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EP0680627B1 - Toner electrostatique renfermant des derives d'acide aminodiacetique - Google Patents

Toner electrostatique renfermant des derives d'acide aminodiacetique Download PDF

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Publication number
EP0680627B1
EP0680627B1 EP94926166A EP94926166A EP0680627B1 EP 0680627 B1 EP0680627 B1 EP 0680627B1 EP 94926166 A EP94926166 A EP 94926166A EP 94926166 A EP94926166 A EP 94926166A EP 0680627 B1 EP0680627 B1 EP 0680627B1
Authority
EP
European Patent Office
Prior art keywords
formula
alkyl
compound
substituted
toner
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
EP94926166A
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German (de)
English (en)
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EP0680627A1 (fr
Inventor
Alfred Oftring
Juergen Schneider
Rainer Dyllick-Brenzinger
Karin Heidrun Beck
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BASF SE
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BASF SE
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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
    • 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
    • G03G9/0975—Organic compounds anionic
    • 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

  • Latent electrostatic image recordings are developed by inductively depositing the toner on the electrostatic image.
  • the charge stabilizers stabilize the electrostatic charge on the toner. This makes the picture more vivid and sharper.
  • electrostatic toners which have N-acylated 3-aminopropionic acid derivatives as charge stabilizers.
  • electrostatic toners which have metal chelates of ethylenediamine-tetraacetic acid as charge stabilizers.
  • US-A-3 974 496 discloses light-sensitive photographic materials which contain, as light-sensitive material, silver salts of iminodiacetic acid and special derivatives thereof.
  • the object of the present invention was therefore to provide new electrostatic toners which have charge stabilizers which have advantageous performance properties.
  • substituted phenyl groups occur in the above formula I, they generally have 1 to 3 substituents.
  • R are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, isooctyl, Nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, 3,5,5,7-tetramethylnonyl, isotridecyl (the above names isooctyl, isononyl, isodecyl and isotridecyl are trivial names and come from the alcohols obtained after oxo synthesis - cf.
  • M ⁇ means the equivalent of a cation. It is either a proton or is derived from ammonium or metal ions.
  • Ammonium ions in the sense of the invention are understood to mean unsubstituted or substituted ammonium cations.
  • Substituted ammonium cations are, for example, monoalkyl, dialkyl, trialkyl, tetraalkyl or benzyltrialkylammonium cations or those cations which differ from nitrogen-containing five or derive six-membered saturated heterocycles, such as pyrrolidinium, piperidinium, morpholinium, piperazinium or N-alkylpiperazinium cations or their N-monoalkyl or N, N-dialkyl-substituted products.
  • Alkyl is generally to be understood as straight-chain or branched C 1 -C 20 -alkyl which can be substituted by hydroxyl groups and / or interrupted by ether oxygen atoms.
  • Suitable metal ions derive e.g. from metals of group IA, IIA, IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB or VIII of the Periodic Table of the Elements.
  • electrostatic toners containing a compound of formula I in which RC 1 -C 18 alkyl, benzyl, which is optionally substituted by C 1 -C 4 alkyl or hydroxy, or phenyl optionally substituted by carboxyl.
  • Electrostatic toners containing a compound of the formula I in which RC 4 -C 16 -alkyl, benzyl which is substituted by C 1 -C 4 -alkyl and hydroxy, or phenyl substituted by carboxyl are particularly preferred.
  • Electrostatic toners containing a compound of the formula I in which RC 6 denotes C 12 -alkyl, 2-hydroxy-3,5-di-tert-butylbenzyl or 2-carboxylphenyl are very particularly preferred.
  • the iminodiacetic acid derivatives of the formula I are generally compounds which are known or can be obtained by methods known per se.
  • iminodiacetic acid esters of the formula II in the YC 1 -C 4 alkyl with a compound of formula III RX (III), in which R has the abovementioned meaning and X denotes chlorine, bromine or iodine, alkylate and saponify the resulting alkylated ester (J. General Chem. USSR, volume 44, pages 574 to 577, 1974).
  • Those iminodiacetic acid derivatives which contain an ortho-standing phenolate structure in the general formula can be prepared from commercially available phenols or phenol derivatives by a one-step Mannich reaction. In particular, they can be synthesized using the method described in Helv. Chim. Acta 35, 1785 (1952), or Keihei Ueno, Ed., "Chemistry of EDTA Complexane” pages 99-105, 1977. This synthesis is explained using example H1.
  • the synthesis of the alkyl and aryliminodiacetic acids can also be carried out by the known reaction of the commercially available amine starting component with halocarboxylic acids.
  • the synthesis of anthranilic acid diacetic acid can be carried out by reacting anthranilic acid with chloroacetic acid in an aqueous medium (Chem. Abstracts, volume 88, 89303p, 1978, or EP-A-520 547).
  • the free acid is isolated in a manner known per se, e.g. by acidifying the solution of a readily soluble salt down to the isoelectric point of the amino acid.
  • the synthesis of the generally moderately to poorly water soluble metal salts with divalent or higher cations is carried out by reacting the free acid or soluble salts of the amino acids with salts of the desired cation.
  • the end products generally crystallize out of the solution and can thus be isolated and dried.
