TW201348897A - Charge control agent and toner using same - Google Patents

Abstract

The present invention provides a charge control agent which contains, as an active ingredient, one or more pyridine dicarboxylic acid derivatives represented by general formula (1). (In general formula (1), R1, R2 and R3 may be the same as or different from each other, and each represents a hydrogen atom or the like; R4 and R5 may be the same as or different from each other, and each represents a hydrogen atom or the like; R6 and R7 may be the same as or different from each other, and each represents an optionally substitute cycloalkyl group having 5-10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted condensed polycyclic aromatic group. In this connection, R1, R2 and R3 may combine with respective adjacent groups to form a ring.)

Description

Charge control agent and toner using the same

The present invention relates to a charge control agent used in an image forming apparatus for developing an electrostatic latent image in the fields of electrophotography, electrographic recording, and the like, and a negatively chargeable toner containing a charge control agent Agent.

In an electrophotographic image forming process, an electrostatic latent image is formed on an inorganic photoreceptor such as selenium, selenium alloy, cadmium sulfide or amorphous germanium or an organic photoreceptor using a charge generating agent and a charge transporting agent, by coloring The agent is developed and transferred to a paper or plastic film to be fixed to obtain a visible image.

The photoreceptor is positively charged and negatively charged according to its configuration, and when the print portion remains as an electrostatic latent image by exposure, development is performed by a charged toner of the opposite sign, and the other On the other hand, in the case where the printing portion is neutralized and subjected to reversal development, development is carried out by a charged toner of the same symbol.

The toner contains a binder resin, a colorant, and other additives. A charge control agent is usually added in order to impart desired charging characteristics (charge rate, charge level, charge stability, etc.), stability over time, environmental stability, and the like. By adding the charge control agent, the characteristics of the toner are greatly improved.

Nowadays, as a positive triboelectric charge control agent known in the art, aniline black dyes are known, A dye, a copper phthalocyanine pigment, a quaternary ammonium salt, a polymer having a quaternary ammonium salt in a side chain, and the like. As the negative triboelectric charge control agent, a metal salt of a monoazo dye, a metal salt of salicylic acid, a naphthoic acid or a dicarboxylic acid, a copper phthalocyanine pigment, a resin containing an acid component, and the like are known.

Further, in the case of predicting a color toner which will be expanded in the market in the future, it is indispensable for a light color which does not affect the hue, and preferably a colorless charge control agent. Among these light-colored or colorless charge control agents, metal negative salt compounds having a hydroxybenzoic acid derivative (for example, refer to Patent Documents 1 to 3) and aromatic dicarboxylic acid metal salt compounds (for example, for a negatively chargeable toner) For example, refer to Patent Document 4), a metal-salt compound of an ortho-aminobenzoic acid derivative (for example, refer to Patent Documents 5 to 6), an organoboron compound (for example, refer to Patent Documents 7 to 8), and a bisphenol compound (for example, refer to the patent literature) 9) Cup (n) aromatic hydrocarbon compound (for example, refer to Patent Documents 10 to 15) and cyclic phenol sulfide (for example, refer to Patent Documents 16 to 18). Further, as the positively chargeable toner, there are a quaternary ammonium salt compound (see, for example, Patent Documents 19 to 21).

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Publication No. Sho 55-042752

Patent Document 2: Japanese Patent Laid-Open No. 61-069073

Patent Document 3: Japanese Patent Laid-Open No. 61-221756

Patent Document 4: Japanese Patent Laid-Open Publication No. SHO 57-111541

Patent Document 5: Japanese Patent Laid-Open No. 61-141453

Patent Document 6: Japanese Patent Laid-Open No. 62-094856

Patent Document 7: U.S. Patent No. 4,767,688

Patent Document 8: Japanese Patent Laid-Open No. 1-306061

Patent Document 9: Japanese Patent Laid-Open No. 61-003149

Patent Document 10: Japanese Patent No. 2568675

Patent Document 11: Japanese Patent No. 2899038

Patent Document 12: Japanese Patent No. 3359657

Patent Document 13: Japanese Patent No. 33138871

Patent Document 14: Japanese Patent No. 3325730

Patent Document 15: Japanese Patent Laid-Open Publication No. 2003-162100

Patent Document 16: Japanese Patent Laid-Open Publication No. 2003-295522

Patent Document 17: WO2007-111346

Patent Document 18: WO2007-119797

Patent Document 19: Japanese Patent Laid-Open Publication No. SHO 57-119364

Patent Document 20: Japanese Patent Laid-Open No. SHO 58-009154

Patent Document 21: Japanese Patent Laid-Open No. SHO 58-098742

However, these charge control agents are mostly complexes or salts containing heavy metals such as chromium, and have problems in terms of waste restriction, and are not necessarily safe. Moreover, there are the following disadvantages: the charging effect required today is low, and the rising speed of charging is insufficient, so the initial photocopying image lacks clarity, or the quality of the photocopying image in continuous photocopying is easily changed, and thus cannot be applied. The polymerized toner is medium. Therefore, a charge control agent which has a high charge imparting effect and can be applied to a polymerized toner is desired.

SUMMARY OF THE INVENTION An object of the present invention is to provide a charge control agent which has a high charge amount and is safe in terms of waste limitation. Further, it is an object of the invention to provide a negatively chargeable toner for electrostatic image development and a negatively chargeable polymerized toner having high chargeability using the charge control agent.

The present invention has been made in order to achieve the above object, and the following contents are mainly intended.

In other words, the present invention provides a charge control agent containing one or two or more kinds of the pyridinedicarboxylic acid derivatives represented by the formula (1) as an active ingredient.

In the formula (1), R ₁ , R ₂ and R ₃ may be the same or different and each represents a hydrogen atom, a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a 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, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, and 2 carbon atoms which may have a substituent a straight-chain or branched alkenyl group of ~6, a linear or branched alkoxy group having 1 to 8 carbon atoms which may have a substituent, and a cycloalkane having 5 to 10 carbon atoms which may have a substituent An oxy group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group R ₄ and R ₅ may be the same or different and each represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, and a carbon atom which may have a substituent of 5 a cycloalkyl group of ~10, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, substituted or An unsubstituted heterocyclic group or a substituted or unsubstituted condensed polycyclic aromatic group, and R ₆ and R ₇ may be the same or different and each represents a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent. A substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted condensed polycyclic aromatic group. Here, R ₁ , R ₂ and R ₃ may be bonded to each other by adjacent groups to form a ring.

The pyridinedicarboxylic acid derivative represented by the above formula (1) may also be a compound represented by the following formula (1A).

In the formula (1A), R ₁ , R ₂ and R ₃ may be the same or different and each represents a hydrogen atom, a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a 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, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, and 2 carbon atoms which may have a substituent a straight-chain or branched alkenyl group of ~6, a linear or branched alkoxy group having 1 to 8 carbon atoms which may have a substituent, and a cycloalkane having 5 to 10 carbon atoms which may have a substituent An oxy group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group R ₄ and R ₅ may be the same or different and each represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, and a carbon atom which may have a substituent of 5 a cycloalkyl group of ~10, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, substituted Non-substituted heterocyclic group, or a substituted or non-substituted condensed polycyclic aromatic group, R ₆ and R ₇ may be identical or different, it represents a substituent having a carbon atom of the cycloalkyl group having 5 to 10 A substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted condensed polycyclic aromatic group. Here, R ₁ , R ₂ and R ₃ may be bonded to each other by adjacent groups to form a ring.

The pyridinedicarboxylic acid derivative represented by the above formula (1) may be a compound represented by the following formula (1A-1).

In the formula (1A-1), R ₁ , R ₂ and R ₃ may be the same or different and each represents a hydrogen atom, a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a cyano group, or a trifluoromethyl group. a base, a nitro group, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, and a carbon atom which may have a substituent a linear or branched alkenyl group of 2 to 6 or a linear or branched alkoxy group having 1 to 8 carbon atoms which may have a substituent, and a carbon number of 5 to 10 which may have a substituent a cycloalkoxy group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aromatic group The oxy group, R ₄ and R ₅ may be the same or different and each represents a hydrogen atom, a ruthenium atom, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, and a carbon atom which may have a substituent. a cycloalkyl group of 5 to 10, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, substituted Or unsubstituted heterocyclic group, or substituted or unsubstituted condensed polycyclic aromatic group, R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ And R ₁₇ may be the same or different and represent a hydrogen atom, a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a cyano group, a trifluoromethyl group, a nitro group, and a carbon atom which may have a substituent. a linear or branched alkyl group of ~8, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent a linear or branched alkoxy group having 1 to 8 carbon atoms which may have a substituent, a cycloalkoxy group having 5 to 10 carbon atoms which may have a substituent, a substituted or unsubstituted aromatic group A hydrocarbyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group. Here, 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 may also be bonded to each other by adjacent groups. Knot to form a ring.

In the pyridinedicarboxylic acid derivative represented by the above formula (1) and the pyridinedicarboxylic acid derivative represented by the above formula (1A-1), R ₆ and R ₇ may be a carbon atom which may have a substituent of 5 ~10 cycloalkyl.

Further, the present invention provides a toner comprising a charge control agent, a colorant, and a binder resin, wherein the charge control agent contains one or more of the pyridinedicarboxylic acid derivatives represented by the above formula (1) as effective. ingredient.

The present invention further provides a polymerized toner comprising a charge control agent, a colorant, and a binder resin, wherein the charge control agent contains one or more of the pyridinedicarboxylic acid derivatives represented by the above formula (1). Active ingredients.

The charge control agent containing one or two or more kinds of the pyridinedicarboxylic acid derivatives represented by the above formula (1) as an active ingredient has a high charge amount and has excellent properties in terms of waste limitation and is safe. It is preferably used for charge control of toner. Therefore, the present invention can also be used for controlling the charge of the toner by containing one or two or more kinds of the pyridine dicarboxylic acid derivatives represented by the above formula (1) as an active ingredient, or the above-mentioned The use of a charge control agent which is one or more of the pyridinedicarboxylic acid derivatives represented by the formula (1) as an active ingredient in charge control of the toner. The above toner may also be a polymerized toner.

Furthermore, the present invention may be a charge control method of a toner using a charge control agent containing one or two or more kinds of the pyridine dicarboxylic acid derivatives represented by the above formula (1) as an active ingredient. In this case, the above toner may also be a polymerized toner.

In the present invention, the charge control agent containing one or two or more kinds of the pyridinedicarboxylic acid derivatives represented by the general formula (1) as an active ingredient has a higher rate of rise and higher in charge than the previous charge control agent. With charge, it has charging characteristics that are particularly excellent in stability over time and environmental stability. In addition, it does not contain heavy metals such as chromium, which are a concern in environmental problems, and is excellent in dispersibility and stability of compounds.

The charge control agent of the present invention is excellent in charge control property, environmental resistance and durability, and can be used for pulverizing a toner or a polymerized toner, and can obtain fog-free image density, dot reproducibility, and fine lines. An image with good reproducibility. The charge control agent is useful as a charge control agent for electrophotography which exhibits sufficient triboelectric chargeability of the toner, particularly a charge control agent for a color toner, and further as a charge control agent for a polymerized toner. And useful.

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made without departing from the spirit and scope of the invention.

The charge control agent of the present embodiment contains one or two or more kinds of the pyridine dicarboxylic acid derivatives represented by the above formula (1) as an active ingredient. First, the pyridinedicarboxylic acid derivative represented by the formula (1) will be described.

The "linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent" represented by R ₁ , R ₂ and R ₃ (R ₁ to R ₃ ) in the formula (1), "Catalysts of 5 to 10 carbon atoms which may have a substituent" or "linear or branched alkenyl groups of 2 to 6 carbon atoms which may have a substituent"" The linear or branched alkyl group, the "cycloalkyl group having 5 to 10 carbon atoms" or the "linear or branched alkenyl group having 2 to 6 carbon atoms" may specifically be a methyl group. , ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, isoheptyl, n-octyl , isooctyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, vinyl, allyl, isopropenyl and 2-butenyl, etc., R ₁ to R ₃ may also be Adjacent groups are bonded to each other via a single bond, an oxygen atom or a sulfur atom to form a ring.

The linear or branched alkyl group having 1 to 8 carbon atoms having a substituent represented by R ₁ to R ₃ in the formula (1), and the carbon atom having a substituent of 5 to 10 The "substituent" in the cycloalkyl group or the "linear or branched alkenyl group having 2 to 6 carbon atoms having a substituent" may specifically be a halogen atom, a trifluoromethyl group or a cyano group. Nitro, hydroxy; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl a linear or branched alkyl group having 1 to 8 carbon atoms such as isopentyl, neopentyl, n-hexyl, n-heptyl, isoheptyl, n-octyl or isooctyl; methoxy, B a linear or branched alkoxy group having 1 to 8 carbon atoms such as an oxy group or a propoxy group; an alkenyl group such as an allyl group; an aralkyl group such as a benzyl group, a naphthylmethyl group or a phenethyl group; An aryloxy group such as a benzyl group or a tolyloxy group; an aralkyloxy group such as a benzyloxy group or a phenethyloxy group; a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, an anthracenyl group Sulfhydryl, mercapto, propofolyl An aromatic hydrocarbon group such as a terphenyl group or a condensed polycyclic aromatic group; a pyridyl group, a furanyl group, a pyranyl group, a thienyl group, a furyl group, a pyrrolyl group, a pyrrolidinyl group, an imidazolyl group, an imidazoline group Base, imidazolidinyl, pyrazolyl, pyrazolinyl, pyrazolyl, hydrazine Base Peptidyl, piperidine Piperazinyl, thiolanyl, thioalkyl, quinolyl, isoquinolinyl, benzofuranyl, benzothienyl, fluorenyl, carbazolyl, benzo Azolyl, benzothiazolyl, quin a heterocyclic group such as quinoxalyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothiophenyl or porphyrin; arylvinyl such as styryl or naphthylvinyl; a mercapto group such as a mercapto group or a benzamidine group; a dialkylamino group such as a dimethylamino group or a diethylamino group; an aromatic hydrocarbon group or a condensed polycyclic aromatic group such as a diphenylamino group or a dinaphthylamino group; a disubstituted amino group substituted with a group; a diarylalkylamino group such as a dibenzylamino group or a diphenylethylamino group; a dipyridylamino group, a dithienylamino group, a dipiperidinylamino group, etc. a disubstituted amino group substituted with a cyclo group; a dienylamino group such as a diallylamino group; selected from an alkyl group, an aromatic hydrocarbon group, a condensed polycyclic aromatic group, an aralkyl group, a heterocyclic group or an alkenyl group; The substituent may be substituted with a substituent such as a disubstituted amine group, and the substituent may be further substituted with another substituent, or may be bonded to each other via a single bond, an oxygen atom or a sulfur atom to form a ring.

Among the "linear or branched alkyl groups having 1 to 8 carbon atoms which may have a substituent" represented by R ₁ to R ₃ in the formula (1), it is preferred to have a substituent. A linear or branched alkyl group having 1 to 4 carbon atoms.

Further, among the "cycloalkyl groups having 5 to 10 carbon atoms which may have a substituent" represented by R ₁ to R ₃ in the formula (1), it is preferred that the number of carbon atoms which may have a substituent is 5 ~6 cycloalkyl".

Further, among the "linear or branched alkenyl groups having 2 to 6 carbon atoms which may have a substituent" represented by R ₁ to R ₃ in the formula (1), it is preferred that "may have a substitution" A linear or branched alkenyl group having 2 to 4 carbon atoms.

