WO2013129015A1 - Agent de contrôle de charge et toner l'utilisant - Google Patents

Agent de contrôle de charge et toner l'utilisant Download PDF

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Publication number
WO2013129015A1
WO2013129015A1 PCT/JP2013/052073 JP2013052073W WO2013129015A1 WO 2013129015 A1 WO2013129015 A1 WO 2013129015A1 JP 2013052073 W JP2013052073 W JP 2013052073W WO 2013129015 A1 WO2013129015 A1 WO 2013129015A1
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group
carbon atoms
substituted
substituent
atom
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PCT/JP2013/052073
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English (en)
Japanese (ja)
Inventor
育夫 木村
一徳 辻
雅也 東條
昌史 浅貝
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保土谷化学工業株式会社
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Priority to JP2013523427A priority Critical patent/JP5329010B1/ja
Publication of WO2013129015A1 publication Critical patent/WO2013129015A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C07D215/50—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
    • C07D217/22—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the nitrogen-containing ring
    • C07D217/26—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • 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

  • the present invention relates to a charge control agent used in an image forming apparatus for developing an electrostatic latent image in fields such as electrophotography and electrostatic recording, and a negatively chargeable toner containing the charge control agent.
  • an electrostatic latent image is formed on an inorganic photoreceptor such as selenium, selenium alloy, cadmium sulfide, amorphous silicon, or an organic photoreceptor using a charge generator and a charge transport agent. Is developed with toner, transferred onto paper or plastic film, and fixed to obtain a visible image.
  • an inorganic photoreceptor such as selenium, selenium alloy, cadmium sulfide, amorphous silicon, or an organic photoreceptor using a charge generator and a charge transport agent.
  • the photosensitive member has positive and negative charging characteristics depending on the structure.
  • development is performed with a reverse sign charging toner, while on the other hand, the printed part is discharged to perform reverse development.
  • development is performed with a toner having the same sign.
  • the toner is composed of a binder resin, a colorant, and other additives.
  • a charge control agent is generally added. By adding the charge control agent, the toner characteristics are greatly improved.
  • nigrosine dyes, azine dyes, copper phthalocyanine pigments, quaternary ammonium salts, and polymers having quaternary ammonium salts in the side chain are known.
  • Known negative triboelectric charge control agents include metal complex salts of monoazo dyes, metal complex salts of salicylic acid, naphthoic acid or dicarboxylic acid, copper phthalocyanine pigments, resins containing acid components, and the like.
  • a light-colored, preferably colorless, charge control agent that does not affect the hue is indispensable.
  • These light-colored or colorless charge control agents include metal complex salts of hydroxybenzoic acid derivatives (see, for example, Patent Documents 1 to 3) and aromatic dicarboxylic acid metal salt compounds (for example, Patent Document 4) for negatively chargeable toners.
  • Metal complex salt compounds of anthranilic acid derivatives for example, see Patent Documents 5 to 6
  • organoboron compounds for example, see Patent Documents 7 to 8
  • biphenol compounds for example, see Patent Document 9
  • calix n
  • allene compounds see, for example, Patent Documents 10 to 15
  • cyclic phenol sulfides see, for example, Patent Documents 16 to 18
  • quaternary ammonium salt compounds for example, see Patent Documents 19 to 21 for positively chargeable toners.
  • charge control agents are complexes or salts made of heavy metals such as chromium, which are problems regarding waste regulations and are not necessarily safe.
  • the charge imparting effect required today is low and the charge rising speed is insufficient, so that the initial copy image lacks clarity, the quality of the copy image during continuous copying tends to fluctuate,
  • a charge control agent that has a high charge imparting effect and can be applied to polymerized toners has been desired.
  • the object of the present invention is to provide a safe charge control agent having a high charge amount and no problem with waste regulations. It is another object of the present invention to provide a negatively chargeable toner for developing an electrostatic image and a negatively chargeable polymerized toner having high charging performance using the charge control agent.
  • the present invention has been obtained as a result of intensive studies to achieve the above object, and has the following gist.
  • the present invention provides a charge control agent containing one or more pyridinedicarboxylic acid derivatives represented by the general formula (1) as an active ingredient.
  • R 1 , R 2 and R 3 may be the same or different from each other, and are a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, cyano group, A trifluoromethyl group, a nitro group, an optionally substituted linear or branched alkyl group having 1 to 8 carbon atoms, and an optionally substituted carbon atom having 5 to 10 carbon atoms A cycloalkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a straight chain having 1 to 8 carbon atoms which may have a substituent, or A branched alkyloxy group, an optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, substituted or Unsubstit
  • R 1 , R 2 and R 3 may be bonded to each other at adjacent groups to form a ring.
  • the pyridinedicarboxylic acid derivative represented by the general formula (1) may be a compound represented by the following general formula (1A).
  • R 1 , R 2 and R 3 may be the same or different from each other, and are a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, cyano group, A trifluoromethyl group, a nitro group, an optionally substituted linear or branched alkyl group having 1 to 8 carbon atoms, and an optionally substituted carbon atom having 5 to 10 carbon atoms
  • R 1 , R 2 and R 3 may be bonded to each other at adjacent groups to form a ring.
  • the pyridinedicarboxylic acid derivative represented by the general formula (1) may be a compound represented by the following general formula (1A-1).
  • R 1 , R 2 and R 3 may be the same or different from each other, and are a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, cyano Group, a trifluoromethyl group, a nitro group, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, and a carbon atom having 5 to 5 carbon atoms which may have a substituent 10 cycloalkyl groups, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and a linear chain having 1 to 8 carbon atoms which may have a substituent A branched or branched alkyloxy group, an optionally substituted cycloalkyloxy group having 5 to
  • R 1 , R 2 and R 3 , R 8 , R 9 , R 10 , R 11 and R 12 , or R 13 , R 14 , R 15 , R 16 and R 17 are mutually adjacent groups. It may combine to form a ring.
  • R 6 and R 7 may have a substituent. It may be a cycloalkyl group having 5 to 10 carbon atoms.
  • the present invention also provides a toner containing a charge control agent containing one or more pyridinedicarboxylic acid derivatives represented by the above general formula (1) as active ingredients, a colorant, and a binder resin.
  • a charge control agent containing one or more pyridinedicarboxylic acid derivatives represented by the above general formula (1) as active ingredients, a colorant, and a binder resin.
  • the present invention further provides a polymerization comprising a charge control agent containing one or more pyridinedicarboxylic acid derivatives represented by the general formula (1) as an active ingredient, a colorant, and a binder resin.
  • a charge control agent containing one or more pyridinedicarboxylic acid derivatives represented by the general formula (1) as an active ingredient, a colorant, and a binder resin.
  • toner Provide toner.
  • the charge control agent containing one or more pyridinedicarboxylic acid derivatives represented by the above general formula (1) as an active ingredient has a high charge amount, and is safe and has no problem with waste regulations. Therefore, it can be suitably used for toner charge control. Therefore, the present invention relates to the use of a charge control agent containing one or more pyridinedicarboxylic acid derivatives represented by the above general formula (1) as an active ingredient for charge control of the toner, or the above general formula. It can also be said that the charge control agent containing one or more pyridinedicarboxylic acid derivatives represented by (1) as an active ingredient is applied to toner charge control.
  • the toner may be a polymerized toner.
  • the present invention can also be referred to as a toner charge control method using a charge control agent containing one or more pyridinedicarboxylic acid derivatives represented by the general formula (1) as an active ingredient.
  • the toner may be a polymerized toner.
  • the charge control agent containing one or more pyridinedicarboxylic acid derivatives represented by the general formula (1) as an active ingredient has a higher charge rising speed than conventional charge control agents, and has a high charge. And charging characteristics particularly excellent in stability over time and environmental stability. In addition, it does not contain heavy metals such as chromium, which is a concern for environmental problems, and is excellent in dispersibility and compound stability.
  • the charge control agent according to the present invention is excellent in charge control characteristics, environmental resistance, and durability, and has no fog, image density, dot reproducibility, fine line reproducibility when used for pulverized toner or polymerized toner. Can obtain a good image.
  • the charge control agent is useful for an electrophotographic charge control agent that expresses sufficient triboelectric chargeability in the toner, particularly for a color toner, and further for a polymerized toner.
  • the charge control agent according to the present embodiment contains one or more pyridinedicarboxylic acid derivatives represented by the general formula (1) as an active ingredient.
  • the pyridinedicarboxylic acid derivative represented by the general formula (1) will be described.
  • R 1 , R 2 and R 3 (R 1 to R 3 ) in the general formula (1) “a linear or branched group having 1 to 8 carbon atoms which may have a substituent.
