EP0371360B1 - Toners électrophotographiques - Google Patents

Toners électrophotographiques 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
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP89121373A
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German (de)
English (en)
Other versions
EP0371360A2 (fr
EP0371360A3 (en
Inventor
Horst Dr. Harnisch
Roderich Dr. Raue
Klaus Dr. Wunderlich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
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Bayer AG
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Publication date
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Publication of EP0371360B1 publication Critical patent/EP0371360B1/fr
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/097—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)

Claims (4)

  1. Encres électrophotographiques ("toners") contenant un additif renforçant la charge cationique qui répond à la formule générale :
    Figure imgb0017
     dans laquelle
    R¹ et R²   représentent chacun, indépendamment l'un de l'autre, l'hydrogène, un groupe alkyle en C₁-C₂₂, allyle, cyclohexyle, phényl-alkyle en C₁-C₂ ou phényle,
    An⁻   représente un anion,
    le cycle A et les radicaux cycliques et acycliques pouvant porter 1 à 2 substituants non ioniques, l'hydrogène représenté à droite du crochet étant sur un atome d'azote.
  2. Encres électrophotographiques selon la revendication 1, caractérisées en ce que
    R¹ et R² représentent chacun, indépendamment l'un de l'autre, l'hydrogène, un groupe alkyle non substitué en C₄-C₁₈, benzyle ou cyclohexyle et
    les substituants non ioniques sont des groupes alkyle en C₁-C₄, alcoxy en C₁-C₄, hydroxy, des halogènes tels que le chlore et le brome, des groupes cyano, un groupe carbamoyle ou sulfamoyle qui peut lui-même être substitué par un ou deux groupes alkyle en C₁-C₄, les groupes (alcoxy en C₁-C₄)-carbonyle ou phényle.
  3. Encres électrophotographiques selon la revendication 1, caractérisées en ce que
    R¹ = R².
  4. Encres électrophotographiques selon la revendication 1, caractérisées en ce que, outre l'additif renforçant la charge cationique, elles contiennent des particules de résines et de pigments.
EP89121373A 1988-12-01 1989-11-18 Toners électrophotographiques Expired - Lifetime EP0371360B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3840488A DE3840488A1 (de) 1988-12-01 1988-12-01 Elektrophotographische toner
DE3840488 1988-12-01

Publications (3)

Publication Number Publication Date
EP0371360A2 EP0371360A2 (fr) 1990-06-06
EP0371360A3 EP0371360A3 (en) 1990-11-07
EP0371360B1 true EP0371360B1 (fr) 1993-03-31

Family

ID=6368236

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89121373A Expired - Lifetime EP0371360B1 (fr) 1988-12-01 1989-11-18 Toners électrophotographiques

Country Status (5)

Country Link
US (1) US4997740A (fr)
EP (1) EP0371360B1 (fr)
JP (1) JPH02188763A (fr)
CA (1) CA2004107A1 (fr)
DE (2) DE3840488A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3935858A1 (de) * 1989-10-27 1991-05-02 Bayer Ag Verfahren zur herstellung von pigmenten auf isoindolbasis
JPH05289407A (ja) * 1992-04-09 1993-11-05 Tomoegawa Paper Co Ltd 正帯電性カラー用現像剤
US5559247A (en) * 1994-04-26 1996-09-24 Mitsui Toatsu Chemicals, Inc. Carboxylate and heat-sensitive recording material using same
JP3720092B2 (ja) * 1995-09-06 2005-11-24 保土谷化学工業株式会社 静電荷像現像用トナー
WO1998031667A1 (fr) * 1997-01-16 1998-07-23 Ciba Specialty Chemicals Holding Inc. Amino-iminoisoindolenine benzene sulfonates, procede servant a preparer des sels de nitrate et de benzene sulfonate de derives d'amino-aminoisoindolenine

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2752346A (en) * 1949-08-25 1956-06-26 Bayer Ag Process for production of isoindolenine derivatives
NL102119C (fr) * 1949-08-25 1900-01-01
DD207908A1 (de) * 1981-09-24 1984-03-21 Wolfgang Klar Verfahren zur grosstechnischen herstellung von 1-amino-3-imino-iso-indolenin-nitrat (i-nitrat)
JPS61156137A (ja) * 1984-12-28 1986-07-15 Canon Inc 静電荷像現像トナ−
JPS61258268A (ja) * 1985-05-13 1986-11-15 Canon Inc 静電荷像現像用電荷付与材
JPS61259265A (ja) * 1985-05-14 1986-11-17 Canon Inc 静電荷像現像用電荷付与材
JPS63201665A (ja) * 1987-02-18 1988-08-19 Ricoh Co Ltd 静電荷像現像用トナ−
JPH01259387A (ja) * 1988-04-11 1989-10-17 Ricoh Co Ltd 摩擦帯電付与部材
DE3821199A1 (de) * 1988-06-23 1989-12-28 Basf Ag Elektrostatischer toner

Also Published As

Publication number Publication date
DE58903960D1 (en) 1993-05-06
DE3840488A1 (de) 1990-06-07
JPH02188763A (ja) 1990-07-24
US4997740A (en) 1991-03-05
EP0371360A2 (fr) 1990-06-06
CA2004107A1 (fr) 1990-06-01
EP0371360A3 (en) 1990-11-07

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