The linear or branched alkoxy group having 1 to 8 carbon atoms which may have a substituent represented by R ₁ to R ₃ in the formula (1) or the number of carbon atoms which may have a substituent In the cyclopentaloxy group of 5 to 10, "a linear or branched alkoxy group having 1 to 8 carbon atoms" or "a cycloalkoxy group having 5 to 10 carbon atoms" may specifically be as follows: Oxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, isoheptyloxy, n-octyloxy a group, an isooctyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, a 1-adamantyloxy group, a 2-adamantanyloxy group, etc., and R ₁ to R ₃ may also be derived from a phase. The adjacent groups are bonded to each other via a single bond, an oxygen atom or a sulfur atom to form a ring.

The linear or branched alkoxy group having 1 to 8 carbon atoms having a substituent represented by R ₁ to R ₃ in the formula (1) or the number of carbon atoms having a substituent of 5 to 5 Specific examples of the "substituent" in the cycloalkyloxy group of 10 include a halogen atom, a trifluoromethyl group, a cyano group, a nitro group, a hydroxyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; Base, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, isoheptyl, positive a linear or branched alkyl group having 1 to 8 carbon atoms such as an octyl group or an isooctyl group; a linear or branched carbon group having 1 to 8 carbon atoms such as a methoxy group, an ethoxy group or a propoxy group; Alkenyloxy group; allyl group such as allyl group; aralkyl group such as benzyl group, naphthylmethyl group or phenethyl group; aryloxy group such as phenoxy group or tolyloxy group; aralkyl group such as benzyloxy group and phenethyloxy group; Oxyl; phenyl, biphenyl, terphenyl, furyl, fluorenyl, phenanthryl, anthracenyl, fluorenyl, fluorenyl, fluorenyl, alkadienyl, hydrazine, etc. Aromatic hydrocarbon group or condensed polycyclic aromatic group; pyridyl group, fur Furanyl, pyranyl, thienyl, furyl, pyrrolyl, pyrrolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyrazolyl, pyrazolinyl, pyrazolyl, hydrazine Base Peptidyl, piperidine Base, tetrahydrothiophenyl, thioalkyl, quinolyl, isoquinolinyl, benzofuranyl, benzothienyl, fluorenyl, carbazolyl, benzo Azolyl, benzothiazolyl, quin a heterocyclic group such as a phenyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group or a porphyrin group; an arylvinyl group such as a styryl group or a naphthylvinyl group; a mercapto group such as a benzyl group; a dialkylamino group such as a dimethylamino group or a diethylamino group; a diphenylamino group or a dinaphthylamino group substituted with an aromatic hydrocarbon group or a condensed polycyclic aromatic group; a substituted diamino group; a diarylalkylamino group such as a dibenzylamino group or a diphenylethylamino group; a dipyridylamino group, a dithienylamino group, a dipiperidinylamino group or the like substituted with a heterocyclic group; a disubstituted amino group; a dienylamino group such as a diallylamino group; a substituent selected from an alkyl group, an aromatic hydrocarbon group, a condensed polycyclic aromatic group, an aralkyl group, a heterocyclic group or an alkenyl group; Substituents such as substituted disubstituted amine groups may be further substituted with other substituents, or may be bonded to each other via a single bond, an oxygen atom or a sulfur atom to form a ring.

Further, among the "linear or branched alkoxy groups having 1 to 8 carbon atoms which may have a substituent" represented by R ₁ to R ₃ in the formula (1), it is preferred to have "may have A linear or branched alkoxy group having 1 to 4 carbon atoms in the substituent.

Further, among the "cycloalkyloxy groups having 5 to 10 carbon atoms which may have a substituent" represented by R ₁ to R ₃ in the formula (1), it is preferred that the number of carbon atoms which may have a substituent 5 to 6 cycloalkoxy groups".

As the "substituted or unsubstituted aromatic hydrocarbon group" represented by R ₁ to R ₃ in the formula (1), "substituted or unsubstituted heterocyclic group" or "substituted or unsubstituted Specific examples of the "aromatic hydrocarbon group", the "heterocyclic group" or the "condensed polycyclic aromatic group" in the condensed polycyclic aromatic group include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, and a fluorenyl group. , phenanthryl, anthracenyl, fluorenyl, fluorenyl, fluorenyl, allyldienyl, triphenyl, pyridyl, furyl, pyranyl, thienyl, pyrrolidinyl, imidazolyl, imidazoline Base, imidazolidinyl, pyrazolyl, pyrazolinyl, pyrazolyl, hydrazine Base Peptidyl, piperidine Base, tetrahydrothiophenyl, thioalkyl, quinolyl, isoquinolinyl, benzofuranyl, benzothienyl, fluorenyl, carbazolyl, benzo Azolyl, benzothiazolyl, quin a phenyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothienyl group, a porphyrin group, etc., and R ₁ to R ₃ may also be bonded to each other via a single bond, an oxygen atom or a sulfur atom. Bonded to each other to form a ring.

The substituent in the "substituted aromatic hydrocarbon group", the "substituted heterocyclic group" or the "substituted condensed polycyclic aromatic group" represented by R ₁ to R ₃ in the formula (1) Specific examples thereof include a halogen atom, a cyano group, a trifluoromethyl group, a nitro group, and a hydroxyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a methyl group, an ethyl group, a n-propyl group, and an isopropyl group; , n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, isoheptyl, n-octyl, isooctyl and other carbon atoms 1~ a linear or branched alkyl group of 8; a cycloalkyl group having 5 to 10 carbon atoms such as a cyclopentyl group or a cyclohexyl group; a carbon such as a vinyl group, an allyl group, a 2-butenyl group or a 1-hexenyl group; a linear or branched alkenyl group having 2 to 6 atoms; a linear or branched alkoxy group having 1 to 8 carbon atoms such as a methoxy group, an ethoxy group or a propoxy group; a cycloalkoxy group having 5 to 10 carbon atoms such as a cyclohexyloxy group; an aralkyl group such as a benzyl group, a naphthylmethyl group or a phenethyl group; a phenoxy group, a tolyloxy group, a biphenyloxy group, and a terphenyloxy group; Base, naphthyloxy, decyloxy, phenanthryloxy, decyloxy An aryloxy group such as a decyloxy group, a decyloxy group or a decyloxy group; an aralkyloxy group such as a benzyloxy group or a phenethyloxy group; a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl group, An aromatic hydrocarbon group or a condensed polycyclic aromatic group such as an anthracenyl group, a fluorenyl group, a fluorenyl group, a fluorenyl group, a propadienyl fluorenyl group or a terphenyl group; a pyridyl group, a furanyl group, a pyranyl group, a thienyl group , furyl, pyrrolyl, pyrrolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyrazolyl, pyrazolinyl, pyrazolyl, hydrazine Base Peptidyl, piperidine Base, tetrahydrothiophenyl, thioalkyl, quinolyl, isoquinolinyl, benzofuranyl, benzothienyl, fluorenyl, carbazolyl, benzo Azolyl, benzothiazolyl, quin a heterocyclic group such as a phenyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group or a porphyrin group; an arylvinyl group such as a styryl group or a naphthylvinyl group; a mercapto group such as a benzyl group; a dialkylamino group such as a dimethylamino group or a diethylamino group; a diphenylamino group or a dinaphthylamino group substituted with an aromatic hydrocarbon group or a condensed polycyclic aromatic group; a substituted diamino group; a diarylalkylamino group such as a dibenzylamino group or a diphenylethylamino group; a dipyridylamino group, a dithienylamino group, a dipiperidinylamino group or the like substituted with a heterocyclic group; a disubstituted amino group; a dienylamino group such as a diallylamino group; a substituent selected from an alkyl group, an aromatic hydrocarbon group, a condensed polycyclic aromatic group, an aralkyl group, a heterocyclic group or an alkenyl group; Substituents such as substituted disubstituted amine groups may be further substituted with other substituents, or may be bonded to each other via a single bond, an oxygen atom or a sulfur atom to form a ring.

Specific examples of the "aryloxy group" in the "substituted or unsubstituted aryloxy group" represented by R ₁ to R ₃ in the formula (1) include phenoxy group, tolyloxy group and biphenyl group. An oxy group, a triphenyloxy group, a naphthyloxy group, a decyloxy group, a phenanthryloxy group, a decyloxy group, a decyloxy group, a decyloxy group, a decyloxy group or the like, and R ₁ to R ₃ may also be bonded to each other via an adjacent group. A single bond, an oxygen atom or a sulfur atom is bonded to each other to form a ring.

Specific examples of the "substituent" in the "substituted aryloxy group" represented by R ₁ to R ₃ in the formula (1) include a halogen atom, a cyano group, a trifluoromethyl group, a nitro group and a hydroxyl group. a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl , neopentyl, n-hexyl, n-heptyl, isoheptyl, n-octyl, isooctyl and the like, a straight or branched alkyl group having 1 to 8 carbon atoms; a carbon atom such as a cyclopentyl group or a cyclohexyl group; a cycloalkyl group of 5 to 10; a linear or branched alkenyl group having 2 to 6 carbon atoms such as a vinyl group, an allyl group, a 2-butenyl group or a 1-hexenyl group; a methoxy group; a linear or branched alkoxy group having 1 to 8 carbon atoms such as an oxy group or a propoxy group; a cycloalkoxy group having 5 to 10 carbon atoms such as a cyclopentyloxy group or a cyclohexyloxy group; a benzyl group; Aralkyl group such as naphthylmethyl or phenethyl; phenoxy, tolyloxy, biphenyloxy, terphenyloxy, naphthyloxy, anthracenyloxy, phenanthryloxy, decyloxy, decyloxy An aryloxy group such as a decyloxy group or a decyloxy group; a benzyloxy group, a phenethyloxy group, etc. An oxy group; an aromatic hydrocarbon group such as a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a fluorenyl group, a fluorenyl group, a fluorenyl group, a fluorenyl group, an allyl group, a fluorenyl group Or a condensed polycyclic aromatic group; pyridyl, furanyl, pyranyl, thienyl, furyl, pyrrolyl, pyrrolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyrazole Base, pyrazolinyl, pyrazolyl, hydrazine Base Peptidyl, piperidine Base, tetrahydrothiophenyl, thioalkyl, quinolyl, isoquinolinyl, benzofuranyl, benzothienyl, fluorenyl, carbazolyl, benzo Azolyl, benzothiazolyl, quin a heterocyclic group such as a phenyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group or a porphyrin group; an arylvinyl group such as a styryl group or a naphthylvinyl group; a mercapto group such as a benzyl group; a dialkylamino group such as a dimethylamino group or a diethylamino group; a diphenylamino group or a dinaphthylamino group substituted with an aromatic hydrocarbon group or a condensed polycyclic aromatic group; a substituted diamino group; a diarylalkylamino group such as a dibenzylamino group or a diphenylethylamino group; a dipyridylamino group, a dithienylamino group, a dipiperidinylamino group or the like substituted with a heterocyclic group; a disubstituted amino group; a dienylamino group such as a diallylamino group; a substituent selected from an alkyl group, an aromatic hydrocarbon group, a condensed polycyclic aromatic group, an aralkyl group, a heterocyclic group or an alkenyl group; Substituents such as substituted disubstituted amine groups may be further substituted with other substituents, or may be bonded to each other via a single bond, an oxygen atom or a sulfur atom to form a ring.

R ₁ to R ₃ in the formula (1) are preferably a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, or may have a substituent. The cycloalkyl group having 5 to 10 carbon atoms is more preferably a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent, and more preferably a hydrogen atom. Or helium atom.

The linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent as represented by R ₄ and R ₅ in the formula (1), and the number of carbon atoms which may have a substituent of 5 "A linear alkyl group having a carbon number of 1 to 8" or a branched alkyl group having a carbon number of from 1 to 8 in a cycloalkyl group of "10" or "a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent""A cycloalkyl group having 5 to 10 carbon atoms" or a "linear or branched alkenyl group having 2 to 6 carbon atoms" is the same as those described above for R ₁ to R ₃ . The substituents which these groups may have are also the same as those shown for R ₁ to R ₃ .

As the "substituted or unsubstituted aromatic hydrocarbon group" represented by R ₄ and R ₅ in the formula (1), "substituted or unsubstituted heterocyclic group" or "substituted or unsubstituted" The "aromatic hydrocarbon group", the "heterocyclic group" or the "condensed polycyclic aromatic group" in the condensed polycyclic aromatic group are the same as those described above for R ₁ to R ₃ , and the groups may be used. The substituents having the same are also the same as those shown for R ₁ to R ₃ .

R ₄ and R ₅ in the formula (1) are preferably a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, or may have a substituent. The cycloalkyl group having 5 to 10 carbon atoms is more preferably a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent, and more preferably a hydrogen atom. Or helium atom.

The "cycloalkyl group having 5 to 10 carbon atoms" in the "cycloalkyl group having 5 to 10 carbon atoms which may have a substituent" represented by R ₆ and R ₇ in the formula (1) may specifically Listed: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, 1-adamantyl, 2-adamantyl and the like.

The "aromatic hydrocarbon group" in the "substituted or unsubstituted aromatic hydrocarbon group" or the "substituted or unsubstituted condensed polycyclic aromatic group" represented by R ₆ and R ₇ in the formula (1) Or "condensed polycyclic aromatic group", specifically, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, a fluorenyl group, a fluorenyl group, a fluorenyl group, a fluorenyl group, and a propadiene. Mercapto group and triphenyl group.

The "cycloalkyl group having 5 to 10 carbon atoms having a substituent" represented by R ₆ and R ₇ in the formula (1), "substituted aromatic hydrocarbon group" or "substituted condensed polycyclic aromatic group" Specific examples of the "substituent group" in the "group" include a halogen atom, a trifluoromethyl group, a cyano group, a nitro group, a hydroxyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a methyl group and an ethyl group; , n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, isoheptyl, n-octyl, iso a linear or branched alkyl group having 1 to 8 carbon atoms such as an octyl group; a linear or branched alkoxy group having 1 to 8 carbon atoms such as a methoxy group, an ethoxy group or a propoxy group; Allyl group such as allyl group; aralkyl group such as benzyl group, naphthylmethyl group or phenethyl group; aryloxy group such as phenoxy group or tolyloxy group; aralkyloxy group such as benzyloxy group and phenethyloxy group; Aromatic hydrocarbon group or condensed polycyclic ring such as phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, anthracenyl, fluorenyl, fluorenyl, fluorenyl, alkadienyl, hydrazine Aromatic group; pyridyl group, furyl group (furanyl), pyranyl, thienyl, furyl, pyrrolyl, pyrrolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyrazolyl, pyrazolinyl, pyrazolyl, hydrazine Base Peptidyl, piperidine Base, tetrahydrothiophenyl, thioalkyl, quinolyl, isoquinolinyl, benzofuranyl, benzothienyl, fluorenyl, carbazolyl, benzo Azolyl, benzothiazolyl, quin a heterocyclic group such as a phenyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group or a porphyrin group; an arylvinyl group such as a styryl group or a naphthylvinyl group; a mercapto group such as a benzyl group; a dialkylamino group such as a dimethylamino group or a diethylamino group; a diphenylamino group or a dinaphthylamino group substituted with an aromatic hydrocarbon group or a condensed polycyclic aromatic group; a substituted diamino group; a diarylalkylamino group such as a dibenzylamino group or a diphenylethylamino group; a dipyridylamino group, a dithienylamino group, a dipiperidinylamino group or the like substituted with a heterocyclic group; a disubstituted amino group; a dienylamino group such as a diallylamino group; a substituent selected from an alkyl group, an aromatic hydrocarbon group, a condensed polycyclic aromatic group, an aralkyl group, a heterocyclic group or an alkenyl group; Substituents such as substituted disubstituted amine groups may be further substituted with other substituents, or may be bonded to each other via a single bond, an oxygen atom or a sulfur atom to form a ring.

The "cycloalkyl group having 5 to 10 carbon atoms having a substituent" represented by R ₆ and R ₇ in the formula (1), "substituted aromatic hydrocarbon group" or "substituted condensed polycyclic aromatic group" The "substituent" in the "group" is preferably a halogen atom, a trifluoromethyl group, a cyano group, a nitro group, a hydroxyl group, a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, and carbon. A linear or branched alkoxy group having an atomic number of 1 to 8.

