908A1 (en) * 1981-09-24 1984-03-21 Wolfgang Klar METHOD FOR THE MANIPULAR PRODUCTION OF 1-AMINO-3-IMINO-ISO-INDOLENIN NITRATE (I-NITRATE)
JPS61156137A (en) * 1984-12-28 1986-07-15 Canon Inc Electrostatic image developing toner
JPS61258268A (en) * 1985-05-13 1986-11-15 Canon Inc Charge providing material for developing electrostatic charge image
JPS61259265A (en) * 1985-05-14 1986-11-17 Canon Inc Charge providing material for developing electrostatic charge image
JPS63201665A (en) * 1987-02-18 1988-08-19 Ricoh Co Ltd Toner for developing electrostatic images
JPH01259387A (en) * 1988-04-11 1989-10-17 Ricoh Co Ltd Triboelectrostatic charge imparting member
DE3821199A1 (en) * 1988-06-23 1989-12-28 Basf Ag ELECTROSTATIC TONER

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JPH02188763A (en) 1990-07-24
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DE58903960D1 (en) 1993-05-06
DE3840488A1 (en) 1990-06-07
EP0371360A2 (en) 1990-06-06

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