  • Another possibility is to react the free acids with the metal oxides or hydroxides of the desired cations. Further details for the synthesis of these salts are given in the examples.
  • the proportion of the compounds of the formula I in the electrostatic toners is generally 0.01 to 10% by weight, based on the weight of the toner.
  • the polymeric binders contained in the new electrostatic toners are known per se. They are generally thermoplastic and have a softening point of 40 to 200 ° C, preferably 50 to 130 ° C and in particular 65 to 115 ° C.
  • Examples of polymeric binders are polystyrene, copolymers of styrene with an acrylate or methacrylate, copolymers of styrene with butadiene and / or acrylonitrile, polyacrylates, 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, epoxy resins, polyamides or polyurethanes.
  • the toners according to the invention can contain colorants, magnetically attractable material, waxes and flow agents in known amounts.
  • the colorants can be organic dyes or pigments such as nigrosine, aniline blue, 2,9-dimethylquinacridone, C.I. Disperse Red 15 (C.I. 6010), 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) or C.I. Solvent Yellow 16 (C.I. 12 700) or inorganic pigments such as carbon black, red lead, yellow lead oxide or chrome yellow. Generally, the amount of the colorant present in the toner does not exceed 15% by weight based on the weight of the toner.
  • the magnetically attractable material can be, for example, iron, nickel, chromium oxide, iron oxide or a ferrite of the formula MeFe204, in which Me is a divalent metal, e.g. Iron, cobalt, zinc, nickel or manganese.
  • Me is a divalent metal, e.g. Iron, cobalt, zinc, nickel or manganese.
  • the toners according to the invention are produced by customary processes, for example by mixing the constituents in a kneader and then pulverizing them or by melting the polymeric binder or a mixture of the polymeric binders, then finely dividing one or more compounds of the formula I and 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 (usually 0.1 to 50 ⁇ m). It is also possible to dissolve the polymeric binder and the charge stabilizer in a common solvent and to add the other additives to the solution. The solution can be used as a liquid toner.
  • the liquid can also be spray-dried in a manner known per se, the solvents evaporated or the liquid freeze-dried and the solid residue ground into particles of the desired particle size.
  • toner preparation can then be used in a xerographic imaging system, for example according to US-A-4,265,990.
  • the compounds of formula I mentioned above are advantageous charge stabilizers. They generally satisfy the application profile initially mentioned and are particularly distinguished by the fact that, when added to a toner preparation, they give it a favorable electrostatic charging profile, i.e. the toners can be quickly and highly charged.
  • the charge stabilizers to be used according to the invention furthermore ensure that the charge is kept constant at a high level.
  • Example H4 0.2 g of the compound from Example H4 were introduced into a solution of 10 g of an uncrosslinked styrene / butyl acrylate resin in 100 ml of p-xylene at room temperature and then freeze-dried and ground. Toner particles with an average particle size of 50 ⁇ m were produced by screening.
  • Example H2 0.2 g of the compound from Example H2 were introduced into a solution of 10 g of a linear polyester resin in 100 ml of p-xylene at room temperature and then freeze-dried and ground. Toner particles with an average particle size of 50 ⁇ m were produced by screening.
  • Example H3 0.2 g of the compound from Example H3 were introduced into a solution of 10 g of a linear polyester resin in 100 ml of p-xylene at room temperature and then freeze-dried and ground. Toner particles with an average particle size of 50 ⁇ m were produced by screening.
  • Example H4 0.2 g of the compound from Example H4 were introduced into a solution of 10 g of a linear polyester resin in 100 ml of p-xylene at room temperature and then freeze-dried and ground. Toner particles with an average particle size of 50 ⁇ m were produced by screening.
  • Example H5 0.2 g of the compound from Example H5 was introduced into a solution of 10 g of a linear polyester resin in 100 ml of p-xylene at room temperature and then freeze-dried and ground. Toner particles with an average particle size of 50 ⁇ m were produced by screening.
  • Example H6 0.2 g of the compound from Example H6 were introduced into a solution of 10 g of a linear polyester resin in 100 ml of p-xylene at room temperature and then freeze-dried and ground. Toner particles with an average particle size of 50 ⁇ m were produced by screening.
  • a developer 99% by weight of a steel carrier, which had an average particle size of 100 ⁇ m, was precisely weighed in with 1% by weight of the toner and activated on a roller stand for a period specified below. The electrostatic charge of the developer was then determined. About 5 g of the activated developer were filled into a hard-blow-off cell, which was electrically connected to an electrometer, in a commercially available q / m meter (Epping GmbH, Neufahrn).
  • the mesh sizes of the sieves used in the measuring cell were 63 ⁇ m for the examples.
  • the toner was almost completely removed from the carrier particles by a strong air flow (approx. 4,000 cm 3 / min) and simultaneous suction, the latter remaining in the measuring cell.
  • the charge on the carrier was registered on the electrometer. It corresponded to the amount of charging of the toner particles, but with the opposite sign. The amount of q with the opposite sign was therefore used to calculate the q / m value.
  • the mass of blown-off toner was determined by weighing the measuring cell back and the electrostatic charge q / m was calculated therefrom.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Developing Agents For Electrophotography (AREA)