R ₆ and R ₇ in the formula (1) are preferably a cycloalkyl group having 5 to 10 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group which may have a substituent. More preferably, R ₆ and R ₇ are each a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, or both substituted or unsubstituted aromatic hydrocarbon groups. In this case, R ₆ and R ₇ may be the same or different. R ₆ and R ₇ are each a substituted or unsubstituted aromatic hydrocarbon group, and more preferably R ₆ is represented by the following general formula (1A-2), and R ₇ is a general formula ( 1A-3).

In the general formula (1A-2) and the general formula (1A-3), R ₈ to R ₁₇ may be the same or different and each represents a hydrogen atom, a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, and a cyanogen. a linear, trifluoromethyl group, a nitro group, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, and may have a linear or branched alkenyl group having 2 to 6 carbon atoms in the substituent, a linear or branched alkoxy group having 1 to 8 carbon atoms which may have a substituent, and a carbon atom which may have a substituent a 5 to 10 cycloalkoxy group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or Unsubstituted aryloxy group. Here, R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ or R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ may be bonded to each other by adjacent groups to form a ring. * indicates a bond.

The "linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent" represented by R ₈ to R ₁₇ in the formula (1A-2) and the formula (1A-3), "Catalysts of 5 to 10 carbon atoms which may have a substituent" or "linear or branched alkenyl groups of 2 to 6 carbon atoms which may have a substituent"" the straight-chain or branched alkyl group of "alkyl" or "ring carbon atoms" 5 to 10 carbon atoms and 2 to 6 of the straight-chain or branched alkenyl group of "based on the above-described R ₁ The same groups as shown by ~R ₃ may have the same substituents as those described for R ₁ to R ₃ .

As the "substituted or unsubstituted aromatic hydrocarbon group" represented by R ₈ to R ₁₇ in the general formula (1A-2) and the general formula (1A-3), "substituted or unsubstituted heterocyclic group" Or "aromatic hydrocarbon group", "heterocyclic group" or "condensed polycyclic aromatic group" in the "substituted or unsubstituted condensed polycyclic aromatic group", and the above-mentioned R ₁ to R ₃ The substituents may be the same, and the substituents which these groups may have are also 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 formula (1A-2) and the formula (1A-3) is as described above. R ₁ to R ₃ are the same groups, and the substituents may have the same substituents as those described for R ₁ to R ₃ .

R ₈ to R ₁₇ in the formula (1A-2) and the formula (1A-3) are preferably a halogen atom, a trifluoromethyl group, a cyano group, a nitro group, a hydroxyl group, a halogen atom or a carbon atom number of 1. a linear or branched alkyl group of ~8, a linear or branched alkoxy group having 1 to 8 carbon atoms.

The pyridinedicarboxylic acid derivative represented by the above formula (1) may be, for example, a pyridinedicarboxylic acid derivative represented by the following formula (1A) or the following formula (1A-1).

In the formula (1A), R ₁ to R _{7 are} as described above.

In the formula (1A-1), R ₁ to R ₅ and R ₈ to R _{17 are} as described above.

The pyridinedicarboxylic acid derivative represented by the formula (1) of the present embodiment can be produced by a known method. For example, the present embodiment can be synthesized by reacting a corresponding dichloride of dipicolinic acid with a corresponding alicyclic hydrocarbon having an amine group, an aromatic hydrocarbon or a condensed polycyclic aromatic group in the presence of a base or the like. Pyridine dicarboxylic acid derivative. Further, it can also be synthesized by reacting the corresponding pyridinedicarboxylic acid with a corresponding alicyclic hydrocarbon having an amine group, an aromatic hydrocarbon or a condensed polycyclic aromatic compound in the presence of a dehydrating condensing agent.

Specific examples of preferred compounds of the pyridinedicarboxylic acid derivative represented by the formula (1) of the present invention are shown below, but the present invention is not limited to the compounds.

Further, in the following structural formula, the description of the hydrogen atom is omitted. Further, even in the case where a stereoisomer is present, the planar structural formula is also described.

In the present embodiment, the charge control agent is preferably used by adjusting the volume average particle diameter to a range of from 0.1 μm to 20 μm, and more preferably to a range of from 0.1 μm to 10 μm. When the volume average particle diameter is less than 0.1 μm, the charge control agent which appears on the surface of the toner tends to be extremely small, and it is difficult to obtain a target charge control effect. Further, if it is larger than 20 μm, the toner is detached from the toner. The charge control agent is increased, which tends to cause adverse effects such as contamination inside the machine, and is therefore unsatisfactory.

Further, in the case where a charge control agent is used for the polymerization of the toner, it is preferred to The average particle diameter is adjusted to 1.0 μm or less and used, and it is preferably adjusted to a range of 0.01 μm to 1.0 μm. When the volume average particle diameter exceeds 1.0 μm, there is a case where the particle size distribution of the finally obtained toner for electrophotography is broadened or free particles are generated, resulting in deterioration in performance or reliability. On the other hand, if the average particle diameter is within the above range, not only the above disadvantages are not present, but also the following aspects are advantageous: the uneven distribution among the toners is reduced, the dispersion in the toner becomes good, and the performance and reliability are obtained. The deviation becomes smaller.

The method of including the charge control agent of the present embodiment in the toner, such as a method of adding and pulverizing together with a coloring agent or the like, and kneading the powder (pulverized toner), or a single polymerization property A method of adding a charge control agent to a body to carry out polymerization to obtain a toner (polymerized toner), a method of previously adding to the inside of the toner particles (inner addition), and pre-manufacturing the toner particles A method of adding (external addition) to the surface of the toner particles. The amount of the preferable charge control agent added to the toner particles is preferably an amount of 0.1 to 10 parts by mass, based on 100 parts by mass of the binder resin, more preferably Good is 0.2~5 parts by mass. Further, in the case of externally adding to the toner particles, the amount of the charge control agent added is preferably an amount of preferably 0.01 to 5 by mass based on 100 parts by mass of the binder resin. More preferably, it is 0.01 to 2 parts by mass. Further, it is preferably mechanically fixed to the surface of the toner particles.

Further, in the present embodiment, the charge control agent containing the pyridinedicarboxylic acid derivative represented by the formula (1) as an active ingredient can be used in combination with other known negatively chargeable charge control agents. Preferred charge control agents for use include azo-based iron complex or staggered salt, azo-chromium complex or staggered salt, azo-based manganese complex or staggered salt, and azo-based cobalt. a compound or a wrong salt, an azo zirconium complex or a wrong salt, a chromium complex or a wrong salt of a carboxylic acid derivative, a zinc complex or a wrong salt of a carboxylic acid derivative, or an aluminum wrong of a carboxylic acid derivative a zirconium complex or a wrong salt of a salt or a salt of a carboxylic acid. The above carboxylic acid derivative is preferably an aromatic hydroxycarboxylic acid, more preferably 3,5-di-t-butylsalicylic acid. Further, a boron complex or a wrong salt or a negatively charged resin can be cited. Type charge control agent, etc.

In the present embodiment, the amount of addition of the charge control agent and the other charge control agent of the present embodiment is preferably a charge control agent other than the charge control agent of the present embodiment with respect to 100 parts by mass of the binder resin. It is 0.1 to 10 parts by mass.

The binder resin used in the toner of the present embodiment can be used arbitrarily as long as it is known. Examples thereof include a vinyl polymer such as a styrene monomer, an acrylate monomer, or a methacrylate monomer, or a copolymer containing two or more of these monomers, and a polyester polymer or a polyol. Resin, phenol resin, polyoxyl resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, terpene resin, benzofuran-indene resin, polycarbonate resin, Petroleum resin, etc.

The styrene-based monomer, the acrylate-based monomer, and the methacrylate-based monomer which form the above-mentioned ethylene-based polymer or copolymer are exemplified below, but are not limited thereto.

Examples of the styrene-based monomer include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-phenyl styrene, p-ethyl styrene, and 2,4-dimethyl. Styrene, p-n-pentyl styrene, p-tert-butyl styrene, p-n-hexyl styrene, p-n-octyl styrene, p-n-decyl styrene, p-n-decyl styrene, p-dodecane Styrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, etc. .

Examples of the acrylate-based monomer include acrylic acid or methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-dodecyl acrylate, and acrylic acid 2- Acrylic acid such as ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate or phenyl acrylate or an ester thereof.

Examples of the methacrylate monomer include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and methyl group. N-octyl acrylate, n-dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacryl A methacrylic acid such as dimethylaminoethyl acrylate or diethylaminoethyl methacrylate or an ester thereof.

Examples of the other monomer forming the vinyl polymer or copolymer include the following (1) to (18). (1) monoolefins such as ethylene, propylene, butylene, and isobutylene; (2) polyenes such as butadiene and isoprene; and (3) halogenated vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride. Ethylene; (4) vinyl acetate such as vinyl acetate, vinyl propionate or vinyl benzoate; (5) vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; (6) ethylene Ketones such as methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; (7) N-vinyl pyrrole, N-vinyl oxazole, N-vinyl fluorene, N-vinyl pyrrolidine N-vinyl compound such as ketone; (8) vinyl naphthalene; (9) acrylic acid or methacrylic acid derivative such as acrylonitrile, methacrylonitrile or acrylamide; (10) maleic acid, A An unsaturated dibasic acid such as maleic acid, methylene succinic acid, alkenyl succinic acid, fumaric acid or methyl fumaric acid; (11) maleic anhydride, A An unsaturated dibasic acid anhydride such as a maleic anhydride, a methylene succinic anhydride or an alkenyl succinic anhydride; (12) a maleic acid monomethyl ester, a maleic acid monoethyl ester, a maleic acid Dibutyl succinate, methyl cis-butene Monomethyl diacid, monoethyl male methacrylate, methyl maleic acid monobutyl ester, methylene succinic acid monomethyl ester, alkenyl succinic acid monomethyl ester, anti-butene Monoester of unsaturated dibasic acid such as monomethyl diacid or monomethyl fumarate; (13) unsaturated ester of dimethyl maleate or dimethyl fumarate (1) an α,β-unsaturated acid such as crotonic acid or cinnamic acid; (15) an α,β-unsaturated acid anhydride such as butyric anhydride or cinnamic anhydride; (16) the α,β-unsaturated An acid having a lower fatty acid, an alkenyl malonic acid, an alkenyl glutaric acid, an alkenyl adipic acid, an acid anhydride, and a monoester having a carboxyl group; (17) 2-hydroxyethyl acrylate Acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, etc. Acrylic or hydroxyalkyl methacrylate; (18) 4-(1-hydroxy-1-methylbutyl)styrene a monomer having a hydroxyl group such as 4-(1-hydroxy-1-methylhexyl)styrene.

In the toner of the embodiment, the vinyl polymer or copolymer of the binder resin Further, it may have a crosslinked structure obtained by crosslinking a crosslinking agent containing two or more vinyl groups, and a crosslinking agent used in this case as an aromatic divinyl compound. For example, divinylbenzene or divinylnaphthalene can be mentioned. Examples of the diacrylate compound obtained by linking an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and 1,4-butanediol diacrylate. 5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate or the replacement of the acrylate of the above compound with methacrylate.

Examples of the diacrylate compound obtained by linking an alkyl chain having an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and polyethylene. Alcohol #400 diacrylate, polyethylene glycol #600 diacrylate, dipropylene glycol diacrylate or the acrylate of the above compound is replaced by methacrylate.

In addition, a diacrylate compound or a dimethacrylate compound which is linked by a chain containing an aromatic group and an ether bond may also be mentioned. The polyester diacrylate is exemplified by MANDA (manufactured by Nippon Kayaku Co., Ltd.).

Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and The acrylate of the above compound is replaced by methacrylate, triallyl cyanurate or triallyl trimellitate.

The crosslinking agent is preferably used in an amount of 0.01 to 10 parts by mass, particularly preferably 0.03 to 5 parts by mass, based on 100 parts by mass of the other monomer components. Among the above-mentioned crosslinkable monomers, those which are preferably used for the toner resin in terms of fixability and offset resistance include aromatic divinyl compounds (especially diethylene). A bisphenol compound obtained by linking a bond chain containing an aromatic group and one ether bond. Among these, a combination of a monomer such as a styrene-based copolymer or a styrene-acrylate copolymer is preferred.

In the present embodiment, examples of the polymerization initiator used in the production of the ethylene-based polymer or copolymer include 2,2'-azobisisobutyronitrile and 2,2'-azobis ( 4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methyl Butyronitrile), 2,2'-azobisisobutyric acid dimethyl ester, 1,1'-azobis(1-cyclohexanecarbonitrile), 2-(aminomethylmercaptoazo)-isobutyl Nitrile, 2,2'-azobis(2,4,4-trimethylpentane), 2-phenylazo-2',4'-dimethyl-4'-methoxyvaleronitrile, 2,2'-azobis(2-methylpropane), methyl ketone peroxide, acetoxyacetone peroxide, cyclohexanone peroxide, etc., 2,2-double (third Base oxidized butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, peroxidation Tert-butyl cumene, dicumyl peroxide, α-(t-butylperoxy) isopropylbenzene, isobutyl peroxide, octoate octanoate, cerium peroxide, laurel , 3,5,5-trimethylhexyl peroxide, benzammonium peroxide, m-tolyl peroxide Diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, diethyl peroxydicarbonate Oxypropyl isopropyl ester, bis(3-methyl-3-methoxybutyl)peroxycarbonate, acetamidine cyclohexyl sulfone peroxide, tert-butyl peroxyacetate, isobutyric acid peroxide Tributyl ester, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy laurate, tert-butyl peroxybenzoate, tert-butyl peroxydicarbonate, peroxidation Di-tert-butyl phthalate, tert-butyl peroxyallyl carbonate, isoamyl peroxy-2-ethylhexanoate, di-tert-butyl peroxydihydroterephthalate, Dibutyl succinate and the like.

In the case where the binder resin is a styrene-acrylate resin, the following resins are preferred in terms of fixability, offset property, and preservability: tetrahydrofuran (hereinafter abbreviated as THF) soluble component of the resin component In the molecular weight distribution obtained by gel permeation chromatography (hereinafter abbreviated as GPC), at least one peak exists in a region having a molecular weight of 3,000 to 50,000 (in terms of number average molecular weight), and is in a region having a molecular weight of 100,000 or more. Resin with at least 1 peak in memory. Moreover, the component having a molecular weight distribution of 100,000 or less in the THF soluble component reaches 50 ~90% of the bonding resin is also preferred. Further, it is more preferable to have a main peak in a region having a molecular weight of 5,000 to 30,000, preferably in a region of 5,000 to 20,000.

When the binder resin is a vinyl polymer such as a styrene-acrylate resin, the acid value is preferably from 0.1 mgKOH/g to 100 mgKOH/g, more preferably from 0.1 mgKOH/g to 70 mgKOH/g. More preferably, it is 0.1 mgKOH/g~50 mgKOH/g.

The following may be mentioned as a monomer which comprises a polyester-type polymer. Examples of the glycol component include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, and triethylene glycol. , 5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or polymerized ethylene oxide on bisphenol A, A diol or the like obtained by a cyclic ether such as propylene oxide.

In order to crosslink the polyester resin, it is preferred to use a trihydric or higher alcohol in combination. Examples of the trihydric or higher polyhydric alcohol include sorbitol, 1,2,3,6-hexanetetraol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-. Butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylol Propane, 1,3,5-trihydroxybenzene, and the like.