  • alkenyl group “Linear or branched alkyl group having 1 to 8 carbon atoms”, “Cycloalkyl group having 5 to 10 carbon atoms” or “Linear or branched chain having 2 to 6 carbon atoms” in “Alkenyl group”
  • alkenyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n -Hexyl, n-heptyl, isoheptyl Group, n- octyl group, isooctyl group, a cyclopentyl group, a cyclohexyl group, 1-adamantyl, 2-adamantyl, vinyl group, allyl group, etc. may be mentioned. Isopropenyl group
  • a linear or branched alkyl group having 1 to 8 carbon atoms having a substituent represented by R 1 to R 3 in the general formula (1), “5 to 10 carbon atoms having a substituent”
  • Specific examples of the “substituent” in the “cycloalkyl group” or “straight-chain or branched alkenyl group having 2 to 6 carbon atoms” include deuterium atom, trifluoromethyl group, cyano group Group, nitro group, hydroxyl group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group Straight chain having 1 to 8 carbon atoms such as n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-
  • Aryl vinyl group Acyl group such as acetyl group and benzoyl group; Dialkylamino group such as dimethylamino group and diethylamino group; Aromatic hydrocarbon group such as diphenylamino group and dinaphthylamino group Or a disubstituted amino group substituted with a condensed polycyclic aromatic group; a diaralkylamino group such as a dibenzylamino group or a diphenethylamino group; a dipyridylamino group, a dithienylamino group or a dipiperidinylamino group A disubstituted amino group substituted with a heterocyclic group; a dialkenylamino group such as a diallylamino group; an alkyl group, an aromatic hydrocarbon group, a condensed polycyclic aromatic group, an aralkyl group, a heterocyclic group or an alkenyl group; And a group such as
  • a linear or branched alkyloxy group having 1 to 8 carbon atoms which may have a substituent represented by R 1 to R 3 in the general formula (1) or “having a substituent.
  • R 1 ⁇ R 3 is a neighboring groups to each other, a single bond, and bonded to each other through an oxygen atom or a sulfur atom ring May be formed.
  • a linear or branched alkyloxy group having 1 to 8 carbon atoms having a substituent represented by R 1 to R 3 in the general formula (1) or “a carbon atom having 5 to 5 carbon atoms having a substituent”
  • Specific examples of the “substituent” in “10 cycloalkyloxy groups” include deuterium atom, trifluoromethyl group, cyano group, nitro group, hydroxyl group; fluorine atom, chlorine atom, bromine atom, iodine atom, etc.
  • Halogen atom methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group A linear or branched alkyl group having 1 to 8 carbon atoms such as isoheptyl group, n-octyl group, isooctyl group, etc .; methyloxy group, ethyloxy group, pro A linear or branched alkyloxy group having 1 to 8 carbon atoms such as a ruoxy group; an alkenyl group such as an allyl group; an aralkyl group such as a benzyl group, a naphthylmethyl group or a phenethyl group; a phenyloxy group or a toly
  • Dialkylamino group such as dimethylamino group and diethylamino group
  • Diaralkylamino groups such as amino groups and diphenethylamino groups
  • Disubstituted amino groups substituted with heterocyclic groups such as dipyridylamino groups, dithienylamino groups, and dipiperidinylamino groups
  • Dialkenyl groups such as diallylamino groups
  • Examples of the “substituent” in the “substituted aromatic hydrocarbon group”, “substituted heterocyclic group” or “substituted condensed polycyclic aromatic group” represented by R 1 to R 3 in the general formula (1) include Deuterium atom, cyano group, trifluoromethyl group, nitro group, hydroxyl group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyl group, ethyl group, n-propyl group, isopropyl group , N-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group, etc.
  • aryloxy group in the “substituted or unsubstituted aryloxy group” represented by R 1 to R 3 in the general formula (1) include a phenyloxy group, a tolyloxy group, and a biphenylyloxy group.
  • R 1 to R 3 May be bonded to each other through a single bond, oxygen atom or sulfur atom to form a ring.
  • substituted aryloxy group represented by R 1 to R 3 in the general formula (1)
  • substituents in the “substituted aryloxy group” represented by R 1 to R 3 in the general formula (1) include deuterium atom, cyano group, trifluoromethyl group, nitro group, hydroxyl group
  • a linear or branched alkenyl group of 1 to 8 carbon atoms such as a methyloxy group, an ethyloxy group or a propyloxy group; a cyclopentyloxy group, a cyclohexyloxy group or the like;
  • R 1 to R 3 in the general formula (1) are a hydrogen atom, a deuterium atom, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, or a substituent.
  • a cycloalkyl group having 5 to 10 carbon atoms which may have a group is preferable, and a straight chain or branched chain having 1 to 4 carbon atoms which may have a hydrogen atom, a deuterium atom, or a substituent.
  • the alkyl group is more preferably a hydrogen atom or a deuterium atom.
  • a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent represented by R 4 and R 5 in the general formula (1), “having a substituent In the “cycloalkyl group having 5 to 10 carbon atoms” or “the linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent”.
  • Examples of “8 linear or branched alkyl group”, “C5-C10 cycloalkyl group” or “C2-C6 linear or branched alkenyl group” include the above R The groups are the same as those shown for 1 to R 3 , and the substituents that these groups may have are the same as those shown for R 1 to R 3 .
  • Substituted or unsubstituted aromatic hydrocarbon group “substituted or unsubstituted heterocyclic group” or “substituted or unsubstituted condensed polycyclic aromatic” represented by R 4 and R 5 in the general formula (1)
  • the “aromatic hydrocarbon group”, “heterocyclic group” or “condensed polycyclic aromatic group” in the “group” is the same group as those described above for R 1 to R 3 , and these groups Substituents that may have are the same as those described for R 1 to R 3 .
  • R 4 and R 5 in the general formula (1) are a hydrogen atom, a deuterium atom, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, or a substituted group.
  • a cycloalkyl group having 5 to 10 carbon atoms which may have a group is preferable, and a straight chain or branched chain having 1 to 4 carbon atoms which may have a hydrogen atom, a deuterium atom, or a substituent.
  • the alkyl group is more preferably a hydrogen atom or a deuterium atom.
  • Cycloalkyl group having 5 to 10 carbon atoms in “cycloalkyl group having 5 to 10 carbon atoms which may have a substituent” represented by R 6 and R 7 in formula (1) Specific examples thereof include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a 1-adamantyl group, and a 2-adamantyl group.
  • the “fused polycyclic aromatic group” specifically, phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthryl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group And a triphenylenyl group.
  • C6-C10 substituted cycloalkyl group “substituted aromatic hydrocarbon group” or “substituted condensed polycyclic aromatic group represented by R 6 and R 7 in general formula (1)
  • substituted specifically, deuterium atom, trifluoromethyl group, cyano group, nitro group, hydroxyl group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, isoheptyl, n- Straight or branched alkyl group having 1 to 8 carbon atoms such as octyl group, isooctyl group, etc .; carbon atoms
  • Arylalkyloxy groups such as phenethyloxy groups; phenyl groups, biphenylyl groups, terphenylyl groups, naphthyl groups, anthracenyl groups, phenanthryl groups, fluorenyl groups, indenyl groups, pyrenyl groups, perylenyl groups, fluoranthenyl groups, triphenylenyl groups, etc.
  • Aromatic hydrocarbon group or condensed polycyclic aromatic group pyridyl group, furanyl group, pyranyl group, thienyl group, furyl group, pyrrolyl group, pyrrolidinyl group, imidazolyl group, imidazolinyl group, imidazolidinyl group, pyrazolyl group, pyrazolinyl group, Pyrazolidinyl group, pyridazinyl group, pyrazinyl group, piperidinyl group, piperazinyl group, thiolanyl group, thianyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalyl Group, benzimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, carbolin
  • C6-C10 substituted cycloalkyl group “substituted aromatic hydrocarbon group” or “substituted condensed polycyclic aromatic group represented by R 6 and R 7 in general formula (1)
  • R 6 and R 7 in the general formula (1) are preferably a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, or a substituted or unsubstituted aromatic hydrocarbon group. More preferably, R 6 and R 7 are both optionally substituted cycloalkyl groups having 5 to 10 carbon atoms, or both are substituted or unsubstituted aromatic hydrocarbon groups. preferable. Also in this case, R 6 and R 7 may be the same as or different from each other. As an embodiment in which R 6 and R 7 are both substituted or unsubstituted aromatic hydrocarbon groups, R 6 is represented by the following general formula (1A-2), and R 7 is represented by the following general formula (1A-3) ) Is more preferable.
  • R 8 to R 17 may be the same as or different from each other, and are a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine.
  • R 8 to R 17 in the general formula (1A-2) and the general formula (1A-3) “a linear or branched group having 1 to 8 carbon atoms which may have a substituent.
  • the substituents which these groups may have are the same as those shown for R 1 to R 3 .
  • the “aryloxy group” in the “substituted or unsubstituted aryloxy group” represented by R 8 to R 17 in the general formula (1A-2) and the general formula (1A-3) is the above R 1 to
  • the groups are the same as those shown for R 3 , and the substituents that these groups may have are the same as those shown for R 1 to R 3 .
  • R 8 to R 17 in the general formula (1A-2) and the general formula (1A-3) include a deuterium atom, a trifluoromethyl group, a cyano group, a nitro group, a hydroxyl group, a halogen atom, and one carbon atom.
  • a linear or branched alkyl group having 8 to 8 carbon atoms or a linear or branched alkyloxy group having 1 to 8 carbon atoms is preferable.
  • the pyridinedicarboxylic acid derivative represented by the general formula (1) may be, for example, a pyridinedicarboxylic acid derivative represented by the following general formula (1A) or the following general formula (1A-1).
  • R 1 to R 7 are as described above.
  • R 1 to R 5 and R 8 to R 17 are as described above.
  • the pyridinedicarboxylic acid derivative represented by the general formula (1) according to this embodiment can be produced by a known method. For example, by reacting the corresponding dichloride of pyridinedicarboxylic acid and the alicyclic hydrocarbon, aromatic hydrocarbon or condensed polycyclic aromatic having the corresponding amino group in the presence of a base or the like, this embodiment The pyridinedicarboxylic acid derivative according to the above can be synthesized. It can also be synthesized by reacting the corresponding pyridinedicarboxylic acid with an alicyclic hydrocarbon, aromatic hydrocarbon or condensed polycyclic aromatic having a corresponding amino group in the presence of a dehydrating condensing agent.