Abstract

Toner électrostatique renfermant un liant polymère et, comme stabilisateur de charge, un composé ayant la formule (I), dans laquelle M+ désigne l'équivalent d'un cation, et R désigne un alkyle en C¿1?-C18 éventuellement substitué ou un phényle éventuellement substitué, et utilisation des composés précités comme stabilisateurs de charge dans des toners électrostatiques.

Claims (6)

  1. Toner électrostatique contenant un liant polymère et, en tant que stabilisateur de charges, un composé de formule I
    Figure imgb0007
     dans laquelle
    M⊕ signifie l'équivalent d'un cation et
    R signifie un groupement alkyle en C1-C21, qui est éventuellement substitué par un groupement carboxyle ou phényle, qui peut être substitué par un groupement alkyle en C1-C10, un groupement hydroxy ou un reste de formule L-N(CH2-COO⊖M⊕)2 où L est mis pour un groupement alkylène en C1-C4 et M⊕ prend la signification susmentionnée, et qui peut être interrompu par 1 à 4 atomes d'oxygène en fonction éther, par 1 à 4 groupements imino ou (alkyl en C1-C4)imino ou par le reste de formule N-CH2-COO⊖M⊕ où M⊕ prend la signification susmentionnée, ou un groupement phényle, qui est éventuellement substitué par un groupement carboxyle,
    étant spécifié que, lorsque R représente un groupement alkyle contenant un ou plusieurs hétéroatomes, on trouve au moins 5 atomes de carbone liés entre eux dans le reste R.
  2. Toner électrostatique selon la revendication 1, contenant un composé de formule I, dans lequel M⊕ représente un proton ou dérive d'un ion ammonium ou métallique.
  3. Toner électrostatique selon la revendication 1, contenant un composé de formule I, dans lequel R représente un groupement alkyle en C1-C18, benzyle, qui est éventuellement substitué par un groupement alkyle en C1-C4 ou hydroxy, ou bien un groupement phényle éventuellement substitué par un groupement carboxyle.
  4. Toner électrostatique selon la revendication 1, contenant un composé de formule I, dans lequel R représente un groupement alkyle en C4-C16, un groupement benzyle, qui est substitué par un groupement alkyle en C1-C4 ou hydroxy, ou bien un groupement phényle substitué par un groupement carboxyle.
  5. Toner électrostatique selon la revendication 1, contenant 0,01-10 % en poids, par rapport au poids du toner, d'un composé de formule I.
  6. Utilisation de composés de formule I selon la revendication 1 en tant que stabilisateurs de charges dans des toners électrostatiques.
EP94926166A 1993-08-13 1994-08-09 Toner electrostatique renfermant des derives d'acide aminodiacetique Expired - Lifetime EP0680627B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4327179A DE4327179A1 (de) 1993-08-13 1993-08-13 Elektrostatische Toner, enthaltend Aminodiessigsäurederivate
DE4327179 1993-08-13
PCT/EP1994/002635 WO1995005624A1 (fr) 1993-08-13 1994-08-09 Toner electrostatique renfermant des derives d'acide aminodiacetique