Examples of the acid component forming the polyester-based polymer include benzenedicarboxylic acid such as phthalic acid, isophthalic acid, and terephthalic acid or an acid anhydride thereof, succinic acid, adipic acid, and sebacic acid. Alkyl dicarboxylic acids such as sebacic acid or anhydrides thereof, maleic acid, methyl maleic acid, methylene succinic acid, alkenyl succinic acid, fumaric acid, methyl butyl An unsaturated dibasic acid such as enedic acid, an unsaturated dibasic acid anhydride such as maleic anhydride, methyl maleic anhydride, methylene succinic anhydride or alkenyl succinic anhydride. Further, examples of the trivalent or higher polycarboxylic acid component include trimellitic acid, pyromellitic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4. -butane tricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetrakis(methylenecarboxy)methane, 1,2, 7,8-octanetetracarboxylic acid, Enpol trimer acid or such anhydrides, partial lower alkyl esters, and the like.

When the binder resin is a polyester resin, the fixability and the bias resistance of the toner are In terms of mobility, it is preferred that at least one peak exists in a molecular weight of 3,000 to 50,000 in the molecular weight distribution of the THF soluble component of the resin component, and the molecular weight of the THF soluble component is less than 100,000. A bonding resin having a composition of 60 to 100% is also preferred. Further, it is more preferable that at least one peak exists in a region having a molecular weight of 5,000 to 20,000.

In the present embodiment, the molecular weight distribution of the binder resin is measured by GPC using THF as a solvent. The molecular weight is, for example, a standard polystyrene-equivalent number average molecular weight measured by an HLC-8220 GPC apparatus (manufactured by Tosoh Corporation).

When the binder resin is a polyester resin, the acid value is preferably from 0.1 mgKOH/g to 100 mgKOH/g, more preferably from 0.1 mgKOH/g to 70 mgKOH/g, and even more preferably from 0.1 mgKOH/g to 50. mgKOH/g.

Further, the hydroxyl value is preferably 30 mgKOH/g or less, more preferably 10 mgKOH/g to 25 mgKOH/g.

In the present embodiment, two or more kinds of amorphous polyester resin and crystalline polyester resin may be used in combination. In this case, it is preferred to select materials in consideration of their respective compatibility.

As the amorphous polyester resin, those synthesized from a polyvalent carboxylic acid component, preferably an aromatic polycarboxylic acid and a polyol component can be preferably used.

As the crystalline polyester resin, those synthesized from a dicarboxylic acid component, preferably an aliphatic dicarboxylic acid and a glycol component can be preferably used.

The binder resin which can be used in the toner of the present embodiment can be used as a resin containing a monomer component reactive with the two resin components in the vinyl polymer component and/or the polyester resin component. Examples of the monomer constituting the polyester resin component that can react with the ethylene-based polymer include phthalic acid, maleic acid, methyl maleic acid, methylene succinic acid, and the like. An unsaturated dicarboxylic acid or an anhydride thereof or the like. Examples of the monomer constituting the vinyl polymer component include those having a carboxyl group or a hydroxyl group, or acrylic acid or methacrylic acid esters.

When a polyester polymer, a vinyl polymer, or another binder resin is used in combination, it is preferred that the resin having an acid value of 60% by mass or more of the entire binder resin is 0.1 mgKOH/g to 50 mgKOH/g. .

In the present embodiment, the acid value of the binder resin component of the toner composition can be determined by the following method, and the basic operation is based on JIS (Japanese Industrial Standards) K-0070.

(1) The sample is used by previously removing an additive other than the binder resin (polymer component), or the acid value and content of the component other than the binder resin and the crosslinked binder resin are obtained in advance. Accurately weigh 0.5 to 2.0 g of the pulverized product of the sample, and set the weight of the polymer component to W g . For example, when the acid value of the binder resin is measured from the toner, the acid value and content of the colorant or the magnetic material are measured in advance, and the acid value of the binder resin is determined by calculation.

(2) The sample was placed in a 300 (ml) beaker, and 150 (ml) of a toluene/ethanol (volume ratio of 4/1) was added to dissolve.

(3) Using a 0.1 mol/L KOH ethanol solution, titration was performed using a potentiometric titration apparatus.

(4) The amount of the KOH solution used at this time was set to S (ml), and the blank sample was measured, and the amount of the KOH solution used at this time was set to B (ml), and the calculation was performed by the following formula (1). Where f is the coefficient of KOH concentration.

Acid value (mgKOH/g) = [(S-B) × f × 5.61] / W (1)

The binder resin of the toner and the composition containing the binder resin preferably have a glass transition temperature (Tg) of from 35 to 80 ° C, particularly preferably from 40 to 75 ° C, from the viewpoint of toner storage stability. When the Tg is lower than 35 ° C, the toner is easily deteriorated in a high temperature environment, and the offset is likely to occur at the time of fixing. Moreover, when Tg exceeds 80 ° C, the fixing property tends to be lowered.

In the polymerized toner of the present embodiment, a binder resin having a softening point of 80 to 140 ° C can be preferably used. When the softening point of the binder resin is less than 80 ° C, the image stability of the toner and the toner after fixing and storage may be deteriorated. The other side In the case where the softening point exceeds 140 ° C, there is a case where the low-temperature fixability is deteriorated.

Examples of the magnetic material that can be used in the present embodiment include (1) magnetic iron oxide such as magnetite, maghemite, and ferrite, and iron oxide containing other metal oxides, and (2) iron and cobalt. Metal of nickel or an alloy of such metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, lanthanum, cerium, lanthanum, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and 3) Mixtures of these, etc.

Specific examples of the magnetic material include Fe ₃ O ₄ , γ-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., the above magnetic materials may be used alone or in combination Use two or more. A preferred magnetic material is a fine powder of triiron tetroxide or γ-ferric oxide.

Further, magnetic iron oxide such as magnetite, maghemite or ferrite containing a heterogeneous element or a mixture thereof may be used. If the heterogeneous elements are exemplified, lithium, barium, boron, magnesium, aluminum, strontium, phosphorus, strontium, zirconium, tin, sulfur, calcium, barium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc , gallium, etc. As a preferred heterogeneous element, it may be selected from magnesium, aluminum, lanthanum, phosphorus or zirconium. The heterogeneous element may be inserted into the iron oxide crystal lattice, may be inserted into the iron oxide in the form of an oxide, or may be present on the surface in the form of an oxide or a hydroxide, but is preferably contained in the form of an oxide.

The above heterogeneous element may be mixed into the salt of each heterogeneous element at the time of formation of the magnetic substance, and inserted into the particle by pH adjustment. Further, after the magnetic particles are generated, the pH can be adjusted or a salt of each element can be added and the pH can be adjusted to precipitate on the surface of the particles.

The amount of use of the magnetic material is set to 10 to 200 parts by mass, preferably 20 to 150 parts by mass, per 100 parts by mass of the binder resin. The number average particle diameter of the magnetic bodies is preferably from 0.1 μm to 2 μm, more preferably from 0.1 μm to 0.5 μm. The number average particle diameter can be obtained by measuring a photograph taken by a transmission electron microscope by a digitizer or the like.

Further, as the magnetic material, it is preferable that the magnetic gas characteristics when applying 10 K Oersted are a coercive force of 20 to 150 Oe, a saturation magnetization of 50 to 200 emu/g, and residual magnetization. For 2~20 emu/g.

The above magnetic body can also be used as a colorant. As a coloring agent of this embodiment, in the case of a black toner, a black or blue dye or pigment particle is mentioned. As the pigment of black or blue, there are carbon black, aniline black, acetylene black, phthalocyanine blue, indanthrene blue and the like. Examples of the black or blue dye include an azo dye and an anthraquinone dye. A dye, a methine dye, or the like.

In the case of being used as a color toner, the following may be mentioned as a coloring agent. As the magenta coloring agent, a condensed azo compound, a diketopyrrolopyrrole compound, an anthraquinone compound, a quinacridone compound, a basic dye, a lake dye, a naphthol dye, a benzimidazolone compound, or the like can be used. Thioindigo compound, hydrazine compound. Specifically, as the pigment-based magenta coloring agent, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 , 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60 , 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207, 209, CI Pigment Violet 19, CI Reduction Red 1, 2, 10 13, 15, 23, 29, 35, etc.

The above pigments may be used singly, but in terms of the image quality of the full-color image, it is more preferable to use a dye and a pigment in combination to enhance the definition.

As the dye-based magenta coloring agent, CI solvent red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, CI dispersion red 9 , CI solvent violet 8, 13, 14, 21, 27, CI disperse violet 1 and other oil-soluble dyes, CI alkaline red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24 , 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, CI alkaline violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28 and other basic dyes .

As the cyan coloring agent, a copper phthalocyanine compound and a derivative thereof, a hydrazine, a basic dye lake compound can be used. Specifically, as the pigment-based blue-green colorant, CI Pigment Blue 2, 3, 15, 16, 17, CI Reduced Blue 6, CI Acid Blue 45, or 1 to 5 ortho-orders on the phthalocyanine skeleton may be mentioned. Copper phthalocyanine pigment of benzylidene imino group.

As the yellow colorant, a condensed azo compound, an isoindolinone compound, an anthraquinone compound, an azo metal complex, a methine compound, or an allyl decylamine compound can be used. Specifically, examples of the yellow pigment include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, and 73. , 83, CI reduced yellow 1, 3, 20 and so on.

Examples of the orange pigment include red chrome yellow, molybdenum orange, permanent orange GTR, pyrazole orange, sulfur-resistant orange, benzidine orange G, indanthrene brilliant orange RK, and indanthrene bright orange GK. Examples of the violet pigment include manganese violet, fast violet B, and methyl violet lake. Examples of the green pigment include chromium oxide, chrome green, pigment green, peacock green lake, and terminal yellow green G. Examples of the white pigment include zinc white, titanium oxide, antimony white, and zinc sulfide.

The amount of the coloring agent used is preferably set to 0.1 to 20 parts by mass based on 100 parts by mass of the binder resin.

The toner of this embodiment can also be used as a two-component developer by mixing with a carrier. In the present embodiment, as the carrier, a carrier such as a usual ferrite or magnetite may be used, or a resin-coated carrier may be used.

The resin-coated carrier contains a carrier core particle and a coating material as a resin covering the surface of the carrier core particle. The resin used in the coating material is preferably a styrene-acrylate resin such as a styrene-acrylate copolymer or a styrene-methacrylate copolymer, or an acrylic acid such as an acrylate copolymer or a methacrylate copolymer. Ester resin, PTFE resin such as polytetrafluoroethylene, trifluoromonochloroethylene polymer, polyvinylidene fluoride, polyfluorene oxide resin, polyester resin, polyamide resin, polyvinyl butyral, amino acrylate Resin. In addition, an ionic polymer resin, a polyphenylene sulfide resin, or the like can be used as a coating (coating) material for the carrier. Resin. These resins may be used singly or in combination of plural kinds.

Further, a binder type carrier core in which a magnetic powder is dispersed in a resin can also be used. In the resin-coated carrier, as a method of coating the surface of the carrier core with at least a resin coating material, a method of dissolving or suspending the resin in a solvent and applying it to the carrier core to adhere thereto, or simply using a powder may be applied. The method of mixing the body state. The ratio of the resin coating material to the resin-coated carrier may be appropriately determined, and is preferably 0.01 to 5% by mass, and more preferably 0.1 to 1% by mass based on the resin-coated carrier.

Examples of the use of the magnetic material coated with a coating (coating agent) of a mixture of two or more types include (1) dimethyl dichloromethane and dimethyl hydrazine oil (quality) with respect to 100 parts by mass of the titanium oxide fine powder. a mixture of 12 parts by mass of the mixture of 1:5), (2) a mixture of dimethyldichloromethane and dimethyl hydrazine oil (mass ratio 1:5) with respect to 100 parts by mass of the cerium oxide micropowder 20 parts by mass were processed.

Among the above resins, a styrene-methyl methacrylate copolymer, a mixture of a fluororesin and a styrene copolymer or a polyoxyxylene resin is preferred, and a polyoxyxylene resin is preferred.

Examples of the mixture of the fluorine-containing resin and the styrene-based copolymer include a mixture of polyvinylidene fluoride and a styrene-methyl methacrylate copolymer, and copolymerization of polytetrafluoroethylene and styrene-methyl methacrylate. a mixture of the mixture, a vinylidene fluoride-tetrafluoroethylene copolymer (copolymer mass ratio of 10:90 to 90:10) and a copolymer of styrene-ethyl 2-ethylhexyl acrylate (copolymerization mass ratio of 10:90) ~90:10) A mixture of styrene-2-ethylhexyl acrylate-methyl methacrylate copolymer (mass ratio of copolymer: 20 to 60: 5 to 30: 10: 50).

Examples of the polyoxyxylene resin include a nitrogen-containing polyfluorene oxide resin and a modified polyxanthene resin produced by reacting a nitrogen-containing decane coupling agent with a polyfluorene oxide resin.

As the magnetic material of the carrier core, an oxide such as ferrite, iron excess ferrite, magnetite or γ-iron oxide, a metal such as iron, cobalt or nickel or an alloy thereof can be used. Further, examples of the elements contained in the magnetic materials include iron, cobalt, nickel, aluminum, copper, and lead. Magnesium, tin, zinc, antimony, bismuth, antimony, calcium, manganese, selenium, titanium, tungsten, vanadium. Preferred examples of the magnetic material include copper-zinc-iron ferrite containing copper, zinc and iron as main components, and manganese-magnesium-iron ferrite containing manganese, magnesium and iron as main components. .

The resistance value of the carrier is preferably adjusted to 10 ⁶ Ω by adjusting the degree of unevenness on the surface of the carrier and the amount of the resin to be coated. Cm~10 ¹⁰ Ω. Cm. The particle size of the carrier can be set to 4 μm to 200 μm, preferably 10 μm to 150 μm, more preferably 20 μm to 100 μm. It is especially preferred that the resin coated carrier has a 50% particle size of 20 μm to 70 μm.

In the two-component developer, it is preferred to use 1 to 200 parts by mass of the toner of the present embodiment with respect to 100 parts by mass of the carrier, and more preferably 2 to 50 parts by mass with respect to 100 parts by mass of the carrier. Share.

The toner of this embodiment may further contain a wax. In the present embodiment, the wax used is as follows. For example, an aliphatic hydrocarbon wax such as a low molecular weight polyethylene, a low molecular weight polypropylene, a polyolefin wax, a microcrystalline wax, a paraffin wax, or a sax wax, or an oxide of an aliphatic hydrocarbon wax such as an oxidized polyethylene wax, or the like Block copolymers such as candid wax, carnauba wax, wood wax, jojoba wax and other plant waxes, beeswax, lanolin, cetyl wax and other animal waxes, ground wax, pure ground wax, petrolatum, etc. Mineral wax, montan acid ester wax, ramie wax, etc., which are mainly composed of fatty acid esters, deoxidized carnauba wax, etc., which partially or completely deoxidize one or more fatty acid esters.

Examples of the wax include saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid or a linear alkyl carboxylic acid having a linear alkyl group, brassic acid, tungstic acid, and strontium. An unsaturated fatty acid such as oxalic acid, a saturated alcohol such as stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnaubaol, hexadecanol, tridecyl alcohol or long-chain alkyl alcohol, or a polyhydric alcohol such as sorbitol. Fatty acid decylamine such as linoleamide, oleic acid amine, laurylamine, fatty acid guanamine such as methylene biguanide, ethyl bis-laurate, hexamethylene distearylamine, etc. Unsaturated fatty acid guanamines such as ethyl bis decylamine, hexamethylene bis decylamine, N,N'-dioleyl decylamine, N,N'-dioleyl quinone diamine , m-xylene double hard An aromatic diamine, such as lipoteuramine or N,N'-distearyl metaxylamine, a fatty acid metal salt such as calcium stearate, calcium laurate, zinc stearate or magnesium stearate, A wax obtained by grafting an aliphatic hydrocarbon wax with a vinyl monomer such as styrene or acrylate, a partial ester compound of a fatty acid such as a behenic acid monoglyceride or a polyhydric alcohol, by hydrogenating a vegetable fat A methyl ester compound having a hydroxyl group is obtained.