  • the charge control agent is preferably used by adjusting the volume average particle diameter within the range of 0.1 ⁇ m to 20 ⁇ m, and particularly preferably adjusted within the range of 0.1 ⁇ m to 10 ⁇ m. If the volume average particle size is smaller than 0.1 ⁇ m, the amount of the charge control agent appearing on the toner surface tends to be extremely small, and the target charge control effect tends to be difficult to be obtained. It is not preferable because the charge control agent tends to increase and adverse effects such as in-machine contamination tend to occur.
  • the volume average particle diameter is preferably adjusted to 1.0 ⁇ m or less, particularly preferably adjusted to be in the range of 0.01 ⁇ m to 1.0 ⁇ m. .
  • the volume average particle size exceeds 1.0 ⁇ m, the particle size distribution of the finally obtained electrophotographic toner may be broadened or free particles may be generated, which may lead to a decrease in performance or reliability.
  • the average particle diameter is within the above range, there are no disadvantages, and the uneven distribution among the toners is reduced, the dispersion in the toner is improved, and the variation in performance and reliability is advantageous.
  • a method for adding the charge control agent according to the present embodiment to the toner a method of adding a kneading agent to the binder resin together with a colorant, kneading, and pulverization (pulverized toner), or charge control to a polymerizable monomer monomer
  • the amount of the charge control agent that is preferably added to the toner particles is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the binder resin.
  • the amount is 5 parts by mass.
  • the amount of the pyridinedicarboxylic acid derivative with respect to 100 parts by mass of the binder resin is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 2 parts by mass. is there. Further, it is preferable that the toner particles are fixed mechanochemically.
  • the charge control agent containing the pyridinedicarboxylic acid derivative represented by the general formula (1) as an active ingredient can be used in combination with other known negatively chargeable charge control agents.
  • Preferred charge control agents to be used in combination include azo iron complexes or complex salts, azo chromium complexes or complex salts, azo manganese complexes or complex salts, azo cobalt complexes or complex salts, azo zirconium complexes or complex salts, and chromium complexes of carboxylic acid derivatives.
  • a complex salt, a zinc complex or complex salt of a carboxylic acid derivative, an aluminum complex or complex salt of a carboxylic acid derivative, and a zirconium complex or complex salt of a carboxylic acid derivative is preferably an aromatic hydroxycarboxylic acid, more preferably 3,5-di-tert-butylsalicylic acid.
  • a boron complex or complex salt, a negatively chargeable resin type charge control agent and the like can be mentioned.
  • the amount of charge control other than the charge control agent according to the present embodiment is 100 parts by mass of the binder resin.
  • the agent is preferably 0.1 to 10 parts by mass.
  • binder resin can be used as the binder resin used in the toner according to the exemplary embodiment.
  • Vinyl polymers such as styrene monomers, acrylate monomers, methacrylate monomers, or copolymers composed of two or more of these monomers, polyester polymers, polyol resins, phenol resins, Examples include silicone resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, terpene resins, coumarone indene resins, polycarbonate resins, petroleum resins, and the like.
  • styrene monomer examples include styrene monomer, acrylate monomer, and methacrylate monomer that form the vinyl polymer or copolymer are illustrated below, but are not limited thereto.
  • Styrene monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-amylstyrene, p -Tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-chloro Examples thereof include styrene such as styrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrost
  • acrylate monomers include acrylic acid or methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-dodecyl acrylate, 2-acrylate
  • acrylic acid such as ethylhexyl, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate or esters thereof.
  • Methacrylate monomers include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, 2-ethyl methacrylate.
  • methacrylic acid or esters thereof such as hexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.
  • Examples of other monomers that form the vinyl polymer or copolymer include the following (1) to (18).
  • Monoolefins such as ethylene, propylene, butylene and isobutylene;
  • Polyenes such as butadiene and isoprene;
  • Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride;
  • Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate;
  • Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; (6) Vinyl methyl ketone, vinyl hexyl ketone and methyl.
  • Vinyl ketones such as isopropenyl ketone; (7) N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone; (8) vinyl naphthalenes; (9) acrylonitrile, methacrylate.
  • the vinyl polymer or copolymer of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups.
  • the cross-linking agent include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene.
  • diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, or those obtained by replacing the acrylate of the above compound with methacrylate.
  • diacrylate compounds linked by an alkyl chain containing an ether bond examples include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, Examples include propylene glycol diacrylate or those obtained by replacing acrylate of the above-mentioned compound with methacrylate.
  • polyester diacrylates examples include trade name MANDA (manufactured by Nippon Kayaku Co., Ltd.).
  • Polyfunctional cross-linking agents include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and those obtained by replacing acrylates of the above compounds with methacrylate, Examples include lucyanurate and triallyl trimellitate.
  • crosslinking agents can be used in an amount of preferably 0.01 to 10 parts by weight, particularly preferably 0.03 to 5 parts by weight, with respect to 100 parts by weight of other monomer components.
  • cross-linkable monomers those that are preferably used in the toner resin from the viewpoint of fixability and anti-offset properties include one aromatic divinyl compound (especially divinylbenzene is preferred), one aromatic group and one ether bond. Examples thereof include diacrylate compounds linked by a linking chain.
  • a combination of monomers that becomes a styrene copolymer or a styrene-acrylate copolymer is preferable.
  • examples of the polymerization initiator used for producing the vinyl polymer or copolymer include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate 1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo- 2 ', 4'-dimethyl-4'-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide Ketone peroxides such as oxide and cyclohexanone peroxide, 2,2-bis
  • the binder resin is a styrene-acrylate resin
  • the molecular weight distribution is 3,000 by molecular weight distribution by gel permeation chromatography (hereinafter abbreviated as GPC) soluble in the resin component tetrahydrofuran (hereinafter abbreviated as THF).
  • GPC gel permeation chromatography
  • THF-soluble component is preferably a binder resin in which a component having a molecular weight distribution of 100,000 or less is 50 to 90%. More preferably, it has a main peak in a region having a molecular weight of 5,000 to 30,000, and most preferably in a region having a molecular weight of 5,000 to 20,000.
  • the acid value is preferably 0.1 mgKOH / g to 100 mgKOH / g, and preferably 0.1 mgKOH / g to 70 mgKOH / g. More preferably, it is 0.1 mgKOH / g to 50 mgKOH / g.
  • Examples of the monomer constituting the polyester polymer include the following.
  • Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1, Examples thereof include 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or diol obtained by polymerizing cyclic ethers such as ethylene oxide and propylene oxide with bisphenol A.
  • a trihydric or higher alcohol examples include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene It is done.
  • Examples of the acid component that forms the polyester polymer include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or anhydrides thereof, and alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid or the like.
  • Unsaturated dibasic acids such as anhydride, maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc.
  • unsaturated dibasic acid anhydrides such as anhydride, maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succin
  • Trivalent or higher polyvalent carboxylic acid components include trimellitic acid, pyromellitic acid, 2,5,7-naphthalene tricarboxylic acid, 1,2,4-naphthalene tricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxy) methane, 1,2,7,8-octanetetracarboxylic acid, empol trimer Body acids, or anhydrides thereof, partial lower alkyl esters, and the like.
  • the molecular weight distribution of the THF-soluble component of the resin component has at least one peak in the molecular weight region of 3,000 to 50,000, which indicates toner fixability and offset resistance.
  • the THF-soluble component is preferably a binder resin in which a component having a molecular weight of 100,000 or less is 60 to 100%. More preferably, at least one peak is present in a region having a molecular weight of 5,000 to 20,000.
  • the molecular weight distribution of the binder resin is measured by GPC using THF as a solvent.
  • the molecular weight is, for example, a number average molecular weight in terms of standard polystyrene measured with an HLC-8220 GPC apparatus (manufactured by Tosoh Corporation).
  • the acid value is preferably 0.1 mgKOH / g to 100 mgKOH / g, more preferably 0.1 mgKOH / g to 70 mgKOH / g, and 0.1 mgKOH / g. More preferably, it is ⁇ 50 mg KOH / g.
  • the hydroxyl value is preferably 30 mgKOH / g or less, more preferably 10 mgKOH / g to 25 mgKOH / g.
  • a mixture of two or more of an amorphous polyester resin and a crystalline polyester resin may be used. In this case, it is preferable to select the material in consideration of the compatibility of each.
  • amorphous polyester resin those synthesized from a polyvalent carboxylic acid component, preferably an aromatic polyvalent carboxylic acid and a polyhydric alcohol component, are suitably used.
  • crystalline polyester resin one synthesized from a divalent carboxylic acid component, preferably an aliphatic dicarboxylic acid and a dihydric alcohol component, is suitably used.
  • a resin including a monomer component capable of reacting with both of these resin components in the vinyl polymer component and / or the polyester resin component can also be used.
  • monomers that can react with the vinyl polymer among the monomers constituting the polyester resin component include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof.
  • the monomer constituting the vinyl polymer component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.
  • the total binder resin has a resin having an acid value of 0.1 mgKOH / g to 50 mgKOH / g of 60% by mass or more. preferable.
  • the acid value of the binder resin component of the toner composition is determined by the following method, and the basic operation conforms to JIS K-0070.
  • the sample is used by removing additives other than the binder resin (polymer component) in advance, or the acid value and content of components other than the binder resin and the crosslinked binder resin are obtained in advance. .