Publications (2)

Publication Number Publication Date
EP0680627A1 EP0680627A1 (fr) 1995-11-08
EP0680627B1 true EP0680627B1 (fr) 1997-10-29

Family

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EP94926166A Expired - Lifetime EP0680627B1 (fr) 1993-08-13 1994-08-09 Toner electrostatique renfermant des derives d'acide aminodiacetique

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Country Link
US (1) US5663028A (fr)
EP (1) EP0680627B1 (fr)
JP (1) JPH09501777A (fr)
DE (2) DE4327179A1 (fr)
WO (1) WO1995005624A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0757294A1 (fr) * 1995-07-28 1997-02-05 Eastman Kodak Company Compositions de toners contenant des liants polymériques réticulés et des savons de N-alkyl-sarcosine
JP4736834B2 (ja) * 2006-02-10 2011-07-27 コニカミノルタビジネステクノロジーズ株式会社 静電荷像現像用トナー

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1668927C3 (de) * 1968-02-02 1978-03-02 Hoechst Ag, 6000 Frankfurt Verfahren zur Herstellung von Alkalisalzen von Aminopolycarbonsäuren
US3733355A (en) * 1970-07-28 1973-05-15 Hooker Chemical Corp Production of nitrilotriacetic acid and the analogs therefor
JPS511434B2 (fr) * 1972-05-15 1976-01-17
US3794496A (en) * 1972-05-26 1974-02-26 Itek Corp Photographic processes and imaging media therefor
US4082748A (en) * 1976-08-27 1978-04-04 The Dow Chemical Company Process for production of oxazine diones
US4265990A (en) * 1977-05-04 1981-05-05 Xerox Corporation Imaging system with a diamine charge transport material in a polycarbonate resin
JPS58211159A (ja) * 1982-06-02 1983-12-08 Konishiroku Photo Ind Co Ltd 磁性トナ−
JPS6021056A (ja) * 1983-07-14 1985-02-02 Fuji Photo Film Co Ltd 静電荷像用液体現像剤
GB2148287B (en) * 1983-10-05 1987-04-15 Nippon Catalytic Chem Ind Preparation of aminocarboxylic acid salts from amino alcohols
JPH0623864B2 (ja) * 1984-08-20 1994-03-30 富士写真フイルム株式会社 荷電調節剤の製造方法
US4673631A (en) * 1984-12-15 1987-06-16 Canon Kabushiki Kaisha Toner, charge-imparting material and composition containing metal complex
JPH0616181B2 (ja) * 1985-04-30 1994-03-02 キヤノン株式会社 トナ−
EP0520457B1 (fr) * 1991-06-26 1998-04-22 Fuji Photo Film Co., Ltd. Composition de traitement photographique comprenant des agents complexants

Also Published As

Publication number Publication date
EP0680627A1 (fr) 1995-11-08
WO1995005624A1 (fr) 1995-02-23
DE59404476D1 (de) 1997-12-04
JPH09501777A (ja) 1997-02-18
DE4327179A1 (de) 1995-02-16
US5663028A (en) 1997-09-02

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