Examples of the wax which can be preferably used include a polyolefin obtained by radically polymerizing an olefin under high pressure, and a polyolefin obtained by purifying a low molecular weight by-product obtained by polymerizing a high molecular weight polyolefin, and used at a low pressure. A polyolefin obtained by polymerization of a catalyst of a ruthenium catalyst or a metallocene catalyst, a polyolefin obtained by polymerization using radiation, electromagnetic waves or light, and a low molecular weight polyolefin obtained by thermally decomposing a high molecular weight polyolefin, paraffin, Microcrystalline wax, Fischer-Tropsch wax, synthetic hydrocarbon wax synthesized by the Synthol method, the Hydrochol method, the Arge method, etc. a compound having a number of compounds as a monomer, a hydrocarbon wax having a functional group such as a hydroxyl group or a carboxyl group, a mixture of a hydrocarbon wax and a hydrocarbon wax having a functional group, and the wax is used as a precursor and styrene is used. A wax obtained by graft-modifying a vinyl monomer such as a maleic acid ester, an acrylate, a methacrylate or a maleic anhydride.

Further, it is preferable to use a pressed sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a solution crystallization method to narrow the molecular weight distribution, or to remove the wax. A low molecular weight solid fatty acid, a low molecular weight solid alcohol, a low molecular weight solid compound or other impurities are obtained.

In order to obtain a balance between fixability and offset resistance, the wax used in the present embodiment preferably has a melting point of 50 to 140 ° C, more preferably 70 to 120 ° C. If it is less than 50 ° C, the blocking resistance tends to decrease, and if it exceeds 140 ° C, it is difficult to exhibit an offset resistance effect.

Further, by using two or more different kinds of waxes, the plasticizing action and the releasing action as the action of the wax can be simultaneously exhibited.

As the kind of the wax having plasticizing action, for example, a wax having a lower melting point or a wax having a branched structure or a structure having a polar group as a molecular structure, and as a wax having a releasing action, a wax having a higher melting point, a wax having a linear structure in a molecular structure, or a functional group is not mentioned. Non-polar wax. As a use example, a combination of a difference in melting point of two or more different waxes of 10 ° C to 100 ° C, a combination of a polyolefin and a graft-modified polyolefin, and the like can be given.

In the case of selecting two kinds of waxes, in the case of a wax having the same structure, a wax having a relatively low melting point exerts a plasticizing action, and a wax having a relatively high melting point exerts a releasing action. At this time, when the difference in melting point is 10 to 100 ° C, functional separation can be effectively exhibited. If it is less than 10 ° C, it is difficult to exhibit a functional separation effect, and when it exceeds 100 ° C, it is difficult to enhance the function by interaction. In this case, it is preferred that at least one of the waxes has a melting point of 70 to 120 ° C, more preferably 70 to 100 ° C. When the melting point is within this range, there is a tendency that the functional separation effect is easily exhibited.

Further, among the waxes, those having a branched structure, a polar group having a functional group, or a component having a different main component, are plasticized, and a relatively linear structure is relatively A non-polar or unmodified straight line having no functional group exerts a release action. As a preferable combination of the wax, a combination of a polyethylene homopolymer or copolymer containing ethylene as a main component and a polyolefin homopolymer or copolymer mainly composed of an olefin other than ethylene; polyolefin and grafting; a combination of modified polyolefins; a combination of an alcohol wax, a fatty acid wax or an ester wax and a hydrocarbon wax; a Fischer-Tropsch wax or a combination of a polyolefin wax and a paraffin wax or a microcrystalline wax; a combination of a Fischer-Tropsch wax and a polyolefin wax; A combination of microcrystalline wax; a combination of carnauba wax, canary wax, rice bran wax or montan wax and a hydrocarbon wax.

In either case, it is preferably the peak top temperature having the largest peak in the region of 70 to 110 ° C in the endothermic peak observed in the DSC (Differential Scanning Calorimeter) measurement of the toner. More preferably, it has a peak top temperature of a maximum peak in a region of 70 to 110 °C. Thereby, it is easy to obtain the balance of toner preservability and fixability.

In the toner of the embodiment, the wax is 100 parts by mass with respect to the binder resin. The total content is preferably 0.2 to 20 parts by mass, more preferably 0.5 to 10 parts by mass.

In the present embodiment, the melting point of the wax is the peak top temperature of the maximum peak of the endothermic peak of the wax measured in DSC.

In the present embodiment, the DSC measurement of the wax or the toner is preferably carried out using a high-precision internal thermal power compensation type differential scanning calorimeter. The measurement method was carried out in accordance with ASTM (American Society for Testing Material) D3418-82. In the present embodiment, the DSC curve measured when the temperature is raised at a temperature of 10 ° C/min after the temperature rise and temperature reduction are performed once, is used.

In the toner of the embodiment, a fluidity improver may be added. The fluidity improver is one which improves the fluidity of the toner (it becomes easy to flow) by being added to the surface of the toner. For example, fluorine-based resin powders such as carbon black, fine vinylidene fluoride fine powder, and polytetrafluoroethylene fine powder, such as wet-process cerium oxide, dry-process cerium oxide-like fine powder cerium oxide, and fine powder oxidation Titanium, finely powdered alumina, and treated cerium oxide, treated titanium oxide, and treated alumina obtained by surface treatment with a decane coupling agent, a titanium coupling agent or a polyoxygenated oil. Among them, preferred are fine powder of cerium oxide, fine powder of non-titanium oxide, fine powder of non-alumina, and more preferably, cerium oxide treated by surface treatment by a decane coupling agent or a polyoxygenated oil. The particle size of the fluidity improver is preferably from 0.001 μm to 2 μm, more preferably from 0.002 μm to 0.2 μm, in terms of the average primary particle diameter.

The preferred fine powder of cerium oxide is a fine powder formed by vapor phase oxidation of a cerium halide compound, and is called a so-called dry cerium oxide or smoked cerium oxide.

Commercially available cerium oxide fine powder which is produced by vapor phase oxidation of a halogen halide compound is commercially available, for example, under the following trade names. AEROSIL (manufactured by Japan Aerosil Co., Ltd., the same below) -130, -300, -380, -TT600, -MOX170, -MOX80, -COK84: Ca-O-SiL (manufactured by CABOT Co., Ltd., the same below) -M -5, -MS-7, -MS-75, -HS-5, -EH-5, Wacker HDK (manufactured by WACKER-CHEMIEGMBH Co., Ltd., the same below) - N20 V15, -N20E, - T30, -T40: D-CFineSilica (manufactured by Dow Corning Co., Ltd.): Fransol (manufactured by Fransil Co., Ltd.).

Furthermore, it is more preferable to treat the cerium oxide fine powder obtained by hydrophobizing the cerium oxide fine powder produced by vapor phase oxidation of the cerium halide compound. As the cerium oxide micropowder, it is preferred to treat the cerium oxide micropowder in such a manner that the degree of hydrophobicity measured by the methanol titration test is 30 to 80%. The hydrophobization treatment can be carried out, for example, by chemical or physical treatment using an organic ruthenium compound or the like which is reacted or physically adsorbed with cerium oxide fine powder. Among them, a method of treating a cerium oxide fine powder formed by vapor phase oxidation of a cerium halide compound by an organic cerium compound is preferred.

Examples of the organic ruthenium compound include hydroxypropyltrimethoxydecane, phenyltrimethoxydecane, n-hexadecyltrimethoxydecane, n-octadecyltrimethoxydecane, and vinylmethoxydecane. Vinyl triethoxy decane, vinyl triethoxy decane, dimethyl vinyl chlorodecane, divinyl chloro decane, γ-methyl propylene methoxy propyl trimethoxy decane, hexamethyl bis Decane, trimethyldecane, trimethylchlorodecane, dimethyldichlorodecane, methyltrichlorodecane, allyldimethylchlorodecane, allylphenyldichlorodecane, benzyldimethyl chloride Decane, bromomethyldimethylchlorodecane, α-chloroethyltrichlorodecane, β-chloroethyltrichlorodecane, chloromethyldimethylchlorodecane, triorganosilyl mercaptan, trimethyldecyl Mercaptan, triorganodecyl acrylate, vinyl dimethyl ethoxy decane, dimethyl ethoxy decane, trimethyl ethoxy decane, trimethyl methoxy decane, methyl triethoxy Base decane, isobutyl trimethoxy decane, dimethyl dimethoxy decane, diphenyl diethoxy decane, six Dioxazane, 1,3-divinyltetramethyldioxane, 1,3-diphenyltetramethyldioxane, and 2 to 12 oxoxane units per molecule and Each of the units located at the end has 0 to 1 dimethyl polyoxyalkylene bonded to the hydroxyl group of Si, and the like. Further, a polyoxygenated oil such as dimethylpolyphthalic acid oil can be mentioned. These may be used singly or in the form of a mixture of two or more.

The fluidity improving agent preferably has a number average particle diameter of 5 nm to 100 nm, more preferably 5 nm to 50 nm. The specific surface area of nitrogen adsorption by the BET (Brunauer-Emmett-Teller) 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 amount of the fine powder applied is preferably from 0.03 to 8 parts by mass based on 100 parts by mass of the toner particles.

In the toner of the present embodiment, for the purpose of protecting the photoreceptor/carrier, improving the cleanability, adjusting the thermal characteristics, electrical characteristics, physical properties, resistance adjustment, softening point adjustment, and fixing rate, etc., Further, various metal soaps, fluorine-based surfactants, dioctyl phthalate, tin oxide, zinc oxide, carbon black, cerium oxide, or the like as a conductivity imparting agent, or titanium oxide, aluminum oxide, or aluminum oxide (alumina) are added. ) such as inorganic fine powder. Further, the inorganic fine powders may be hydrophobized as needed. Further, a lubricant such as polytetrafluoroethylene, zinc stearate or polyvinylidene fluoride may be used in a small amount, an abrasive such as cerium oxide, cerium carbide or barium titanate, an anti-caking agent, and a small amount of polarity and White fine particles and black fine particles having opposite toner particles are used as developability improving agents.

These additives are also preferably used for controlling the amount of charge, etc. by polyoxyn varnish, various modified polyoxyxylene varnishes, polyoxygenated oils, various modified polyoxyxides, decane coupling agents, and functional groups. Treatment with a treatment agent such as a decane coupling agent or another organic hydrazine compound or various treatment agents.

In this embodiment, the charge control agent and the additive as described above may be added by a mixer such as a Henschel mixer, a ball mill, a Nauta mixer, a V-type mixer, a W-type mixer, or a high-speed mixer. The toner is thoroughly mixed and stirred, and the surface of the toner particles is uniformly subjected to external addition treatment, whereby the intended electrostatic charge developing toner is obtained.

The toner of the present embodiment is also stable to heat, and does not change due to heat during the electrophotographic process, and can maintain stable charging characteristics. Further, it can be uniformly dispersed in any of the binder resins, so that the charge distribution of the fresh toner is very uniform. Therefore, the color adjustment of this embodiment Even if the agent is an untransferred, recovered toner (waste toner), the saturated triboelectric charge amount and the charge distribution are hardly changed as compared with the fresh toner. On the other hand, when the waste toner obtained by the electrostatic charge image developing toner of the present embodiment is reused, the toner can be further produced by using the following method to further reduce the fresh toner and the waste toner. Difference of the toner: a method of selecting a polyester resin containing an aliphatic diol in a binder resin, a method of using a metal crosslinked styrene-acrylate copolymer as a binder resin and adding a large amount of a polyolefin thereto.

The toner of this embodiment can be produced by a known production method. When the production method is exemplified, it is preferable to sufficiently mix the toner constituent materials such as a binder resin, a charge control agent, and a colorant by a mixer such as a ball mill, and heat the kneading device such as a hot roll kneader. The mixture is thoroughly kneaded, cooled and solidified, and classified by pulverization to obtain a toner (pulverization method).

Further, a toner may be produced by dissolving the above mixture in a solvent, atomizing it by spraying, drying and classifying it to obtain a toner. Further, a toner may be produced by mixing a specific material in a monomer constituting the binder resin, preparing an emulsified or suspended liquid, and then polymerizing it to obtain a toner. Agent manufacturing method; in a so-called microcapsule toner containing a core material and a shell material, a method of making a core material or a shell material or a specific material thereof. Further, if necessary, the toner of the present embodiment can be produced by sufficiently mixing the desired additive with the toner particles by a mixer such as a Henschel mixer.

The method for producing the toner according to the embodiment of the above pulverization method will be described in more detail. First, the binder resin and the coloring agent, the charge control agent, and other necessary additives are uniformly mixed. A known agitator such as a Henschel mixer, a high speed mixer, a ball mill or the like can be used for the mixing. The resulting mixture was heat-melted and kneaded using a closed kneader or a uniaxial or biaxial extruder. After the kneaded material is cooled, it is coarsely pulverized using a crusher or a hammer mill, and further finely pulverized by a jet mill, a high-speed rotor rotary mill or the like. broken. Further, an air classifier is used, for example, an Elbow-Jet using an inertial grading method of the Coanda effect, a cyclone (Microplex) by a cyclone (centrifugal) classification method, and a DS (Dean-Stark, Dean). - Stark) separators, etc., are classified to a specific particle size. In the case where the surface of the toner is further treated with an external additive or the like, the toner and the external additive are stirred and mixed by a high speed agitator such as a Henschel mixer, a high speed mixer or the like.

Further, the toner of the present embodiment can also be produced by a suspension polymerization method or an emulsion polymerization method. In the suspension polymerization method, first, a polymerizable monomer, a coloring agent, a polymerization initiator, a charge control agent, and optionally a crosslinking agent, a dispersion stabilizer, and other additives are uniformly dissolved or dispersed to prepare a monomer combination. Things. Thereafter, the monomer composition and the dispersion are stabilized by using a suitable mixer or dispersing machine, such as a homomixer, a homogenizer, an atomizer, a micro-jet homogenizer, a single-flow nozzle, a gas-liquid fluid nozzle, an electric emulsifier, and the like. The agent is dispersed in a continuous phase such as an aqueous phase. It is preferred to adjust the stirring speed, temperature, and time so that the droplets of the polymerizable monomer composition have the desired size of the toner particles, and perform granulation. The polymerization reaction can be carried out simultaneously at 40 to 90 ° C to obtain toner particles having a desired particle diameter. The obtained toner particles were washed, separated by filtration, and dried. The method disclosed above can be used after the production of the toner particles.

When it is produced by the emulsion polymerization method, it is excellent in uniformity as compared with the particles obtained by the above suspension polymerization method, but the average particle diameter is from 0.1 μm to 1.0 μm and is extremely small, so depending on the case, sometimes The method can be carried out by a method of so-called seed polymerization in which emulsified particles are used as a core and then a polymerizable monomer is added to grow the particles, or a method in which the emulsified particles are combined and fused to an appropriate average particle diameter.

Since the production by the polymerization method is not subjected to the pulverization step, it is not necessary to impart brittleness to the toner particles, and the low-softening point substance which is difficult to use in the previous pulverization method can be used in a large amount, so that the selection range of the material can be expanded. The release agent or coloring agent as a hydrophobic material is difficult to be exposed on the surface of the toner particles, so that the toner supporting member and the photosensitive material can be reduced. Contamination of the body, transfer roller and fuser.

By producing the toner of the present embodiment by a polymerization method, characteristics such as image reproducibility, transferability, and color reproducibility can be further improved. Further, in order to cope with minute spots, the particle diameter of the toner can be made small, and a toner having a narrow particle size distribution can be obtained relatively easily.