  • a crushed sample of 0.5 to 2.0 g is precisely weighed, and the weight of the polymer component is defined as Wg.
  • Wg the weight of the polymer component
  • the toner binder resin and the composition containing the binder resin have a glass transition temperature (Tg) of preferably 35 to 80 ° C., particularly preferably 40 to 75 ° C. from the viewpoint of toner storage stability.
  • Tg glass transition temperature
  • the toner binder resin and the composition containing the binder resin have a glass transition temperature (Tg) of preferably 35 to 80 ° C., particularly preferably 40 to 75 ° C. from the viewpoint of toner storage stability.
  • Tg glass transition temperature
  • Tg glass transition temperature
  • a binder resin having a softening point in the range of 80 to 140 ° C. is preferably used.
  • the softening point of the binder resin is less than 80 ° C., the toner and the image stability of the toner after fixing and storage may be deteriorated.
  • the softening point exceeds 140 ° C., the low-temperature fixability may be deteriorated.
  • Magnetic materials that can be used in the present embodiment include (1) magnetic iron oxides such as magnetite, maghemite, and ferrite, and iron oxides containing other metal oxides, (2) metals such as iron, cobalt, and nickel, or Alloys of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and (3) Examples thereof include a mixture thereof.
  • the magnetic material include Fe 3 O 4 , ⁇ -Fe 2 O 3 , ZnFe 2 O 4 , Y 3 Fe 5 O 12 , CdFe 2 O 4 , Gd 3 Fe 5 O 12 , CuFe 2 O 4 , PbFe 12 O, NiFe 2 O 4 , NdFe 2 O, BaFe 12 O 19 , MgFe 2 O 4 , MnFe 2 O 4 , LaFeO 3 , iron powder, cobalt powder, nickel powder, etc. Or two or more types can be used in combination.
  • a particularly suitable magnetic substance is fine powder of iron trioxide or ⁇ -iron trioxide.
  • magnetic iron oxides such as magnetite, maghemite, and ferrite containing different elements, or a mixture thereof can be used.
  • different elements include lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, sulfur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, gallium, etc.
  • Preferred heterogeneous elements are selected from magnesium, aluminum, silicon, phosphorus, or zirconium.
  • the foreign element may be incorporated into the iron oxide crystal lattice, may be incorporated into the iron oxide as an oxide, or may exist as an oxide or hydroxide on the surface. Is preferably contained as an oxide.
  • the aforementioned different elements can be incorporated into the particles by adjusting the pH by mixing salts of the different elements at the time of producing the magnetic material. Moreover, it can be made to deposit on the particle
  • the amount of the magnetic substance used can be 10 to 200 parts by mass, preferably 20 to 150 parts by mass, with respect to 100 parts by mass of the binder resin.
  • These magnetic materials preferably have a number average particle diameter of 0.1 ⁇ m to 2 ⁇ m, and more preferably 0.1 ⁇ m to 0.5 ⁇ m.
  • the number average particle diameter can be obtained by measuring a photograph taken with a transmission electron microscope with a digitizer or the like.
  • the magnetic material preferably has a magnetic property of 10 to 150 oersted, a saturation magnetization of 50 to 200 emu / g, and a residual magnetization of 2 to 20 emu / g when applied with 10K oersted.
  • the magnetic material can also be used as a colorant.
  • the colorant according to this embodiment includes black or blue dye or pigment particles.
  • black or blue pigments include carbon black, aniline black, acetylene black, phthalocyanine blue, and indanthrene blue.
  • black or blue dyes include azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes.
  • examples of the colorant include the following.
  • magenta colorant condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dyes, lake dyes, naphthol dyes, benzimidazolone compounds, thioindigo compounds, and perylene compounds can be used.
  • examples of pigment-based magenta colorants include C.I. I.
  • the pigment may be used alone, it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together.
  • C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. I, disperse thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I.
  • Oil-soluble dyes such as Desperperiolet 1, C.I. I. Basic red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I. I. Examples include basic dyes such as basic violet 1,3,7,10,14,15,21,25,26,27,28.
  • cyan colorant copper phthalocyanine compounds and derivatives thereof, anthraquinones, basic dye lake compounds can be used.
  • examples of the pigment-based cyan colorant include C.I. I. Pigment blue 2, 3, 15, 16, 17, C.I. I. Bat Blue 6, C.I. I. Examples include Acid Blue 45 or copper phthalocyanine pigments in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.
  • yellow colorant condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds can be used.
  • yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 83, C.I. I. Bat yellow 1, 3, 20 and the like.
  • orange pigment examples include red chrome yellow, molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, benzidine orange G, indanthrene brilliant orange RK, and indanthrene brilliant orange GK.
  • purple pigments include manganese purple, fast violet B, and methyl violet lake.
  • green pigment examples include chromium oxide, chrome green, pigment green, malachite green lake, final yellow green G, and the like.
  • white pigments examples include zinc white, titanium oxide, antimony white, and zinc sulfide.
  • the amount of the colorant used is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.
  • the toner of this embodiment may be mixed with a carrier and used as a two-component developer.
  • a carrier a normal carrier such as ferrite or magnetite or a resin-coated carrier can be used as a carrier.
  • the resin-coated carrier is composed of carrier core particles and a coating material that is a resin that coats (coats) the surface of the carrier core particles.
  • a coating material that is a resin that coats (coats) the surface of the carrier core particles.
  • the resin used for the coating material include styrene-acrylate resins such as styrene-acrylic acid ester copolymers and styrene-methacrylic acid ester copolymers, acrylic acid ester copolymers, and methacrylic acid ester copolymers.
  • Fluorine-containing resins such as acrylate resins, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resins, polyester resins, polyamide resins, polyvinyl butyral, and aminoacrylate resins are preferred.
  • a resin that can be used as a coating material for a carrier such as an ionomer resin or a polyphenylene sulfide resin can be used. These resins can be used alone or in combination.
  • a binder type carrier core in which magnetic powder is dispersed in a resin can be used.
  • a resin-coated carrier as a method for coating the surface of the carrier core with at least a resin coating material, the resin is dissolved or suspended in a solvent, and is applied to the carrier core for adhesion, or simply mixed in a powder state. Applicable methods are applicable.
  • the ratio of the resin coating material to the resin-coated carrier may be appropriately determined, but is preferably 0.01 to 5% by mass, more preferably 0.1 to 1% by mass with respect to the resin-coated carrier.
  • Examples of use in which a magnetic material is coated with a coating agent of two or more kinds of mixtures include (1) dimethyldichlorosilane and dimethyl silicon oil (mass ratio 1: 5) with respect to 100 parts by mass of fine titanium oxide powder. Those treated with 12 parts by mass of the mixture, and (2) those treated with 20 parts by mass of the mixture of dimethyldichlorosilane and dimethylsilicone oil (mass ratio 1: 5) with respect to 100 parts by mass of the silica fine powder.
  • styrene-methyl methacrylate copolymer a mixture of fluorine-containing resin and styrene-based copolymer, or silicone resin is preferable, and silicone resin is particularly preferable.
  • Examples of the mixture of the fluorine-containing resin and the styrene copolymer include, for example, a mixture of polyvinylidene fluoride and a styrene-methyl methacrylate copolymer, a mixture of polytetrafluoroethylene and a styrene-methyl methacrylate copolymer, Vinylidene fluoride-tetrafluoroethylene copolymer (copolymer mass ratio 10:90 to 90:10), styrene-2-ethylhexyl acrylate copolymer (copolymer mass ratio 10:90 to 90:10) and styrene And a mixture with an acrylic acid-2-ethylhexyl-methyl methacrylate copolymer (copolymer mass ratio 20 to 60: 5 to 30:10:50).
  • silicone resin examples include nitrogen-containing silicone resins and modified silicone resins produced by reacting a nitrogen-containing silane coupling agent with a silicone resin.
  • ferrite, iron-rich ferrite, magnetite, oxides such as ⁇ -iron oxide, metals such as iron, cobalt, nickel, or alloys thereof can be used.
  • elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, and vanadium.
  • Preferred magnetic materials include copper-zinc-iron-based ferrites mainly composed of copper, zinc and iron components, and manganese-magnesium-iron-based ferrites mainly composed of manganese, magnesium and iron components.
  • the resistance value of the carrier is preferably adjusted to 10 6 ⁇ ⁇ cm to 10 10 ⁇ ⁇ cm by adjusting the degree of unevenness on the surface of the carrier and the amount of resin to be coated.
  • the particle size of the carrier can be 4 ⁇ m to 200 ⁇ m, preferably 10 ⁇ m to 150 ⁇ m, more preferably 20 ⁇ m to 100 ⁇ m.
  • the resin-coated carrier preferably has a 50% particle size of 20 ⁇ m to 70 ⁇ m.
  • the two-component developer it is preferable to use 1 to 200 parts by mass of the toner according to this embodiment with respect to 100 parts by mass of the carrier, and 2 to 50 parts by mass of toner with respect to 100 parts by mass of the carrier. It is more preferable.
  • the toner of this embodiment may further contain a wax.
  • the following wax is used.
  • oxides of aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax, sazol wax, aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or blocks thereof Copolymers, plant waxes such as candelilla wax, carnauba wax, wood wax, jojoba wax, animal waxes such as beeswax, lanolin, whale wax, mineral waxes such as ozokerite, ceresin, petrolatum, montanate ester wax, Examples thereof include waxes mainly composed of fatty acid esters such as caster wax and those obtained by partially or fully deoxidizing fatty acid esters such as deoxidized carnauba wax.
