EP0233544B1 - Toner électrophotographique - Google Patents

Toner électrophotographique Download PDF

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

Definitions

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

Landscapes

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

Claims (5)

  1. Toners électrophotographiques qui contiennent un additif renforçant la charge cationique, de formule générale
    Figure imgb0050
     dans laquelle
    A   est un groupe alkylène en C₁ à C₅ ou -C₆H₄-CH₂-(m ou p),
    m   a la valeur 0 ou 1
    n   a la valeur 1 ou 2
    Figure imgb0051
    R³   est un groupe alkyle en C₁ à C₁₈, carbamoyl-(alkyle en C₁ ou C₂), (alkoxy en C₁ à C₄)-carbonyl-(alkyle en C₁ ou C₂), benzyle, cyclohexyle ou allyle,
    R⁴   est un groupe alkyle en C₁ à C₄ ou une liaison simple se rattachant à D,
    R⁵   est un groupe alkyle en C₁ à C₄,
    D   est un groupe -CH₂, -CH₂-CO-, -CH₂-CO-NH- ou -CH₂-CO-NH-CH₂-
    W   est un groupe
    Figure imgb0052
     -CO-
    ou une liaison simple,
    Z   représente -CH₂-,
    Figure imgb0053
     -O-, -S-, -SO₂-
    ou une liaison simple et
    An⊖   est un anion.
  2. Toners électrophotographiques suivant la revendication 1, caractérisés en ce qu'ils contiennent un additif renforçant la charge cationique, de formule générale
    Figure imgb0054
     dans laquelle
    A¹   est un groupe alkylène en C₂ à C₅,
    Figure imgb0055
    R⁶   est un groupe alkyle en C₁ à C₁₆, carbamoylméthyle ou benzyle,
    R⁷   est un groupe méthyle ou éthyle ou une liaison simple se rattachant à D,
    R⁸   est un groupe méthyle ou éthyle,
    W¹   représente
    Figure imgb0056
    Z¹   représente -CH₂-,
    Figure imgb0057
     -O- ou -SO₂- et
    X⊖   est un anion, et
    D, m et n   ont la définition indiquée dans la revendication 1.
  3. Toners électrophotographiques suivant la revendication 1, caractérisés en ce qu'ils contiennent des particules de résine et de pigment en plus de l'additif renforçant la charge cationique.
  4. Utilisation de composés de formule suivant la revendication 1, comme additifs renforçant la charge positive dans des toners électrophotographiques.
  5. Imides d'acides naphtaliques de formule générale
    Figure imgb0058
     dans laquelle
    A¹   est un groupe alkylène en C₂ à C₅,
    Figure imgb0059
    R⁶   est un groupe alkyle en C₁ à C₁₆, carbamoylméthyle ou benzyle,
    R⁷   est un groupe méthyle ou éthyle ou une liaison simple se rattachant à D,
    R⁸   est un groupe méthyle ou éthyle,
    W¹   représente
    Figure imgb0060
    Z¹   représente -CH₂-,
    Figure imgb0061
     -O- ou -SO₂- et
    X⊖   est un groupe benzène-sulfonate éventuellement substitué par Cl ou par un radical alkyle en C₁ à C₁₂, un groupe (alkyle en C₅ à C₁₈)-sulfonate ou un sel d'un acide (alkyle en C₅ à C₁₈)-carboxylique ou un sel d'un produit de condensation du formaldéhyde et d'acides arylsulfoniques et/ou le cas échéant de 4,4'-dihydroxydiphénylsulfone sulfonée, et
    D, m et n   ont la définition indiquée dans la revendication 1.
EP87101463A 1986-02-15 1987-02-03 Toner électrophotographique Expired - Lifetime EP0233544B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863604827 DE3604827A1 (de) 1986-02-15 1986-02-15 Elektrophotographische toner
DE3604827 1986-02-15

Publications (3)

Publication Number Publication Date
EP0233544A2 EP0233544A2 (fr) 1987-08-26
EP0233544A3 EP0233544A3 (en) 1990-04-04
EP0233544B1 true EP0233544B1 (fr) 1993-09-08