The polymerizable monomer used in the production of the toner of the present embodiment by a polymerization method is, for example, a vinyl polymerizable monomer which can be subjected to radical polymerization. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

Examples of the monofunctional polymerizable monomer include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and 2,4. a styrene-based polymerizable monomer such as dimethyl styrene, p-n-butyl styrene, p-tert-butyl styrene, p-n-hexyl styrene or p-phenyl styrene; methyl acrylate or 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 Acrylate-based polymerizable monomer such as ester, dimethyl phosphate methyl acrylate, dibutyl phosphate acrylate, and 2-benzyl methoxyethyl acrylate; Ester, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate , n-hexyl methacrylate, methacrylic acid 2 a methacrylate-based polymerizable monomer such as ethylhexyl ester, n-octyl methacrylate, diethyl phosphate methacrylate or dibutyl phosphate methacrylate; unsaturated aliphatic monocarboxylic acid Ethyl esters; vinyl acetates such as vinyl acetate, vinyl propionate, vinyl benzoate; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl hexanone, vinyl A ketene such as isopropyl ketone.

A known initiator such as an organic peroxide can be used as the polymerization initiator used in the production of the toner of the present embodiment by a polymerization method. Examples of the water-soluble initiator include ammonium persulfate, potassium persulfate, and 2,2. '-Azobis(N,N'-dimethyleneisobutyl hydrazine) hydrochloride, 2,2'-azo Bis(2-aminodipropane) hydrochloride, azobis(isobutyl hydrazine) hydrochloride, sodium 2,2'-azobisisobutyronitrile sulfonate, ferrous sulfate or hydrogen peroxide.

The polymerization initiator is preferably added in an amount of 0.5 to 20 parts by mass based on 100 parts by mass of the polymerizable monomer, and may be used singly or in combination. Examples of the dispersant used in the production of the polymerized toner include tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, carbon number calcium, carbon number magnesium, aluminum hydroxide, and hemiplegia. Calcium acid, calcium sulfate, barium sulfate, bentonite, cerium oxide, aluminum oxide, and the like. Examples of the organic compound include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, and starch. The dispersant is preferably used in an amount of 0.2 to 2.0 parts by mass based on 100 parts by mass of the polymerizable monomer.

These dispersing agents can also be used as they are, but in order to obtain fine particles having a uniform particle size, the inorganic compound can be produced under high-speed stirring in a dispersion medium.

The toner obtained by the above polymerization method tends to have a small degree of unevenness of the toner particles as compared with the toner obtained by the pulverization method which is not subjected to special treatment, and since it is amorphous, the electrostatic latent image The contact area between the carrier and the toner increases, and the toner adhesion becomes high, resulting in less contamination inside the machine, and it is easy to obtain an image with higher image density and higher quality.

Further, the toner obtained by the pulverization method can be treated by a hot water bath method in which toner particles are dispersed in water and heated, by heat treatment in a hot gas stream or by imparting mechanical energy. A method such as a mechanical impact method reduces the degree of unevenness of the surface of the toner. As an effective means for reducing the degree of unevenness, a mechanical fusion system using dry mechanical chemistry (manufactured by Hosokawa Micron Co., Ltd.), a type I jet mill, and a mixture of a rotor and a gasket can be cited. Hybridizer (manufactured by Nara Machinery Co., Ltd.), Henschel mixer as a mixer with high-speed stirring blades, and the like.

One of the values indicating the degree of unevenness of the toner particles is an average circularity. The average circularity (C) means that the circularity (Ci) is obtained by the following formula (2), and the sum of the circularities of all the particles measured is divided by the following equation (3). The value obtained for all the number of particles (m) measured.

The above circularity (Ci) is measured using a flow type particle image analyzer (for example, FPIA-1000 manufactured by East Asia Medical Electronics Co., Ltd.). As a measuring method, a dispersion obtained by dispersing about 5 mg of the toner in 10 ml of water in which about 0.1 mg of the nonionic surfactant was dissolved was adjusted, and the dispersion was irradiated with ultrasonic waves (20 kHz, 50 W). The dispersion concentration was adjusted to 5,000 to 20,000 pieces/μL in 5 minutes, and the circularity distribution of particles having a circular approximate diameter of 0.60 μm or more and less than 159.21 μm was measured using the above-described flow type particle image analyzer.

The value of the above average circularity is preferably from 0.955 to 0.995, more preferably from 0.960 to 0.985. When the toner particles are adjusted so that the average circularity becomes this value, there is a tendency that the phenomenon that the transfer residual toner is increased is less likely to occur, and retransfering is less likely to occur.

In the case of the toner of the embodiment, the imageability and the productivity of the toner In the aspect of the laser particle size distribution measuring machine such as a micron sizer (for example, manufactured by Shinko Co., Ltd.), in the case of pulverizing the toner, it is preferable to color The particle diameter of the agent is in the range of 2 μm to 15 μm, more preferably in the range of 3 μm to 12 μm, based on the volume-based average particle diameter. When the average particle diameter exceeds 15 μm, the resolution or the sharpness tends to be weakened. When the average particle diameter is less than 2 μm, the resolution is good, but there is a tendency that the yield at the time of toner production is generated. The problem of high cost due to deterioration, or the scattering of toner in the machine, penetration of the skin, etc., hinders health.

On the other hand, in the case of a polymerized toner, it is preferably in the range of 3 μm to 9 μm, more preferably in the range of 4 μm to 8.5 μm, and particularly preferably in the range of 5 μm to 8 μm. When the volume average particle diameter is less than 4 μm, the fluidity of the toner is lowered, the chargeability of each particle is liable to lower, and the charge distribution is broadened, so that fogging on the background or toner scattering from the developer is likely to occur. . Moreover, if it is less than 4 μm, there is a case where cleaning becomes extremely difficult. When the volume average particle diameter is larger than 9 μm, the resolution is lowered. Therefore, there is a case where sufficient image quality cannot be obtained, and it is difficult to satisfy the high image quality requirements in recent years.

Further, in the polymerized toner of the present embodiment, the particle size range (channel) obtained by dividing the particle size distribution measured by the following method is used to describe the cumulative distribution of the volume and the number from the small diameter side, respectively. The cumulative 16% particle size is defined as the volume D16%, the cumulative 50% particle size is defined as the volume D50%, and the cumulative 84% particle size is defined as the volume D84%, from (D84%/D16%) 1/2 The calculated volume average particle size distribution index (GSDv) is preferably from 1.15 to 1.30, more preferably from 1.15 to 1.25.

The particle size distribution of the toner is preferably 2 μm or less in the case of the toner of the present embodiment, for example, based on the particle size measurement using a Coulter counter (TA-II manufactured by Coulter Co., Ltd.). The particle content is from 10 to 90%, more preferably from 12.7 μm or more, based on the number of particles, and is 0 to 30% by volume.

Further, it is desirable that the particle size uniformity is high (volume average particle diameter / number average particle diameter is 1.00~1.30).

In the case of the electrostatic charge developing toner of the present embodiment, the specific surface area of the toner is preferably 1.2 to 5.0 m ² /g in the measurement of the BET specific surface area using nitrogen as the desorbed gas. More preferably 1.5 to 3.0 m ² /g. For the measurement of the specific surface area, for example, a BET specific surface area measuring device (for example, manufactured by Shimadzu Corporation, FlowSorb II 2300) is used, and the adsorbed gas on the surface of the toner is detached at 50 ° C for 30 minutes, and then the liquid nitrogen is used. After cooling and again adsorbing nitrogen gas, the temperature was again raised to 50 ° C, and the specific surface area was defined as a value obtained from the amount of outgas at this time.

In the case of the toner of the present embodiment, the specific gravity (bulk density) is measured, for example, using a powder tester (for example, manufactured by Hosokawa Micron Co., Ltd.). In the case of a non-magnetic toner, it is preferably 0.2 to 0.6 g/cm ³ , and in the case of a magnetic toner, it depends on the kind and content of the magnetic powder, but is preferably 0.2 to 2.0 g/cm. ³ .

In the case of the toner of the present embodiment, 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 type of the magnetic powder and The content is preferably 0.9 to 4.0 g/cm ³ . The true specific gravity of the toner is calculated as follows. The toner was accurately weighed to 1.000 g, which was placed in a 10 mm Φ tablet former, and compression-molded while applying a pressure of 200 kgf/cm ² under vacuum. The height of the cylindrical molded product was measured by a micrometer to calculate the true specific gravity.

The fluidity of the toner is defined, for example, according to a flow angle of repose and a resting angle of repose obtained by an angle of repose measuring device (for example, manufactured by Tsutsui Riken Chemical Co., Ltd.). In the case of the electrostatic charge developing toner using the charge control agent of the present embodiment, the flow repose angle is preferably 5 to 45 degrees. Further, the resting angle of repose is preferably 10 to 50 degrees.

In the case of the toner of the present embodiment, the average value of the shape factor (SF-1) in the case of the pulverized toner is preferably from 100 to 400, and the average value of the shape factor 2 (SF-2) is preferably. It is 100~350.

In the present embodiment, SF-1 and SF-2 which represent the shape factor of the toner are exemplified. If an optical microscope (such as BH-2 manufactured by Olympus Co., Ltd.) equipped with a CCD (Charge Coupled Device) camera is used, it is enlarged to 1000 times in a field of view of 30 or so. The toner particle group is sampled, and the obtained image is transferred to an image analysis device (for example, LUZEXF FS manufactured by NIRECO Co., Ltd.), and the operation is repeated on the toner particles until it reaches about 1000, and is calculated. Shape factor. The shape factor (SF-1) and the shape factor 2 (SF-2) are calculated by the following equation.

SF-1=((ML ² ×π)/4A)×100

(where ML represents the maximum length of the particle and A represents the projected area of a particle)

SF-2=(PM ² /4Aπ)×100

(wherein PM represents the perimeter of the particle and A represents the projected area of a particle).

SF-1 indicates the deformation of the particles. The closer the particles are to the spherical shape, the closer the value is to 100, and the longer the value is, the larger the value becomes. Further, SF-2 indicates the unevenness of the particles, and the closer the particles are to the spherical shape, the closer the numerical value is to 100, and the more complicated the shape of the particles, the larger the numerical value.

For the toner of the present embodiment, the volume resistivity of the toner is preferably 1 × 10 ¹² to 1 × 10 ¹⁶ Ω in the case of the non-magnetic toner. The cm, in the case of the magnetic toner, also depends on the type and content of the magnetic powder, but is preferably 1 × 10 ⁸ to 1 × 10 ¹⁶ Ω. Cm. In this case, the toner volume resistivity is obtained by compression-molding toner particles to prepare a disk-shaped test piece having a diameter of 50 mm and a thickness of 2 mm, and is placed on a solid electrode (for example, manufactured by Ando Electric Co., Ltd.). On SE-70), a high insulation resistance meter (for example, 4339A manufactured by Hewlett Packard Co., Ltd.) is used, and the volume resistivity of the toner is defined as a value one hour after the continuous application of a direct current voltage of 100 V.

In the case of the toner of the present embodiment, the dielectric loss of the toner is preferably 1.0 × 10 ^-3 to 15.0 × 10 ^{-3 in} the case of the non-magnetic toner, and is also in the magnetic toner. In the case of the magnetic powder, it is also preferably 2 × 10 ^-3 to 30 × 10 ^-3 . In this case, the dielectric loss tangent of the toner is compression-molding of the toner particles to prepare a disk-shaped test piece having a diameter of 50 mm and a thickness of 2 mm, and is placed on the solid electrode to use LCR (Inductance). -Capacitance-Resistance, inductive-capacitor-resistance tester (such as 4284A manufactured by Hewlett Packard Co., Ltd.), which defines the dielectric loss tangent of the toner as measured at a measurement frequency of 1 KHz and a peak-to-peak voltage of 0.1 KV. The resulting dielectric loss tangent (Tan δ).

For the toner of the embodiment, the Izod impact value of the toner is preferably 0.1 to 30 kg. Cm/cm. The Izod impact value of the toner in this case is a test piece in which a toner particle is thermally fused to form a plate, and is subjected to a JIS (Japanese Industrial Standards) standard K-7110 (hard plastic impact). Test method).

In the toner of the embodiment, the melt index (MI value) of the toner is preferably from 10 to 150 g/10 min. The melt index (MI value) of the toner in this case is determined in accordance with JIS Standard K-7210 (Method A). In this case, the measurement temperature was 125 ° C and the load was set to 10 kg.

In the toner of the present embodiment, the melting start temperature of the toner is preferably 80 to 180 ° C, and the 4 mm lowering temperature is preferably 90 to 220 ° C. In this case, the toner melting start temperature is compression-molded to produce a cylindrical test piece having a diameter of 10 mm and a thickness of 20 mm, and is provided in a hot melt characteristic measuring device, for example, a rheometer (flow) In the tester) (for example, CFT-500C manufactured by Shimadzu Corporation), the melting start temperature of the toner is defined as a value at which melting starts when the measurement is performed at a load of 20 kgf/cm ² and the piston starts to fall. Also, in the same measurement, the temperature at which the piston was lowered by 4 mm was defined as a temperature of 4 mm.

In the toner of the present embodiment, the glass transition temperature (Tg) of the toner is preferably from 35 to 80 ° C, more preferably from 40 to 75 ° C. The glass transition temperature of the toner in this case is measured by a differential thermal analysis (hereinafter abbreviated as DSC) apparatus, and the temperature is raised at a constant temperature, then quenched, and the temperature is raised again to adjust the glass transition temperature (Tg) of the toner. Defined as based on this When the peak of the phase change is obtained. When the Tg of the toner is less than 35 ° C, the offset resistance and the storage stability tend to be lowered. When the Tg exceeds 80 ° C, the fixing strength in the image tends to decrease.

It is preferable that the peak end temperature of the maximum peak exists in the region of 70 to 120 ° C in the endothermic peak observed in the DSC measurement of the toner of the present embodiment.

In the toner of the present embodiment, the melt viscosity of the toner is preferably from 1,000 to 50,000 poise, more preferably from 1,500 to 38,000 poise. In this case, the toner melt viscosity is obtained by compression-molding toner particles to produce a cylindrical test piece having a diameter of 10 mm and a thickness of 20 mm, and is provided in a hot melt characteristic measuring device such as a rheometer (for example, Shimadzu). In CFT-500C manufactured by Seiko Co., Ltd., the melt viscosity of the toner is defined as a value measured at a load of 20 kgf/cm ² .

The solvent-dissolved residual component of the toner of the present embodiment is preferably 0 to 30% by mass of the THF-insoluble component, 0 to 40% by mass of the ethyl acetate-insoluble component, and 0 to 30% by mass of the chloroform-insoluble component. Here, the solvent dissolves the residual component so that 1 g of the toner is uniformly dissolved and/or dispersed in 100 ml of each solvent of THF, ethyl acetate and chloroform, and the solution and/or dispersion are subjected to pressure filtration to dry the filtrate. The basis weight was calculated, and the ratio of the insoluble matter to the organic solvent in the toner was calculated based on the value, and the solvent-dissolved residual component of the toner was set to the calculated value.

The toner of this embodiment can be used as a one-component development method which is one of image forming methods. The one-component development method is a method in which a thinned toner is supplied to a latent image carrier to develop a latent image. The thinning of the toner is usually performed by using a device including a toner conveying member, a toner layer thickness controlling member, and a toner replenishing auxiliary member, and the replenishing auxiliary member and the toner conveying member, and The toner layer thickness control member and the toner conveying member abut each other.

The case where the toner of the embodiment is applied to the two-component developing method will be specifically described. The so-called two-component development method uses a toner and a carrier (having a charge as a charge) In the form of the material and the toner transporting material, the carrier may use the above-mentioned magnetic material or glass beads. The developer (toner and carrier) is stirred by a stirring member to generate a specific amount of charge, and is transported to the developing portion by a magnetic roller or the like. The developer is held on the surface of the roller by a magnetic force on a magnetic roller to form a magnetic brush which is controlled to a proper height by a developer control panel or the like. The developer moves on the roller accompanying the rotation of the developing roller, and contacts the electrostatic charge latent image holding body or faces at a certain interval in a non-contact state to develop the latent image. In the case of development in a non-contact state, a driving force for flying the toner in a space of a certain interval is usually obtained by generating a DC electric field between the developer and the latent image holder, but for development, Clear images can also be applied in a way that overlaps the communication.