  • waxes are further saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or linear alkyl carboxylic acids having a linear alkyl group, prandidic acid, eleostearic acid, valinalic acid, etc.
  • Preferred waxes include polyolefins obtained by radical polymerization of olefins under high pressure, polyolefins obtained by purifying low molecular weight by-products obtained during the polymerization of high molecular weight polyolefins, and polymerization using a catalyst such as a Ziegler catalyst or a metallocene catalyst under low pressure.
  • these waxes have a sharp molecular weight distribution using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a solution liquid crystal deposition method, or a low molecular weight solid fatty acid, a low A molecular weight solid alcohol, a low molecular weight solid compound or other impurities are preferably used.
  • the wax used in the present embodiment preferably has a melting point of 50 to 140 ° C., more preferably 70 to 120 ° C., in order to balance the fixability and the offset resistance. If it is less than 50 degreeC, there exists a tendency for blocking resistance to fall, and if it exceeds 140 degreeC, it will become difficult to express an offset-proof effect.
  • the plasticizing action and the releasing action which are the actions of the wax can be expressed simultaneously.
  • the type of wax having a plasticizing action include a wax having a low melting point, a wax having a branched structure on the molecular structure, or a wax having a structure having a polar group.
  • the wax having a high molecular weight a linear wax or a non-polar wax having no functional group can be mentioned.
  • use include a combination in which the difference in melting point between two or more different waxes is 10 ° C. to 100 ° C., a combination of polyolefin and graft-modified polyolefin, and the like.
  • the melting point of at least one of the waxes is preferably 70 to 120 ° C., more preferably 70 to 100 ° C. When the melting point is in this range, the function separation effect tends to be easily exhibited.
  • the wax is relatively branched, has a polar group such as a functional group, or is modified with a component different from the main component to exert a plastic action, and has a more linear structure, A non-polar one having no functional group or an unmodified straight one exhibits a releasing action.
  • Preferred combinations of waxes include polyethylene homopolymers or copolymers based on ethylene and polyolefin homopolymers or copolymers based on olefins other than ethylene; combinations of polyolefins and graft modified polyolefins; alcohol waxes, fatty acid waxes or A combination of ester wax and hydrocarbon wax; a combination of Fischer-Tropsch wax or polyolefin wax and paraffin wax or microcrystal wax; a combination of Fischer-Tropsch wax and polyolefin wax; a combination of paraffin wax and microcrystal wax; a carnauba wax; Candelilla wax, rice wax or montan wax and carbonized water The combination of the system wax and the like.
  • the endothermic peak observed in the DSC measurement of the toner preferably has a maximum peak peak top temperature in the region of 70 to 110 ° C., and has a maximum peak peak top temperature in the region of 70 to 110 ° C. It is more preferable. This makes it easy to balance toner storage and fixing properties.
  • the total content of these waxes is preferably 0.2 to 20 parts by mass, and preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin. More preferred.
  • the melting point of the wax is the peak top temperature of the endothermic peak of the wax measured by DSC.
  • the DSC measurement of wax or toner is performed with a highly accurate internal heat input compensation type differential scanning calorimeter.
  • the measurement method is performed according to ASTM D3418-82.
  • a DSC curve is used that is measured when the temperature is raised at a temperature rate of 10 ° C./min after once raising and lowering the temperature and taking a previous history.
  • a fluidity improver may be added to the toner of this embodiment.
  • the fluidity improver improves the fluidity of the toner (becomes easy to flow) when added to the toner surface.
  • fluorocarbon resin powder such as carbon black, vinylidene fluoride fine powder, polytetrafluoroethylene fine powder, wet process silica, fine powder silica such as dry process silica, fine powder unoxidized titanium, fine powder unalumina, and silane
  • the particle size of the fluidity improver is preferably 0.001 ⁇ m to 2 ⁇ m, more preferably 0.002 ⁇ m to 0.2 ⁇ m, as an average primary particle size.
  • a preferable fine powder silica is a fine powder produced by vapor phase oxidation of a silicon halide inclusion, and is called so-called dry silica or fumed silica.
  • Examples of commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include those sold under the following trade names.
  • AEROSIL manufactured by Nippon Aerosil Co., Ltd., the same shall apply hereinafter
  • -130, -300, -380, -TT600, -MOX170, -MOX80, -COK84 Ca-O-SiL (manufactured by CABOT Corp., hereinafter the same shall apply) -M-5 , -MS-7, -MS-75, -HS-5, -EH-5, Wacker HDK (manufactured by WACKER-CHEMIEGMBH Co., Ltd., the same shall apply hereinafter) -N20 V15, -N20E, -T30, -T40: D-CFineSi1ica (Manufactured by Dow Corning): Franco1 (manufactured by Franci1).
  • a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of a silicon halogen compound is more preferable.
  • the treated silica fine powder it is particularly preferable to treat the silica fine powder so that the degree of hydrophobicity measured by a methanol titration test shows a value of 30 to 80%.
  • the hydrophobizing treatment can be performed, for example, by a method of chemically or physically treating with an organosilicon compound that reacts or physically adsorbs with silica fine powder.
  • a method of treating silica fine powder produced by vapor phase oxidation of a silicon halogen compound with an organosilicon compound is preferable.
  • organosilicon compounds include hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, vinylmethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, dimethylvinylchlorosilane, Divinylchlorosilane, ⁇ -methacryloxypropyltrimethoxysilane, hexamethyldisilane, trimethylsilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, ⁇ -Chloroethyltrichlorosilane,
  • the fluidity improver preferably has a number average particle diameter of 5 nm to 100 nm, more preferably 5 nm to 50 nm.
  • the specific surface area by nitrogen adsorption measured by the BET method is preferably 30 m 2 / g or more, more preferably 60 to 400 m 2 / g.
  • the surface-treated fine powder is preferably 20 m 2 / g or more, more preferably 40 to 300 m 2 / g.
  • the application amount of these fine powders is preferably 0.03 to 8 parts by mass with respect to 100 parts by mass of the toner particles.
  • the toner of the present embodiment includes various types of metal soaps for the purpose of protecting the photoconductor / carrier, improving cleaning properties, adjusting thermal characteristics / electrical characteristics / physical characteristics, adjusting resistance, adjusting softening point, improving fixing rate, etc.
  • lubricants such as polytetrafluoroethylene, zinc stearate, and polyvinylidene fluoride, abrasives such as cesium oxide, silicon carbide, and strontium titanate, anti-caking agents, and white particles and black particles that are opposite in polarity to the toner particles A small amount can be used as a developability improver.
  • These additives include silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, and other organosilicon compounds for the purpose of charge control. It is also preferable to treat with a treating agent or various treating agents.
  • the charge control agent is sufficiently mixed and stirred together with the additive and toner as described above by a mixer such as a Henschel mixer, a ball mill, a nauter mixer, a V-type mixer, a W-type mixer, or a super mixer.
  • a mixer such as a Henschel mixer, a ball mill, a nauter mixer, a V-type mixer, a W-type mixer, or a super mixer.
  • the target electrostatic charge developing toner can be obtained by uniformly externally treating the toner particle surface.
  • the toner of this embodiment is thermally stable and does not undergo thermal changes during the electrophotographic process, and can maintain stable charging characteristics. Further, since it is uniformly dispersed in any binder resin, the charge distribution of the fresh toner is very uniform. For this reason, in the toner of this embodiment, even in the untransferred and recovered toner (waste toner), almost no change is observed in the saturated triboelectric charge amount and the charge distribution compared to the fresh toner. On the other hand, when the waste toner from the electrostatic image developing toner of this embodiment is reused, a method of selecting a polyester resin containing an aliphatic diol as a binder resin, a metal-crosslinked styrene-acrylate copolymer is used. By producing a toner by using a binder resin and adding a large amount of polyolefin to the binder resin, the difference between the fresh toner and the waste toner can be further reduced.
  • the toner according to the present embodiment can be manufactured by a known manufacturing method.
  • the above-mentioned toner constituent materials such as a binder resin, a charge control agent, and a colorant are sufficiently mixed by a mixer such as a ball mill, and the resulting mixture is well kneaded by a heating and kneading apparatus such as a hot roll kneader.
  • a method (pulverization method) obtained by solidifying by cooling, classification after pulverization is preferable.
  • toner production method comprising a core material and a shell material by a polymerization method in which a predetermined material is mixed with a monomer to constitute a binder resin to form an emulsion or suspension and then polymerized to obtain a toner.
  • the microcapsule toner can also be manufactured by a method in which a predetermined material is contained in the core material, the shell material, or both.
  • the toner according to the exemplary embodiment can be manufactured by sufficiently mixing a desired additive and toner particles with a mixer such as a Henschel mixer as necessary.
  • the toner manufacturing method according to the present embodiment using the pulverization method will be described in more detail.
  • a binder resin, a colorant, a charge control agent, and other necessary additives are mixed uniformly.
  • a known stirrer such as a Henschel mixer, a super mixer, or a ball mill can be used.
  • the obtained mixture is hot-melt kneaded using a closed kneader or a single-screw or twin-screw extruder.
  • the kneaded product is coarsely pulverized using a crusher or a hammer mill, and further finely pulverized by a pulverizer such as a jet mill or a high-speed rotor rotary mill.
  • classification is performed to a predetermined particle size using an air classifier, for example, an inertia class elbow jet utilizing the Coanda effect, a cyclone (centrifugal) class microplex, a DS separator, and the like.