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Family Applications (1)

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EP87101463A Expired - Lifetime EP0233544B1 (fr) 1986-02-15 1987-02-03 Toner électrophotographique

Country Status (4)

Country Link
US (2) US4812379A (fr)
EP (1) EP0233544B1 (fr)
JP (1) JPS62192755A (fr)
DE (2) DE3604827A1 (fr)

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3738948A1 (de) * 1987-11-17 1989-05-24 Bayer Ag Farblose salze von heteropolysaeuren und kationischen aromatischen imiden als ladungskontrollsubstanzen in tonern
JPH0814721B2 (ja) * 1988-02-09 1996-02-14 株式会社巴川製紙所 正帯電性カラートナー
DE3828193A1 (de) * 1988-08-19 1990-02-22 Bayer Ag Elektrophotographische toner
DE68915431T2 (de) * 1989-03-24 1994-11-17 Agfa Gevaert Nv Teilchenförmiges Tonermaterial.
US5086059A (en) * 1990-06-07 1992-02-04 Du Pont Merck Pharmaceutical Company Bis-naphthalimides as anticancer agents
DE4106122A1 (de) * 1991-02-27 1992-09-03 Bayer Ag Neue naphthalimide, diese enthaltende toner und die verwendung der neuen naphthalimide als additive fuer toner
US5329048A (en) * 1991-03-27 1994-07-12 The Dupont Merck Pharmaceutical Company Process of preparing tetraamino intermediates
US5206250A (en) * 1991-03-27 1993-04-27 Du Pont Merck Pharmaceutical Company Bis-naphthalimides containing amide and thioamide linkers as anticancer agents
US5162188A (en) * 1991-07-18 1992-11-10 Eastman Kodak Company Toners and developers containing amide-containing quaternary ammonium salts as charge control agents
ES2088661T3 (es) * 1991-12-11 1996-08-16 Du Pont Merck Pharma Bis-naftalimidas fuertemente solubles en agua utiles como agentes anti-cancerigenos.
US5376664A (en) * 1992-07-27 1994-12-27 The Du Pont Merck Pharmaceutical Company Unsymmetrical mono-3-nitro bis-naphthalimides as anticancer agents
DE4232739A1 (de) * 1992-09-30 1994-03-31 Knoll Ag Neue asymmetrisch substituierte bis-Naphthalimide
DE4237661A1 (de) * 1992-11-07 1994-05-11 Basf Ag Elektrostatische Toner, enthaltend amphiphile Flüssigkristalle
US5359070A (en) * 1993-02-11 1994-10-25 The Du Pont Merck Pharmaceutical Company Unsymmetrical bis-imides as anticancer agents
US5416089A (en) * 1993-06-24 1995-05-16 The Du Pont Merck Pharmaceutical Company Polycyclic and heterocyclic chromophores for bis-imide tumoricidals
US5358815A (en) * 1993-08-31 1994-10-25 Eastman Kodak Company Toner compositions containing negative charge-controlling additive
US5358814A (en) * 1993-08-31 1994-10-25 Eastman Kodak Company Toner compositions containing as a negative charge-controlling agent a mixture of ortho-benzoic sulfimide and para-anisic acid
US5332637A (en) * 1993-08-31 1994-07-26 Eastman Kodak Company Electrostatographic dry toner and developer compositions with hydroxyphthalimide
US5358818A (en) * 1993-08-31 1994-10-25 Eastman Kodak Company Ortho-benzoic sulfimide as charge-controlling agent
US5358817A (en) * 1993-08-31 1994-10-25 Eastman Kodak Company Toner compositions containing as a negative charge-controlling agent the calcium salt of ortho-benzoic sulfimide
US5358816A (en) * 1993-08-31 1994-10-25 Eastman Kodak Company Zinc salt of ortho-benzoic sulfimide as negative charge-controlling additive for toner and developer compositions
US5561042A (en) * 1994-07-22 1996-10-01 Cancer Therapy And Research Center Diamine platinum naphthalimide complexes as antitumor agents
US5604095A (en) * 1994-07-22 1997-02-18 Cancer Therapy & Research Center Unsymmetrically linked bisnaphthalimides as antitumor agents
US5641782A (en) * 1995-02-16 1997-06-24 The Dupont Merck Pharmaceutical Company 3-aromatic and 3-heteroaromatic substituted bisnaphthalimides
EP3338756B1 (fr) 2016-12-21 2020-02-26 VOCO GmbH Ciment au verre ionomère stable au stockage, modifié par une résine