Further, the charge control agent used in the present embodiment is also suitable as a charge control agent (charge enhancer) in the coating material for electrostatic powder coating. In other words, the coating material for electrostatic coating using the charge enhancer is excellent in environmental resistance, storage stability, particularly thermal stability and durability, and can form a thick film having a coating efficiency of 100% and no coating film defects.

[Examples]

Hereinafter, the present invention will be described in more detail based on the examples, but these are not intended to limit the invention in any way. In the following examples, "parts" all mean "parts by mass".

The purification of the pyridinedicarboxylic acid derivative represented by the formula (1) is carried out by column chromatography, adsorption purification using tannin extract, activated carbon, activated clay, etc., by solvent recrystallization or crystallization, etc. And proceed. The identification of the compounds was carried out by NMR (Nuclear Magnetic Resonance) analysis.

[Synthesis Example 1-1] (Synthesis of Compound 1-2)

In the reaction vessel purged with nitrogen, aniline 8.0 g (86.3 mmol), triethylamine 8.7 g (86.3 mmol), and 50 ml of alkane, while adding 2,6-pyridine dimethyl hydrazine dichloride 8.0 g (39.2 mmol) After 50 ml of the alkane solution, it was further stirred for 5 hours. After standing overnight, the reaction solution was added to 400 ml of dilute hydrochloric acid while stirring. The precipitated crude product was collected by filtration, washed with water, and dried under reduced pressure at 60 ° C, whereby white crystals of 12.05 g (yield: 97.2%) were obtained.

The structure was identified using NMR on the obtained white crystals. The following 15 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).

δ (ppm) = 11.05 (2H), 8.42 - 8.43 (2H), 8.30 - 8.33 (1H), 7.93 - 7.95 (4H), 7.45 - 7.48 (4H), 7.20 - 7.22 (2H).

[Synthesis Example 1-2] (Synthesis of Compound 1-3)

In a reaction vessel purged with nitrogen, o-toluidine 5.5 g (51.5 mmol), triethylamine 5.2 g (51.5 mmol), and 100 ml of alkane, while adding 2,6-pyridine dimethyl hydrazine dichloride 5.0 g (24.5 mmol) After 50 ml of the alkane solution, it was further stirred for 6 hours. After standing overnight, the reaction solution was added to 500 ml of dilute hydrochloric acid while stirring. The precipitated crude product was collected by filtration, washed with water, and dried under reduced pressure at 60 ° C, whereby white crystals of 7.71 g (yield: 90.7%) were obtained.

The structure was identified using NMR on the obtained white crystals. The following 19 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).

δ(ppm)=10.84(2H), 8.38-8.39(2H), 8.29-8.31(1H),7.44-7.45(2H),7.33-7.35(2H),7.27-7.30(2H),7.22-7.25(2H ), 2.31 (6H).

[Synthesis Example 1-3] (Synthesis of exemplified compounds 1-4)

In a reaction vessel purged with nitrogen, m-toluidine 5.5 g (51.5 mmol), triethylamine 5.2 g (51.5 mmol), and 100 ml of alkane, while adding 2,6-pyridine dimethyl hydrazine dichloride 5.0 g (24.5 mmol) After 50 ml of the alkane solution, it was further stirred for 7 hours. After standing overnight, the reaction solution was added to 500 ml of dilute hydrochloric acid while stirring. The precipitated crude product was collected by filtration, washed with water, and dried under reduced pressure at 60 ° C, whereby white crystals of 7.90 g (yield: 92.9%) were obtained.

The structure was identified using NMR on the obtained white crystals. The following 19 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).

δ(ppm)=10.96(2H), 8.40-8.41(2H), 8.29-8.32(1H), 7.77(2H), 7.69-7.70 (2H), 7.32-7.35 (2H), 7.02-7.03 (2H), 2.38 (6H).

[Synthesis Example 1-4] (Synthesis of exemplified compound 1-5)

In a reaction vessel purged with nitrogen, 9.2 g (86.3 mmol) of p-toluidine and 8.7 g (86.3 mmol) of triethylamine were added. 50 ml of alkane, while adding 2,6-pyridine dimethyl hydrazine dichloride 8.0 g (39.2 mmol) 50 ml of alkane solution, add two After 50 ml of the alkane, it was further stirred for 5 hours. After standing overnight, the reaction solution was added to 400 ml of dilute hydrochloric acid while stirring. The precipitated crude product was collected by filtration, washed with water, and dried under reduced pressure at 60 ° C to afford white crystals 11.62 g (yield 86.1%).

The structure was identified using NMR on the obtained white crystals. The following 19 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).

δ (ppm) = 10.97 (2H), 8.39-8.40 (2H), 8.28-8.31 (1H), 7.80-7.82 (4H), 7.25-7.26 (4H), 2.33 (6H).

[Synthesis Example 1-5] (Synthesis of Compounds 1-6)

In a reaction vessel purged with nitrogen, 4-tributylaniline 12.9 g (86.3 mmol), triethylamine 8.7 g (86.3 mmol), and 50 ml of alkane, while adding 2,6-pyridine dimethyl hydrazine dichloride 8.0 g (39.2 mmol) After 50 ml of the alkane solution, it was further stirred for 6 hours. After standing overnight, the reaction solution was added to 400 ml of dilute hydrochloric acid while stirring. The precipitated crude product was collected by filtration, washed with water, and dried under reduced pressure at 60 ° C, whereby 15.78 g (yield: 93.9%) of white crystals were obtained.

The structure was identified using NMR on the obtained white crystals. The following 31 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).

δ (ppm) = 10.97 (2H), 8.39-8.40 (2H), 8.28-8.31 (1H), 7.82-7.83 (4H), 7.45-7.47 (4H), 1.31 (18H).

[Synthesis Example 1-6] (Synthesis of exemplified compound 1-7)

In a reaction vessel purged with nitrogen, m-chloroaniline 6.6 g (51.5 mmol), triethylamine 5.2 g (51.5 mmol), and 100 ml of alkane, while adding 2,6-pyridine dimethyl hydrazine dichloride 5.0 g (24.5 mmol) After 50 ml of the alkane solution, it was further stirred for 6 hours. After standing overnight, the reaction solution was added to 500 ml of dilute hydrochloric acid while stirring. The precipitated crude product was collected by filtration, washed with water, and then dried under reduced pressure at 60 ° C to obtain white crystals 8.76 g (yield 92.2%).

The structure was identified using NMR on the obtained white crystals. The following 13 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).

δ (ppm) = 11.09 (2H), 8.42 - 8.43 (2H), 8.31 - 8.34 (1H), 8.14 (2H), 7.87-7.88 (2H), 7.48-7.51 (2H), 7.26-7.27 (2H).

[Synthesis Example 1-7] (Synthesis of Compound 1-8)

In a reaction vessel purged with nitrogen, m-methoxyaniline 6.3 g (51.5 mmol), triethylamine 5.2 g (51.5 mmol), and 100 ml of alkane, while adding 2,6-pyridine dimethyl hydrazine dichloride 5.0 g (24.5 mmol) After 50 ml of the alkane solution, it was further stirred for 6 hours. After standing overnight, the reaction solution was added to 500 ml of dilute hydrochloric acid while stirring. The precipitated crude product was collected by filtration, washed with water, and dried under reduced pressure at 60 ° C, whereby white crystals of 8.28 g (yield 90.0%) were obtained.

The structure was identified using NMR on the obtained white crystals. The following 19 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).

δ (ppm) = 11.00 (2H), 8.41 - 8.42 (2H), 8.30-8.33 (1H), 7.64 - 7.65 (2H), 7.49-7.50 (2H), 7.35-7.38 (2H), 6.78-6.80 (2H ), 3.81 (6H).

[Synthesis Example 1-8] (Synthesis of Compound 1-9)

In a reaction vessel purged with nitrogen, 2-t-butylaniline 7.7 g (51.5 mmol), triethylamine 5.2 g (51.5 mmol), 100 ml of alkane, while adding 2,6-pyridine dimethyl hydrazine dichloride 5.0 g (24.5 mmol) After 50 ml of the alkane solution, it was further stirred for 6.5 hours. After standing overnight, the reaction solution was added to 500 ml of dilute hydrochloric acid while stirring. Ethyl acetate was added and a liquid separation operation was carried out, whereby an organic layer was collected. The organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and brine, and then dried over anhydrous sodium sulfate. The crude product was purified by column chromatography [carrier: silica gel, eluent: ethyl acetate] to afford 10.5 g (yield 100%) of amorphous crystals.

The structure was identified using NMR on the obtained amorphous crystal. The following 31 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).

δ (ppm) = 10.84 (2H), 8.36-8.38 (2H), 8.28-8.30 (1H), 7.48-7.50 (2H), 7.27-7.32 (4H), 7.15-7.16 (2H), 1.34 (18H).

[Synthesis Example 1-9] (Synthesis of Compound 1-10)

In a reaction vessel purged with nitrogen, 2-(trifluoromethyl)aniline 8.3 g (51.5 mmol), triethylamine 5.2 g (51.5 mmol), two 100 ml of alkane, while adding 2,6-pyridine dimethyl hydrazine dichloride 5.0 g (24.5 mmol) After 50 ml of the alkane solution, it was further stirred for 6 hours. After standing overnight, the reaction solution was added to 500 ml of dilute hydrochloric acid while stirring. The precipitated crude product was collected by filtration, washed with water, and dried under reduced pressure at 60 ° C, whereby white crystals of 9.33 g (yield 84.1%) were obtained.

The structure was identified using NMR on the obtained white crystals. The following 13 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).

δ (ppm) = 10.82 (2H), 8.37-8.38 (2H), 8.30-8.32 (1H), 7.77-7.84 (4H), 7.67-7.68 (2H), 7.56-7.59 (2H).

[Example 1-10] (Manufacture of non-magnetic toner 1-1)

91 parts of a styrene-acrylate copolymer resin (manufactured by Mitsui Chemicals, Inc., trade name: CPR-100, acid value: 0.1 mgKOH/g), by a heating and mixing device (biaxial extrusion kneader) at 130 ° C, 1 part of a synthetic pyridinedicarboxylic acid derivative (exemplified compound 1-4) synthesized in Example 1-3, carbon black (manufactured by Mitsubishi Chemical Corporation, trade name: MA-100), 5 parts, and low molecular weight polypropylene (Sanyo Chemical Manufactured by the company, trade name Viscol 550P) 3 parts melt mixed. The cooled mixture was coarsely pulverized by a hammer mill, and then finely pulverized by a jet mill to carry out classification to obtain a non-magnetic volume having a volume average particle diameter of 9 ± 0.5 μm. Toner 1-1.

(Evaluation of Non-Magnetic Toner 1-1)

The non-magnetic toner 1-1 and the non-coated ferrite carrier (F-150 manufactured by POWDERTECH Co., Ltd.) are mixed and oscillated in a ratio of 4 to 100 parts by mass (toner: carrier) to adjust After the toner was negatively charged, the charge amount was measured by a blow-off powder charge amount measuring device. The result was -36.6 μc/g.

Similarly, the charge amount was also evaluated in the case of mixing with a ferrite carrier (F96-150 manufactured by POWDERTECH Co., Ltd.). The result was -23.7 μc/g.

[Examples 1-11] (Manufacture and evaluation of non-magnetic toner 1-2)

Except that the pyridinedicarboxylic acid derivative (exemplified compound 1-4) synthesized in Synthesis Example 1-3 was replaced with the synthetic pyridinedicarboxylic acid derivative (exemplified compound 1-6) synthesized in Synthesis Example 1-5, The non-magnetic toner 1-2 was prepared in the same manner as in Example 1-10, and the charge amount was evaluated by a blow-off type powder charge amount measuring device. As a result, the charge amount in the case of mixing with a non-coating ferrite carrier (F-150 manufactured by POWDERTECH Co., Ltd.) was -32.3 μc/g. Similarly, the charge amount in the case of mixing with a barium-coated ferrite carrier (F96-150 manufactured by POWDERTECH Co., Ltd.) was -22.5 μc/g.

[Comparative Example 1-1] (Comparative manufacture and evaluation of non-magnetic toner 1-1)

The same procedure as in Example 1-10 except that the pyridinedicarboxylic acid derivative (exemplified compound 1-4) synthesized in Synthesis Example 1-3 was replaced with a salt of 3,5-t-butylsalicylic acid and zinc. The method of preparing the comparative non-magnetic toner 1-1 was carried out, and the charge amount was evaluated by a blow-off type powder charge amount measuring device. As a result, the charge amount in the case of mixing with a non-coating ferrite carrier (F-150 manufactured by POWDERTECH Co., Ltd.) was -23.0 μc/g. Similarly, the charge amount in the case of mixing with a barium-coated ferrite carrier (F96-150 manufactured by POWDERTECH Co., Ltd.) was -15.0 μc/g.

[Synthesis Example 2-1] (Synthesis of exemplified compound 2-2)

In a reaction vessel purged with nitrogen, cyclohexylamine 5.0 g (51.5 mmol), triethylamine 5.2 g (51.5 mmol), and 100 ml of alkane, while adding 2,6-pyridine dimethyl hydrazine dichloride 5.0 g (24.5 mmol) After 50 ml of the alkane solution, it was further stirred for 6 hours. After standing overnight, the reaction solution was added to 500 ml of water while stirring. Hydrochloric acid was added, and the pH of the solution was adjusted to 3, followed by further stirring for 1 hour. The precipitated crude product was collected by filtration, washed with water, and dried under reduced pressure at 60 ° C, whereby white crystals of 7.16 g (yield 88.4%) were obtained.

The structure was identified using NMR on the obtained white crystals. The following 27 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).

δ (ppm) = 8.10-8.38 (5H), 3.80 (2H), 1.21-1.89 (20H).

[Synthesis Example 2-2] (Synthesis of Compound 2-3)

In a reaction vessel purged with nitrogen, 4-tert-butylcyclohexylamine 8.0 g (51.5 mmol), triethylamine 5.2 g (51.5 mmol), and 100 ml of alkane, while adding 2,6-pyridine dimethyl hydrazine dichloride 5.0 g (24.5 mmol) After 50 ml of the alkane solution, it was further stirred for 6 hours. After standing overnight, the reaction solution was added to 500 ml of water while stirring. Hydrochloric acid was added, and the pH of the solution was adjusted to 3, followed by further stirring for 1 hour. The extracting operation was carried out with ethyl acetate, and the organic layer was washed with sodium hydrogen carbonate water, and then dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a residue. After recrystallization from a mixed solvent of ethyl acetate and hexane, the mixture was dried under reduced pressure at 60 ° C to obtain white crystals 3.16 g (yield 29.3%) as a mixture of stereoisomers.

The structure was identified using NMR on the obtained white crystals. The following 43 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).

δ (ppm) = 8.08-8.33 (5H), 3.72-4.18 (2H), 0.87-2.00 (36H).

[Synthesis Example 2-3] (Synthesis of exemplified compound 2-6)

In a reaction vessel purged with nitrogen, 4.4 g (51.5 mmol) of cyclopentylamine, 5.2 g (51.5 mmol) of triethylamine, and two were added. After 100 ml of alkane, add 2,6-pyridine dimethyl hydrazine dichloride 5.0 g (24.5 mmol) to the mixture while stirring. After 50 ml of the alkane solution, it was further stirred for 6 hours. After standing overnight, the reaction solution was added to 500 ml of water while stirring. Hydrochloric acid was added, and the pH of the solution was adjusted to 3, followed by further stirring for 1 hour. The precipitated crude product was collected by filtration, washed with water, and dried under reduced pressure at 60 ° C, whereby white crystals of 6.14 g (yield 84.1%) were obtained.