  • an air classifier for example, an inertia class elbow jet utilizing the Coanda effect, a cyclone (centrifugal) class microplex, a DS separator, and the like.
  • a high-speed agitator such as a Henschel mixer or a super mixer.
  • the toner according to the present embodiment can be manufactured by a suspension polymerization method or an emulsion polymerization method.
  • a suspension polymerization method first, a polymerizable monomer, a colorant, a polymerization initiator, a charge control agent and, if necessary, a crosslinking agent, a dispersion stabilizer and other additives are uniformly dissolved or dispersed.
  • a monomer composition is prepared.
  • the monomer composition and the dispersion stabilizer are mixed into an appropriate stirrer or disperser such as a homomixer, a homogenizer, an atomizer, a microfluidizer, a one-component fluid nozzle, a gas-liquid fluid in a continuous phase (for example, an aqueous phase). Disperse using a nozzle, electric emulsifier or the like.
  • granulation is performed by adjusting the stirring speed, temperature, and time so that the droplets of the polymerizable monomer composition have a desired toner particle size.
  • the polymerization reaction is carried out at 40 to 90 ° C. to obtain toner particles having a desired particle size.
  • the obtained toner particles are washed, filtered, and dried.
  • the method described above can be used.
  • the average particle diameter is extremely small, 0.1 ⁇ m to 1.0 ⁇ m, although it is excellent in uniformity compared to the particles obtained by the suspension polymerization method described above. It can also be produced by a so-called seed polymerization method in which particles are grown by post-addition of a polymerizable monomer, or a method in which emulsified particles are coalesced and fused to an appropriate average particle size.
  • the selection range of can be expanded.
  • the release agent or colorant which is a hydrophobic material, is difficult to be exposed on the surface of the toner particles, so that contamination of the toner carrying member, the photoreceptor, the transfer roller, and the fixing device can be reduced.
  • the toner according to this embodiment By producing the toner according to this embodiment by a polymerization method, characteristics such as image reproducibility, transferability, and color reproducibility can be further improved.
  • the toner particle size can be reduced in order to deal with minute dots, and a toner having a sharp particle size distribution can be obtained relatively easily.
  • Examples of the polymerizable monomer used when the toner according to the exemplary embodiment is manufactured by a polymerization method include vinyl polymerizable monomers capable of radical polymerization.
  • a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.
  • Monofunctional polymerizable monomers include styrene, ⁇ -methyl styrene, ⁇ -methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene, pn-butyl.
  • Styrene polymerizable monomers such as styrene, p-tert-butylstyrene, pn-hexylstyrene, p-phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl Acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, benzyl acrylate, dimethyl phosphate methyl acrylate, dibutyl phosphate ethyl Acrylate polymerizable monomers such as acrylate and 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl me
  • a known polymerization initiator such as an organic peroxide can be used as the polymerization initiator used when the toner according to the present embodiment is produced by the polymerization method.
  • the water-soluble initiator include ammonium persulfate, potassium persulfate, 2, 2'-azobis (N, N'-dimethyleneisobutyroamidine) hydrochloride, 2,2'-azobis (2-aminodipropane) hydrochloride, azobis (isobutylamidine) hydrochloride, 2,2'-azo Examples thereof include sodium bisisobutyronitrile sulfonate, ferrous sulfate, and hydrogen peroxide.
  • the polymerization initiator is preferably added in an amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer, and may be used alone or in combination.
  • the dispersant used in the production of the polymerized toner include inorganic calcium oxides such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, aluminum hydroxide, and metasilicate. Examples thereof include calcium acid, calcium sulfate, barium sulfate, bentonite, silica, and alumina.
  • organic compound examples include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch and the like. These dispersants are preferably used in an amount of 0.2 to 2.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer.
  • the inorganic compound can be produced in a dispersion medium under high-speed stirring.
  • the toner obtained by the polymerization method tends to have a small degree of unevenness of the toner particles compared to the toner by the pulverization method without any special treatment and is indefinite, so that the contact between the electrostatic latent image carrier and the toner The area is increased and the toner adhesion is increased. As a result, there is less in-machine contamination, and a higher image density and a higher quality image can be easily obtained.
  • the toner particles are dispersed in water and heated by a hot water bath method, a heat treatment method in which the toner particles pass through a hot air current, or a mechanical impact method in which mechanical energy is applied and processed.
  • the degree of unevenness on the toner surface can be reduced.
  • Effective devices for reducing the degree of unevenness include a mechano-fusion system (manufactured by Hosokawa Micron Co., Ltd.) applying dry mechanochemical method, an I-type jet mill, and a hybridizer that is a mixing device having a rotor and a liner (Nara Machinery) Manufactured by Seisakusho Co., Ltd.) and a Henschel mixer which is a mixer having high-speed stirring blades.
  • the average circularity (C) is the total number of particles obtained by calculating the circularity (Ci) by the following formula (2) and further measuring the total roundness of all the particles measured as shown by the following formula (3). It means the value divided by (m).
  • the circularity (Ci) is measured using a flow particle image analyzer (for example, FPIA-1000 manufactured by Toa Medical Electronics Co., Ltd.).
  • a flow particle image analyzer for example, FPIA-1000 manufactured by Toa Medical Electronics Co., Ltd.
  • a measurement method a dispersion in which about 5 mg of toner is dispersed in 10 ml of water in which about 0.1 mg of a nonionic surfactant is dissolved is prepared, and ultrasonic waves (20 kHz, 50 W) are irradiated to the dispersion for 5 minutes.
  • the circularity distribution of particles having an equivalent circle diameter of 0.60 ⁇ m or more and less than 159.21 ⁇ m is measured using the flow type particle image analyzer with a dispersion concentration of 5000 to 20000 particles / ⁇ L.
  • the value of the average circularity is preferably 0.955 to 0.995, and more preferably 0.960 to 0.985.
  • the toner particle diameter is preferably in the range of 2 ⁇ m to 15 ⁇ m, more preferably in the range of 3 ⁇ m to 12 ⁇ m in terms of volume average particle diameter.
  • the average particle size exceeds 15 ⁇ m, the resolution or sharpness tends to be dull, and when the average particle size is less than 2 ⁇ m, the resolution is good, but the problem of high cost due to the deterioration of the yield during toner production, Or there is a tendency for health problems such as toner scattering and skin penetration in the machine.
  • the polymerized toner it is preferably in the range of 3 ⁇ m to 9 ⁇ m, more preferably in the range of 4 ⁇ m to 8.5 ⁇ m, and particularly preferably in the range of 5 ⁇ m to 8 ⁇ m.
  • the volume average particle size is smaller than 4 ⁇ m, the toner fluidity is lowered, the chargeability of each particle is liable to be lowered, and the charge distribution is widened. Become.
  • the cleaning property may be extremely difficult. If the volume average particle size is larger than 9 ⁇ m, the resolution decreases, so that sufficient image quality cannot be obtained, and it may be difficult to satisfy recent high image quality requirements.
  • the polymerized toner according to the present embodiment draws a cumulative distribution from the smaller diameter side for each of the volume and the number in the divided particle size range (channel) measured by the following method.
  • the particle size to be defined is defined as volume D16%
  • the particle size to be accumulated 50% is defined as volume D50%
  • the particle size to be accumulated 84% is defined as volume D84%, it is calculated from (D84% / D16%) 1/2.
  • the volume average particle size distribution index (GSDv) is preferably 1.15 to 1.30, more preferably 1.15 to 1.25.
  • the particle content of 2 ⁇ m or less is 10 to 90% on the number basis, for example, by particle size measurement using a Coulter counter (TA-II manufactured by Coulter Co., Ltd.).
  • the content of particles of 12.7 ⁇ m or more is more preferably 0 to 30% on a volume basis.
  • those having a high particle size uniformity are desirable.
  • the specific surface area of the toner is preferably 1.2 to 5.0 m 2 / g in BET specific surface area measurement using nitrogen as a desorption gas. More preferably, it is 1.5 to 3.0 m 2 / g.
  • the specific surface area is measured using, for example, a BET specific surface area measuring apparatus (for example, FlowSorb II2300, manufactured by Shimadzu Corporation), desorbing the adsorbed gas on the toner surface at 50 ° C. for 30 minutes, and then rapidly cooling with liquid nitrogen. The gas is re-adsorbed and then heated again to 50 ° C., which is defined as a value obtained from the degassing amount at this time.
  • the apparent specific gravity was measured using, for example, a powder tester (for example, manufactured by Hosokawa Micron Corporation).
  • a powder tester for example, manufactured by Hosokawa Micron Corporation.
  • 0.2 to 0.6 g / cm 3 is preferable, and in the case of a magnetic toner, 0.2 to 2.0 g / cm 3 is preferable depending on the kind and content of the magnetic powder.
  • the true specific gravity in the case of the non-magnetic toner is preferably 0.9 to 1.2 g / cm 3 , and in the case of the magnetic toner, it depends on the kind and content of the magnetic powder, but 0.9 ⁇ 4.0 g / cm 3 is preferred.
  • the true specific gravity of the toner is calculated as follows. 1.000 g of toner is precisely weighed, put into a 10 mm ⁇ tablet molding machine, and compression molded while applying a pressure of 200 kgf / cm 2 under vacuum. The height of this cylindrical molded product is measured with a micrometer, and the true specific gravity is calculated from this.
  • the fluidity of the toner is defined by, for example, a flow repose angle and a static repose angle by a repose angle measuring device (for example, manufactured by Tsutsui Rika Co., Ltd.).