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3880859A (en) * 1971-06-03 1975-04-29 Basf Ag N-substituted-4-alkoxynaphthalimides
CH560235A5 (fr) * 1972-02-18 1975-03-27 Ciba Geigy Ag
US3953451A (en) * 1972-06-28 1976-04-27 Basf Aktiengesellschaft Compounds of the naphthalimide series
US3940398A (en) * 1975-01-23 1976-02-24 E. R. Squibb & Sons, Inc. 2-[[4-(Azine or diazine or triazine)-1-piperazinyl]alkyl]-1H-benz[de]isoquinoline-1,3(2H)-diones
US4007191A (en) * 1975-10-14 1977-02-08 E. R. Squibb & Sons, Inc. 2-(Piperidinyl or tetrahydropyridinyl)-alkyl)-2,3-dihydro-3-hydroxy-1H-benz(DE)isoquinolin-1-ones
US4139532A (en) * 1976-05-14 1979-02-13 Basf Aktiengesellschaft N-Acylaminonaphthalimides
ES459497A1 (es) * 1977-06-04 1978-04-16 Made Labor Sa Un metodo para la preparacion industrial de naftalimidas y sus derivados.
DE2753152A1 (de) * 1977-11-29 1979-06-07 Basf Ag Naphthalimidderivate
DE2944867A1 (de) * 1979-11-07 1981-05-27 Hoechst Ag, 6000 Frankfurt Kationische verbindungen der naphthalimid-reihe, verfahren zu deren herstellung und deren verwendung
US4508900A (en) * 1980-11-03 1985-04-02 Hoechst Aktiengesellschaft Cationic compounds of the naphthalimide series, process for their preparation and their use
JPS59114546A (ja) * 1982-12-22 1984-07-02 Nippon Kayaku Co Ltd 電子写真印刷用トナ−
US4614820A (en) * 1983-04-01 1986-09-30 Warner-Lambert Co. 3,6-disubstituted-1,8-naphthalimides
US4499266A (en) * 1983-04-01 1985-02-12 Warner-Lambert Company 3,6-Dinitro-1,8-naphthalimides
DE3413833A1 (de) * 1983-04-12 1984-10-18 Canon K.K., Tokio/Tokyo Entwicklungsverfahren und entwickler dafuer
JPH0625874B2 (ja) * 1983-04-23 1994-04-06 キヤノン株式会社 静電荷像現像用摩擦帯電性トナー
US4493883A (en) * 1984-02-21 1985-01-15 Xerox Corporation Electrophotographic toner compositions containing novel imide charge control _additives
US4665071A (en) * 1984-02-21 1987-05-12 Warner-Lambert Company 3,6-disubstituted-1,8-naphthalimides and methods for their production and use
DE3535496A1 (de) * 1985-10-04 1987-04-16 Bayer Ag Verfahren zur fluoreszenzloeschung und neue kationische naphthalin-peri-dicarbonsaeureimid-derivate
US4686166A (en) * 1985-10-07 1987-08-11 Hitachi Chemical Co. Electrophoto toner comprising imido group monomer unit in polymer
US4782064A (en) * 1986-07-21 1988-11-01 American Cyanamid Co. 2-heteroaryl-alkyl-1H-benz[de]-isoquinoline-1,3(2H)-diones

Also Published As

Publication number Publication date
JPH0431584B2 (fr) 1992-05-26
EP0233544A2 (fr) 1987-08-26
JPS62192755A (ja) 1987-08-24
US4841052A (en) 1989-06-20
US4812379A (en) 1989-03-14
DE3787297D1 (de) 1993-10-14
DE3604827A1 (de) 1987-08-20
EP0233544A3 (en) 1990-04-04

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