The structure was identified using NMR on the obtained white crystals. The following 23 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).

δ (ppm) = 8.71 (2H), 8.15 (3H), 4.23 (2H), 1.59-1.97 (16H).

[Synthesis Example 2-4] (Synthesis of exemplified compound 2-7)

In a reaction vessel purged with nitrogen, 5.8 g (51.5 mmol) of cycloheptylamine, 5.2 g of triethylamine (51.5 mmol), and After 100 ml of the alkane, while stirring, 2,6-pyridine dimethyl hydrazine dichloride 5.0 g (24.5 mmol) was added dropwise. After 50 ml of the alkane solution, it was further stirred for 6 hours. After standing overnight, the reaction solution was added to 500 ml of water while stirring. Hydrochloric acid was added, and the pH of the solution was adjusted to 3, followed by further stirring for 1 hour. The precipitated crude product was collected by filtration, washed with water, and dried under reduced pressure at 60 ° C, whereby white crystals 7.89 g (yield: 89.7%) were obtained.

The structure was identified using NMR on the obtained white crystals. The following 31 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).

δ (ppm) = 8.37 (2H), 8.09-8.14 (3H), 3.99 (2H), 1.52-1.93 (24H).

[Example 2-5] (Manufacture of non-magnetic toner 2-1)

91 parts of a styrene-acrylate copolymer resin (manufactured by Mitsui Chemicals, Inc., trade name: CPR-100, acid value: 0.1 mgKOH/g), by a heating and mixing device (biaxial extrusion kneader) at 130 ° C, 1 part of a synthetic pyridinedicarboxylic acid derivative (exemplified compound 2-3) synthesized in Example 2-2, carbon black (manufactured by Mitsubishi Chemical Corporation, trade name: MA-100) 5 Parts and low molecular weight polypropylene (manufactured by Sanyo Chemical Co., Ltd., trade name Viscol 550P) were melt mixed. The cooled mixture was coarsely pulverized by a hammer mill, and then finely pulverized by a jet mill to carry out classification to obtain a non-magnetic toner 2-1 having a volume average particle diameter of 9 ± 0.5 μm.

(Evaluation of Non-Magnetic Toner 2-1)

The non-magnetic toner 2-1 and the non-coated ferrite carrier (F-150 manufactured by POWDERTECH Co., Ltd.) are mixed and oscillated in a ratio of 4 to 100 parts by mass (toner: carrier) to adjust After the toner is negatively charged, the charge amount is measured by a blown powder type charge amount measuring device. The result was -38.2 μc/g.

Similarly, the charge amount was also evaluated in the case of mixing with a ferrite carrier (F96-150 manufactured by POWDERTECH Co., Ltd.). The result was -25.3 μc/g.

[Comparative Example 2-1] (Compared with the manufacture and evaluation of non-magnetic toner 2-1)

The same procedure as in Example 2-5 was carried out except that the pyridinedicarboxylic acid derivative (exemplified compound 2-3) synthesized in Synthesis Example 2-2 was replaced with a salt of 3,5-t-butylsalicylic acid and zinc. In the method, the comparative non-magnetic toner 2-1 was prepared, and the charge amount was evaluated by a blow-off type powder charge amount measuring device. As a result, the charge amount in the case of mixing with a non-coating ferrite carrier (F-150 manufactured by POWDERTECH Co., Ltd.) was -23.0 μc/g. Similarly, the charge amount in the case of mixing with a barium-coated ferrite carrier (F96-150 manufactured by POWDERTECH Co., Ltd.) was -15.0 μc/g.

As is apparent from the above results, the charge amount of the toner using the charge control agent containing the pyridine dicarboxylic acid derivative represented by the general formula (1) of the present invention as an active ingredient becomes high.

[Examples 1-12] (Preparation of resin dispersion)

Polyester resin (manufactured by Mitsubishi Rayon Co., Ltd., DIACRON ER-561) 80 Mixing, 320 parts of ethyl acetate and 32 parts of isopropyl alcohol, using a homogenizer (manufactured by Meinu Co., Ltd., non-bubble mixer NGM-0.5TB), while stirring at 5000~10000 rpm, 0.1 mass is added in an appropriate amount. The ammonia water of % was subjected to phase inversion emulsification, and the solvent was decompressed while being depressurized by an evaporator to obtain a resin dispersion liquid. The volume average particle diameter of the resin particles in the dispersion was 0.2 μm (the resin particle concentration was adjusted to 20% by mass in terms of ion-exchanged water).

(Preparation of charge control agent dispersion)

0.2 parts of sodium dodecylbenzenesulfonate, 0.2 parts of Sorbon T-20 (manufactured by Toho Chemical Co., Ltd.), and 17.6 parts of ion-exchanged water were mixed and dissolved, and then the pyridinedicarboxylic acid synthesized in Synthesis Example 1-3 was further added. Derivative (exemplified compound 1-4) 2.0 parts and zirconia beads (bead size 0.65 mm) , equivalent to 15 ml), dispersed by a paint conditioner (manufactured by UNION NJ (USA), Red Devil No. 5400-5L) for 3 hours. The zirconia beads were removed using a sieve, and adjusted by ion-exchanged water to prepare a 10% by mass of a charge control agent dispersion.

(Preparation of polymerized toner)

Into a reaction vessel equipped with a thermometer, a pH meter, and a stirrer, 125 parts of the above resin dispersion, 1.0 part by weight of a 20% by mass aqueous sodium dodecylbenzenesulfonate solution, and 125 parts of ion-exchanged water were added, and the liquid temperature was controlled at 30 ° C. Stir at 150 rpm for 30 minutes. A 1% by mass aqueous solution of nitric acid was added to adjust the pH to 3.0, and the mixture was further stirred for 5 minutes. While dispersing by a homogenizer (manufactured by IKA Japan, Ultra Turrax T-25), 0.125 parts of polyaluminum chloride was added, and the temperature of the liquid was raised to 50 ° C, and further dispersed for 30 minutes. After 62.5 parts of the above resin dispersion and 4.0 parts of the above-mentioned charge control agent dispersion were added, a 1% by mass aqueous solution of nitric acid was added to adjust the pH to 3.0, and further dispersed for 30 minutes. While stirring at 400 to 700 rpm using a stirrer, 8.0 parts of a 5% by mass aqueous sodium hydroxide solution was added, and stirring was continued until the volume average particle diameter of the toner became 9.5 μm. After the temperature of the liquid was raised to 75 ° C, the mixture was further stirred for 2 hours, and it was confirmed that the volume average particle diameter became 6.0. After μm and the particle shape is spherical, it is rapidly cooled by using ice water. It was collected by filtration and dispersed and washed with ion-exchanged water. The dispersion washing is repeated until the conductivity of the filtrate after dispersion is 20 μS/cm or less. Thereafter, it was dried by a dryer at 40 ° C to obtain toner particles.

The obtained toner was sieved by a sieve of 166 mesh (mesh 90 μm) as a toner for evaluation.

(Evaluation)

The obtained evaluation toner was mixed and oscillated in a ratio of 2 parts of the toner and 100 parts of a ferrite carrier (F96-150 manufactured by POWDERTECH Co., Ltd.) to make the toner negatively charged, and the powder was blown off. The body charge measuring device measures the saturated charge amount in an environment of a temperature of 25 ° C and a humidity of 50%. As a result, the saturated charge amount was -38.9 μc/g.

[Comparative Example 1-2]

The 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 for comparison, and the saturated charge amount was measured. As a result, the saturated charge amount was -20.5 μC/g.

[Example 2-6] (Preparation of resin dispersion)

80 parts of polyester resin (manufactured by Mitsubishi Rayon Co., Ltd., DIACRON ER-561), 320 parts of ethyl acetate, and 32 parts of isopropyl alcohol were mixed, and a homogenizer (manufactured by Meiya Co., Ltd., a bubble-free mixer NGM) was used. -0.5 TB), while stirring at 5,000 to 10,000 rpm, a 0.1% by mass aqueous ammonia solution was added dropwise to carry out phase inversion emulsification, and the solvent was decompressed while being decompressed by an evaporator to obtain a resin dispersion liquid. The volume average particle diameter of the resin particles in the dispersion was 0.2 μm (the resin particle concentration was adjusted to 20% by mass in terms of ion-exchanged water).

(Preparation of charge control agent dispersion)

0.2 parts of sodium dodecylbenzenesulfonate, 0.2 parts of Sorbon T-20 (manufactured by Toho Chemical Co., Ltd.), and 17.6 parts of ion-exchanged water were mixed and dissolved, and the pyridinedicarboxylic acid synthesized in Synthesis Example 2-2 was further added. Derivative (exemplified compound 2-3) 2.0 parts and zirconia beads (bead size 0.65 mm) , equivalent to 15 ml), dispersed by a paint conditioner (manufactured by UNION NJ (USA), Red Devil No. 5400-5L) for 3 hours. The zirconia beads were removed using a sieve, and adjusted by ion-exchanged water to prepare a 10% by mass of a charge control agent dispersion.

(Preparation of polymerized toner)

Into a reaction vessel equipped with a thermometer, a pH meter, and a stirrer, 125 parts of the above resin dispersion, 1.0 part by weight of a 20% by mass aqueous sodium dodecylbenzenesulfonate solution, and 125 parts of ion-exchanged water were added, and the liquid temperature was controlled at 30 ° C. Stir at 150 rpm for 30 minutes. A 1% by mass aqueous solution of nitric acid was added to adjust the pH to 3.0, and the mixture was further stirred for 5 minutes. While dispersing by a homogenizer (manufactured by IKA Japan, Ultra Turrax T-25), 0.125 parts of polyaluminum chloride was added, and the temperature of the liquid was raised to 50 ° C, and further dispersed for 30 minutes. After 62.5 parts of the above resin dispersion and 4.0 parts of the above-mentioned charge control agent dispersion were added, a 1% by mass aqueous solution of nitric acid was added to adjust the pH to 3.0, and further dispersed for 30 minutes. While stirring at 400 to 700 rpm using a stirrer, 8.0 parts of a 5% by mass aqueous sodium hydroxide solution was added, and stirring was continued until the volume average particle diameter of the toner became 9.5 μm. After the temperature of the liquid was raised to 75 ° C, the mixture was further stirred for 2 hours, and it was confirmed that the volume average particle diameter was 6.0 μm, and the particle shape was spherical, and then rapidly cooled with ice water. It was collected by filtration and dispersed and washed with ion-exchanged water. The dispersion cleaning is repeated until the conductivity of the filtrate after dispersion is 20 μS/cm or less. Thereafter, it was dried by a dryer at 40 ° C to obtain toner particles.

The obtained toner was sieved by a sieve of 166 mesh (mesh 90 μm) as a toner for evaluation.

(Evaluation)

The obtained evaluation toner was mixed and oscillated in a ratio of 2 parts of the toner and 100 parts of a ferrite carrier (F96-150 manufactured by POWDERTECH Co., Ltd.) to make the toner negatively charged, and the powder was blown off. The body charge measuring device measures the saturated charge amount in an environment of a temperature of 25 ° C and a humidity of 50%. As a result, the saturated charge amount is -40.5 μc/g.

[Comparative Example 2-2]

The 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 for comparison, and the saturated charge amount was measured. As a result, the saturated charge amount was -20.5 μC/g.

From the above results, it is clear that 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.

In other words, by using a charge control agent containing the pyridine dicarboxylic acid derivative represented by the general formula (1) of the present invention as an active ingredient, it is possible to impart high charging performance to the polymerized toner.

Industrial availability

The pyridinedicarboxylic acid derivative represented by the formula (1) of the present invention has excellent charging properties, and the charge control agent containing the compound as an active component has remarkably high charging performance as compared with the prior charge controlling agent. Further, the above charge control agent is most suitable as a color toner, and is particularly suitable as a polymerized toner. Further, the above-mentioned charge control agent is also extremely useful because it does not contain heavy metals such as chromium compounds which are an environmental concern.

Claims (6)

A charge control agent containing one or two or more kinds of pyridine dicarboxylic acid derivatives represented by the following formula (1) as an active ingredient, [In the formula (1), R ₁ , R ₂ and R ₃ may be the same or different and represent a hydrogen atom, a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a 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, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, and a carbon number which may have a substituent a linear or branched alkenyl group of 2 to 6, a linear or branched alkoxy group having 1 to 8 carbon atoms which may have a substituent, and a ring having 5 to 10 carbon atoms which may have a substituent Alkoxy, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted condensed polycyclic aromatic group, or substituted or unsubstituted aromatic oxygen R ₄ and R ₅ may be the same or different and each represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, and a carbon atom which may have a substituent. a cycloalkyl group of 5 to 10, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, and a substituted Non-substituted heterocyclic group, or a substituted or non-substituted condensed polycyclic aromatic group, R ₆ and R ₇ may be identical or different, it represents a substituent having a carbon atom of the cycloalkyl group having 5 to 10 a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted condensed polycyclic aromatic group; here, R ₁ , R ₂ and R ₃ may be bonded to each other by adjacent groups. ring]. The charge control agent of claim 1, wherein the pyridinedicarboxylic acid derivative represented by the above formula (1) is a compound represented by the following formula (1A), [In the formula (1A), R ₁ , R ₂ and R ₃ may be the same or different and represent a hydrogen atom, a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a 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, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, and a carbon number which may have a substituent a linear or branched alkenyl group of 2 to 6, a linear or branched alkoxy group having 1 to 8 carbon atoms which may have a substituent, and a ring having 5 to 10 carbon atoms which may have a substituent Alkoxy, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted condensed polycyclic aromatic group, or substituted or unsubstituted aromatic oxygen R ₄ and R ₅ may be the same or different and each represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, and a carbon atom which may have a substituent. a cycloalkyl group of 5 to 10, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, and a substituted Non-substituted heterocyclic group, or a substituted or non-substituted condensed polycyclic aromatic group, R ₆ and R ₇ may be identical or different, it represents a substituent having a carbon atom of the cycloalkyl group having 5 to 10 a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted condensed polycyclic aromatic group; here, R ₁ , R ₂ and R ₃ may be bonded to each other by adjacent groups. ring]. The charge control agent according to claim 1, wherein the pyridinedicarboxylic acid derivative represented by the above formula (1) is a compound represented by the following formula (1A-1). [In the formula (1A-1), R ₁ , R ₂ and R ₃ may be the same or different and each represents a hydrogen atom, a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a cyano group, a trifluoro group. a methyl group, a nitro group, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, and a carbon which may have a substituent a linear or branched alkenyl group having 2 to 6 atoms, a linear or branched alkoxy group having 1 to 8 carbon atoms which may have a substituent, and 5 to 10 carbon atoms which may have a substituent a cycloalkoxy group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted The aryloxy group, R ₄ and R ₅ may be the same or different and each represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, and a carbon which may have a substituent. a cycloalkyl group having 5 to 10 atoms, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, The heterocyclyl or unsubstituted, or a substituted or non-substituted condensed polycyclic aromatic _{group, R 8, R 9, R} 10, R 11, R 12, R 13, R 14, R 15, R 16 And R ₁₇ may be the same or different and represent a hydrogen atom, a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a cyano group, a trifluoromethyl group, a nitro group, and a carbon atom which may have a substituent. a linear or branched alkyl group of ~8, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent a linear or branched alkoxy group having 1 to 8 carbon atoms which may have a substituent, a cycloalkoxy group having 5 to 10 carbon atoms which may have a substituent, a substituted or unsubstituted aromatic group a hydrocarbyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group; here, 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 may be bonded to each other by adjacent groups to form a ring]. The charge control agent according to claim 1 or 2, wherein R ₆ and R ₇ are a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent. A toner containing the charge control agent, the colorant, and the binder resin according to any one of claims 1 to 4. A polymerized toner containing the charge control agent, the colorant, and the binder resin according to any one of claims 1 to 4.