  • the flow angle of repose is preferably 5 to 45 degrees in the case of the electrostatic charge developing toner using the charge control agent according to the present embodiment.
  • the rest angle of repose is preferably 10 to 50 degrees.
  • the average value of the shape factor (SF-1) in the case of the pulverized toner is preferably 100 to 400, and the average value of the shape factor 2 (SF-2) is preferably 100 to 350.
  • SF-1 and SF-2 indicating the shape factor of the toner are, for example, toner particles magnified 1000 times using an optical microscope (for example, BH-2 manufactured by Olympus Corporation) equipped with a CCD camera.
  • the group is sampled to be about 30 in one field of view, and the obtained image is transferred to an image analyzer (for example, Luzex FS manufactured by Nireco Co., Ltd.), and the same operation is repeated until there are about 1000 toner particles.
  • the shape factor was calculated.
  • the shape factor (SF-1) and the shape factor 2 (SF-2) are calculated by the following equations.
  • SF-1 ((ML 2 ⁇ ⁇ ) / 4A) ⁇ 100 (In the formula, ML represents the maximum particle length, and A represents the projected area of one particle.)
  • SF-2 (PM 2 / 4A ⁇ ) ⁇ 100 (In the formula, PM represents the perimeter of the particle, and A represents the projected area of one particle.)
  • SF-1 represents the distortion of the particle, and the closer the particle is to a sphere, the closer to 100, and the longer the particle, the larger the value.
  • SF-2 represents the unevenness of the particle. The closer the particle is to a sphere, the closer to 100, and the more complicated the particle shape, the larger the value.
  • the volume resistivity of the toner is preferably 1 ⁇ 10 12 to 1 ⁇ 10 16 ⁇ ⁇ cm in the case of a non-magnetic toner, and the type and content of the magnetic powder in the case of a magnetic toner. However, it is preferably 1 ⁇ 10 8 to 1 ⁇ 10 16 ⁇ ⁇ cm.
  • the toner volume resistivity is obtained by compression-molding toner particles to produce a disk-shaped test piece having a diameter of 50 mm and a thickness of 2 mm, and setting this on a solid electrode (for example, SE-70 manufactured by Ando Electric Co., Ltd.). Using a high insulation resistance meter (for example, 4339A manufactured by Hewlett-Packard Co., Ltd.), it is defined as a value after 1 hour when a DC voltage of 100 V is continuously applied.
  • the toner according to this embodiment preferably has a dielectric loss tangent of 1.0 ⁇ 10 ⁇ 3 to 15.0 ⁇ 10 ⁇ 3 in the case of non-magnetic toner, and the kind of magnetic powder in the case of magnetic toner. Depending on the content, those of 2 ⁇ 10 ⁇ 3 to 30 ⁇ 10 ⁇ 3 are preferable.
  • the dielectric loss tangent of the toner is obtained by compression-molding the toner particles to produce a disk-shaped test piece having a diameter of 50 mm and a thickness of 2 mm, setting this on an electrode for solid, and an LCR meter (for example, Hewlett-Packard) It is defined as a dielectric loss tangent value (Tan ⁇ ) obtained when measured at a measurement frequency of 1 KHz and a peak-to-peak voltage of 0.1 KV using 4284A).
  • the toner according to the exemplary embodiment preferably has an Izod impact value of the toner of 0.1 to 30 kg ⁇ cm / cm.
  • the Izod impact value of the toner in this case is measured in accordance with JIS standard K-7110 (hard plastic impact test method) by thermally melting toner particles to produce a plate-like test piece.
  • the toner according to the present embodiment preferably has a toner melt index (MI value) of 10 to 150 g / 10 min.
  • the melt index (MI value) of the toner in this case is measured according to JIS standard K-7210 (Method A). In this case, the measurement temperature is 125 ° C. and the load is 10 kg.
  • the melting start temperature of the toner is preferably 80 to 180 ° C.
  • the 4 mm drop temperature is preferably 90 to 220 ° C.
  • the toner melting start temperature is obtained by compressing and molding toner particles to produce a cylindrical test piece having a diameter of 10 mm and a thickness of 20 mm, which is then used as a thermal melting characteristic measuring device such as a flow tester (for example, CFT manufactured by Shimadzu Corporation). -500C) and is defined as the value at which melting starts and the piston starts to descend when measured at a load of 20 kgf / cm 2 .
  • the temperature when the piston drops by 4 mm is defined as the 4 mm drop temperature.
  • the glass transition temperature (Tg) of the toner is preferably 35 to 80 ° C., and more preferably 40 to 75 ° C.
  • the glass transition temperature of the toner in this case is measured using a differential thermal analysis (hereinafter abbreviated as DSC) apparatus, and the peak value of the phase change that appears when the temperature is raised at a constant temperature, rapidly cooled, and then reheated. Define what you want more.
  • DSC differential thermal analysis
  • the peak top temperature of the maximum peak is in the region of 70 to 120 ° C.
  • the melt viscosity of the toner is preferably 1000 to 50000 poise, and more preferably 1500 to 38000 poise.
  • the toner melt viscosity is obtained by compressing and molding toner particles to prepare a cylindrical test piece having a diameter of 10 mm and a thickness of 20 mm, and using this, for example, a flow tester (CFT-500C manufactured by Shimadzu Corporation). It is defined as a value when measured at a load of 20 kgf / cm 2 .
  • the solvent-soluble residue of the toner according to the exemplary embodiment is preferably 0 to 30% by mass as a THF-insoluble component, 0 to 40% by mass as an ethyl acetate-insoluble component, and 0 to 30% by mass as a chloroform-insoluble component.
  • the solvent-dissolved residue here is obtained by uniformly dissolving / dispersing 1 g of toner in 100 ml of each solvent of THF, ethyl acetate and chloroform, pressure-filtering the solution / dispersion, drying the filtrate, and quantifying. From this value, the ratio of insoluble matter in the organic solvent in the toner is calculated.
  • the toner according to the present embodiment can be used in a one-component development method which is one of image forming methods.
  • the one-component developing method is a method for developing a latent image by supplying a thinned toner to a latent image carrier.
  • the toner thinning usually includes a toner conveying member, a toner layer thickness regulating member and a toner replenishing auxiliary member, and the replenishing auxiliary member and the toner conveying member, and the toner layer thickness regulating member and the toner conveying member are in contact with each other. It is performed using the device.
  • the two-component development method is a method using toner and a carrier (having a role as a charge imparting material and a toner conveying material), and the above-described magnetic material and glass beads are used for the carrier.
  • the developer toner and carrier
  • the developer is agitated by the agitating member, generates a predetermined amount of charge, and is conveyed to the development site by a magnet roller or the like.
  • a magnet roller On the magnet roller, a developer is held on the roller surface by magnetic force, and a magnetic brush whose layer is regulated to an appropriate height by a developer regulating plate or the like is formed.
  • the developer moves on the roller as the developing roller rotates, and is brought into contact with the electrostatic charge latent image holding member or opposed in a non-contact state at a constant interval to develop and visualize the latent image.
  • a driving force for the toner it is usually possible to obtain a driving force for the toner to fly through a space at a constant interval by generating a direct current electric field between the developer and the latent image holding member. It can also be applied to a method of superimposing alternating current in order to develop an image.
  • the charge control agent used in the present embodiment is also suitable as a charge control agent (charge enhancer) in a coating for electrostatic powder coating. That is, the coating material for electrostatic coating using this charge enhancer is excellent in environmental resistance, storage stability, in particular thermal stability and durability, has a coating efficiency of 100%, and is a thick film free from coating film defects. Can be formed.
  • charge enhancer charge control agent
  • Purification of the pyridinedicarboxylic acid derivative represented by the general formula (1) was performed by purification using column chromatography, adsorption purification using silica gel, activated carbon, activated clay, recrystallization using a solvent, or crystallization. The compound was identified by NMR analysis.
  • Example 1-10 (Production of non-magnetic toner 1-1) Styrene-acrylate copolymer resin (manufactured by Mitsui Chemicals, trade name CPR-100, acid value 0.1 mg KOH / g) 91 parts, pyridinedicarboxylic acid derivative synthesized in Synthesis Example 1-3 (Exemplary Compound 1- 4) 1 part, 5 parts of carbon black (trade name MA-100, manufactured by Mitsubishi Chemical Corporation) and 3 parts of low molecular weight polypropylene (trade name, Biscol 550P, manufactured by Sanyo Chemical Co., Ltd.) are heated and mixed at 130 ° C. (biaxial) The mixture was melt mixed by an extrusion kneader. The cooled mixture was coarsely pulverized with a hammer mill, then finely pulverized with a jet mill, and classified to obtain a nonmagnetic toner 1-1 having a volume average particle size of 9 ⁇ 0.5 ⁇ m.
  • the charge amount was also evaluated when mixed with a silicon-coated ferrite carrier (F96-150 manufactured by Powdertech). As a result, it was ⁇ 23.7 ⁇ c / g.
  • Example 1-11 (Production and evaluation of non-magnetic toner 1-2) Except that the pyridinedicarboxylic acid derivative synthesized in Synthesis Example 1-3 (Exemplary Compound 1-4) was replaced with the pyridinedicarboxylic acid derivative synthesized in Synthesis Example 1-5 (Exemplary Compound 1-6), Example Nonmagnetic toner 1-2 was prepared in the same manner as in 1-10, and the charge amount was evaluated by a blow-off powder charge amount measuring device. As a result, the charge amount when mixed with a non-coated ferrite carrier (F-150 manufactured by Powdertech Co., Ltd.) was ⁇ 32.3 ⁇ c / g.
  • a non-coated ferrite carrier F-150 manufactured by Powdertech Co., Ltd.
  • the charge amount when mixed with a non-coated ferrite carrier was ⁇ 23.0 ⁇ c / g.
  • the charge amount when mixed with a silicon-coated ferrite carrier was -15.0 ⁇ c / g.
  • Example 2-5 Manufacture of non-magnetic toner 2-1
  • Styrene-acrylate copolymer resin manufactured by Mitsui Chemicals, trade name CPR-100, acid value 0.1 mg KOH / g
  • pyridine dicarboxylic acid derivative synthesized in Synthesis Example 2-2 Exemplary Compound 2- 3 1 part, 5 parts of carbon black (trade name MA-100, manufactured by Mitsubishi Chemical Corporation) and 3 parts of low molecular weight polypropylene (trade name, Biscol 550P, manufactured by Sanyo Chemical Co., Ltd.) are heated and mixed at 130 ° C. (biaxial The mixture was melt mixed by an extrusion kneader. The cooled mixture was coarsely pulverized with a hammer mill, then finely pulverized with a jet mill, and classified to obtain a nonmagnetic toner 2-1 having a volume average particle size of 9 ⁇ 0.5 ⁇ m.
  • the charge amount was also evaluated when mixed with a silicon-coated ferrite carrier (F96-150 manufactured by Powdertech). As a result, it was ⁇ 25.3 ⁇ c / g.
  • Comparative Example 2-1 (Production and evaluation of comparative non-magnetic toner 2-1) Except that the pyridinedicarboxylic acid derivative (Exemplary Compound 2-3) synthesized in Synthesis Example 2-2 was replaced with a salt of 3,5-tert-butylsalicylic acid and zinc, the same method as in Example 2-5 was used. Comparative non-magnetic toner 2-1 was prepared, and the charge amount was evaluated with a blow-off powder charge amount measuring device. As a result, the charge amount when mixed with a non-coated ferrite carrier (F-150 manufactured by Powdertech Co., Ltd.) was ⁇ 23.0 ⁇ c / g. Similarly, the charge amount when mixed with a silicon-coated ferrite carrier (F96-150 manufactured by Powdertech) was -15.0 ⁇ c / g.
  • a non-coated ferrite carrier F-150 manufactured by Powdertech Co., Ltd.
  • a silicon-coated ferrite carrier F96-150 manufactured by Powder
  • the toner using the charge control agent containing the pyridinedicarboxylic acid derivative represented by the general formula (1) of the present invention as an active ingredient has a high charge amount.
  • Example 1-12 Preparation of resin dispersion
  • the volume average particle diameter of the resin particles in this dispersion was 0.2 ⁇ m (the resin particle concentration was adjusted to 20% by mass with ion-exchanged water).
  • the mixture was further stirred for 2 hours, and after confirming that the volume average particle diameter was 6.0 ⁇ m and the particle shape was spheroidized, it was rapidly cooled using ice water.
  • the sample was collected by filtration and dispersed and washed with ion exchange water. Dispersion washing was repeated until the electric conductivity of the filtrate after dispersion became 20 ⁇ S / cm or less. Thereafter, the toner particles were obtained by drying with a dryer at 40 ° C. The obtained toner was sieved with a 166 mesh (aperture 90 ⁇ m) sieve to obtain an evaluation toner.
  • Example 1-2 For comparison, a toner was prepared under the same conditions as in Example 1-12 except that the operation of adding the charge control agent dispersion was omitted, and the saturation charge amount was measured. As a result, the saturated charge amount was ⁇ 20.5 ⁇ C / g.
  • Example 2-6 (Preparation of resin dispersion) Mix 80 parts of polyester resin (Made by Mitsubishi Rayon Co., Ltd., DIACRON ER-561), 320 parts of ethyl acetate and 32 parts of isopropyl alcohol, and use a homogenizer (Megaku Co., Ltd., foamless mixer NGM-0.5TB). While stirring at 5000 to 10000 rpm, an appropriate amount of 0.1% by mass of ammonia water was added dropwise for phase inversion emulsification, and the solvent was removed while reducing the pressure with an evaporator to obtain a resin dispersion. The volume average particle diameter of the resin particles in this dispersion was 0.2 ⁇ m (the resin particle concentration was adjusted to 20% by mass with ion-exchanged water).
  • the mixture was further stirred for 2 hours, and after confirming that the volume average particle diameter was 6.0 ⁇ m and the particle shape was spheroidized, it was rapidly cooled using ice water.
  • the sample was collected by filtration and dispersed and washed with ion exchange water. Dispersion washing was repeated until the electric conductivity of the filtrate after dispersion became 20 ⁇ S / cm or less. Thereafter, the toner particles were obtained by drying with a dryer at 40 ° C. The obtained toner was sieved with a 166 mesh (aperture 90 ⁇ m) sieve to obtain an evaluation toner.
  • Example 2-2 For comparison, a toner was prepared under the same conditions as in Example 2-6, except that the operation of adding the charge control agent dispersion was omitted, and the saturation charge amount was measured. As a result, the saturated charge amount was ⁇ 20.5 ⁇ C / g.
  • the polymerized toner containing the pyridinedicarboxylic acid derivative represented by the general formula (1) of the present invention as an active ingredient exhibits excellent charging performance. That is, high charge performance can be imparted to the polymerized toner by using a charge control agent containing the pyridinedicarboxylic acid derivative represented by the general formula (1) of the present invention as an active ingredient.
  • the pyridinedicarboxylic acid derivative represented by the general formula (1) according to the present invention has excellent charging performance, and the charge control agent containing the compound as an active ingredient is clearly higher than the conventional charge control agent. Has charging performance.
  • the charge control agent is optimal for color toners, particularly for polymerized toners. Furthermore, the charge control agent is extremely useful because it does not contain heavy metals such as chromium compounds, which are concerned with environmental problems.

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  • Pyridine Compounds (AREA)

Abstract

La présente invention concerne un agent de contrôle de charge qui contient, comme ingrédient actif, un ou plusieurs dérivés d'acide pyridine dicarboxylique représentés par la formule générale (1). (Dans la formule générale (1), R1, R2 et R3 peuvent être identiques ou peuvent être différents les uns des autres et chacun représente un atome d'hydrogène ou similaire ; R4 et R5 peuvent être identiques ou différents les uns des autres et chacun représente un atome d'hydrogène ou similaire ; R6 et R7 peuvent être identiques ou différents les uns des autres et chacun représente un groupe cycloalkyle facultativement substitué ayant 5-10 atomes de carbone, un groupe hydrocarboné aromatique substitué ou non substitué ou un groupe aromatique polycyclique condensé substitué ou non substitué. A cet égard, R1, R2 et R3 peuvent se combiner avec des groupes adjacents respectifs pour former un cycle).
PCT/JP2013/052073 2012-02-29 2013-01-30 Agent de contrôle de charge et toner l'utilisant WO2013129015A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020034861A (ja) * 2018-08-31 2020-03-05 保土谷化学工業株式会社 電荷制御剤及びそれを用いたトナー
WO2023277594A1 (fr) * 2021-06-30 2023-01-05 주식회사 동진쎄미켐 Nouveau composé pour couche de recouvrement, et dispositif électroluminescent organique le comprenant

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MX2018014015A (es) * 2016-05-18 2020-01-30 Solenis Technologies Lp Metodo para mejorar la adhesion de toner liquido impreso en un sustrato y productos del mismo.

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5233676A (en) * 1975-09-09 1977-03-14 Banyu Pharmaceut Co Ltd Process for preparation of pyridinedicarboxylic acid amides
JPS63306460A (ja) * 1987-06-02 1988-12-14 ゼロックス　コーポレーション 負帯電促進添加剤を含有するトナー組成物
JPH03174540A (ja) * 1989-12-04 1991-07-29 Canon Inc 電子写真感光体
JP2001213865A (ja) * 1999-12-15 2001-08-07 Eastman Kodak Co １，４−ジヒドロピリジン、トナー組成物及び電荷制御剤
JP2010286592A (ja) * 2009-06-10 2010-12-24 Kao Corp 電子写真用トナー

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5233676A (en) * 1975-09-09 1977-03-14 Banyu Pharmaceut Co Ltd Process for preparation of pyridinedicarboxylic acid amides
JPS63306460A (ja) * 1987-06-02 1988-12-14 ゼロックス　コーポレーション 負帯電促進添加剤を含有するトナー組成物
JPH03174540A (ja) * 1989-12-04 1991-07-29 Canon Inc 電子写真感光体
JP2001213865A (ja) * 1999-12-15 2001-08-07 Eastman Kodak Co １，４−ジヒドロピリジン、トナー組成物及び電荷制御剤
JP2010286592A (ja) * 2009-06-10 2010-12-24 Kao Corp 電子写真用トナー

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020034861A (ja) * 2018-08-31 2020-03-05 保土谷化学工業株式会社 電荷制御剤及びそれを用いたトナー
JP7099910B2 (ja) 2018-08-31 2022-07-12 保土谷化学工業株式会社 電荷制御剤及びそれを用いたトナー
WO2023277594A1 (fr) * 2021-06-30 2023-01-05 주식회사 동진쎄미켐 Nouveau composé pour couche de recouvrement, et dispositif électroluminescent organique le comprenant

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