WO2013129015A1

WO2013129015A1 - Charge control agent and toner using same

Info

Publication number: WO2013129015A1
Application number: PCT/JP2013/052073
Authority: WO
Inventors: 育夫木村; 一徳辻; 雅也東條; 昌史浅貝
Original assignee: 保土谷化学工業株式会社
Priority date: 2012-02-29
Filing date: 2013-01-30
Publication date: 2013-09-06
Also published as: JP5329010B1; TW201348897A; JPWO2013129015A1

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 fields such as electrophotography and electrostatic recording, and a negatively chargeable toner containing the charge control agent.

In an electrophotographic image forming process, an electrostatic latent image is formed on an inorganic photoreceptor such as selenium, selenium alloy, cadmium sulfide, amorphous silicon, or an organic photoreceptor using a charge generator and a charge transport agent. Is developed with toner, transferred onto paper or plastic film, and fixed to obtain a visible image.

The photosensitive member has positive and negative charging characteristics depending on the structure. When the printed part is left as an electrostatic latent image by exposure, development is performed with a reverse sign charging toner, while on the other hand, the printed part is discharged to perform reverse development. In the case of carrying out the development, development is performed with a toner having the same sign.

The toner is composed of a binder resin, a colorant, and other additives. In order to impart desirable charging characteristics (charging speed, charge level, charge stability, etc.), aging stability, environmental stability, etc., a charge control agent is generally added. By adding the charge control agent, the toner characteristics are greatly improved.

As a positive triboelectric charge control agent known in the technical field, nigrosine dyes, azine dyes, copper phthalocyanine pigments, quaternary ammonium salts, and polymers having quaternary ammonium salts in the side chain are known. ing. Known negative triboelectric charge control agents include metal complex salts of monoazo dyes, metal complex salts of salicylic acid, naphthoic acid or dicarboxylic acid, copper phthalocyanine pigments, resins containing acid components, and the like.

In the case of color toners that are expected to expand in the future, a light-colored, preferably colorless, charge control agent that does not affect the hue is indispensable. These light-colored or colorless charge control agents include metal complex salts of hydroxybenzoic acid derivatives (see, for example, Patent Documents 1 to 3) and aromatic dicarboxylic acid metal salt compounds (for example, Patent Document 4) for negatively chargeable toners. Metal complex salt compounds of anthranilic acid derivatives (for example, see Patent Documents 5 to 6), organoboron compounds (for example, see Patent Documents 7 to 8), biphenol compounds (for example, see Patent Document 9), calix (n) Examples include allene compounds (see, for example, Patent Documents 10 to 15) and cyclic phenol sulfides (see, for example, Patent Documents 16 to 18). Further, there are quaternary ammonium salt compounds (for example, see Patent Documents 19 to 21) for positively chargeable toners.

Japanese Patent Publication No. 55-042752 JP 61-069073 A JP 61-221756 A JP-A-57-111541 JP 61-141453 A Japanese Patent Laid-Open No. 62-094856 U.S. Pat. No. 4,767,688 JP-A-1-3066861 JP-A 61-003149 Japanese Patent No. 2568675 Japanese Patent No. 2899038 Japanese Patent No. 3359657 Japanese Patent No. 3313871 Japanese Patent No. 3325730 Japanese Patent Laid-Open No. 2003-162100 JP 2003-295522 A WO2007-111346 WO2007-119797 JP 57-119364 A JP 58-009154 A JP 58-098742 A

However, many of these charge control agents are complexes or salts made of heavy metals such as chromium, which are problems regarding waste regulations and are not necessarily safe. In addition, the charge imparting effect required today is low and the charge rising speed is insufficient, so that the initial copy image lacks clarity, the quality of the copy image during continuous copying tends to fluctuate, However, there is a drawback that it cannot be applied to polymerized toner. Therefore, a charge control agent that has a high charge imparting effect and can be applied to polymerized toners has been desired.

The object of the present invention is to provide a safe charge control agent having a high charge amount and no problem with waste regulations. It is another object of the present invention to provide a negatively chargeable toner for developing an electrostatic image and a negatively chargeable polymerized toner having high charging performance using the charge control agent.

The present invention has been obtained as a result of intensive studies to achieve the above object, and has the following gist.

That is, the present invention provides a charge control agent containing one or more pyridinedicarboxylic acid derivatives represented by the general formula (1) as an active ingredient.

In the general formula (1), R ₁ , R ₂ and R ₃ may be the same or different from each other, and are a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, cyano group, A trifluoromethyl group, a nitro group, an optionally substituted linear or branched alkyl group having 1 to 8 carbon atoms, and an optionally substituted carbon atom having 5 to 10 carbon atoms A cycloalkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a straight chain having 1 to 8 carbon atoms which may have a substituent, or A branched alkyloxy group, an optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, substituted or Unsubstituted fused polycyclic aromatic groups, or Represents a substituted or unsubstituted aryloxy group, and R ₄ and R ₅ may be the same or different from each other, and may have a hydrogen atom, a deuterium atom, or a C 1-8 carbon atom which may have a substituent. A linear or branched alkyl group, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, a straight chain having 2 to 6 carbon atoms which may have a substituent, or A branched alkenyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, wherein R ₆ and R ₇ are the same as each other Or a cycloalkyl group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted condensed polycyclic aromatic group which may have a substituent. Show. Here, R ₁ , R ₂ and R ₃ may be bonded to each other at adjacent groups to form a ring.

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

In general formula (1A), R ₁ , R ₂ and R ₃ may be the same or different from each other, and are a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, cyano group, A trifluoromethyl group, a nitro group, an optionally substituted linear or branched alkyl group having 1 to 8 carbon atoms, and an optionally substituted carbon atom having 5 to 10 carbon atoms A cycloalkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a straight chain having 1 to 8 carbon atoms which may have a substituent, or A branched alkyloxy group, an optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, substituted or Unsubstituted fused polycyclic aromatic groups, Or a substituted or unsubstituted aryloxy group, R ₄ and R ₅ may be the same as or different from each other, and may have a hydrogen atom, a deuterium atom, or a substituent having 1 to 8 carbon atoms. A linear or branched alkyl group, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, a straight chain having 2 to 6 carbon atoms which may have a substituent, or A branched alkenyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, wherein R ₆ and R ₇ are the same as each other Or a cycloalkyl group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted condensed polycyclic aromatic group which may have a substituent. Show. Here, R ₁ , R ₂ and R ₃ may be bonded to each other at adjacent groups to form a ring.

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

In general formula (1A-1), R ₁ , R ₂ and R ₃ may be the same or different from each other, and are a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, cyano Group, a trifluoromethyl group, a nitro group, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, and a carbon atom having 5 to 5 carbon atoms which may have a substituent 10 cycloalkyl groups, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and a linear chain having 1 to 8 carbon atoms which may have a substituent A branched or branched alkyloxy group, an optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, Substituted or unsubstituted fused polycyclic aromatics Group, or a substituted or unsubstituted aryloxy group, R ₄ and R ₅ may be the same or different from each other, and may have a hydrogen atom, a deuterium atom, or an optionally substituted carbon atom having 1 to 8 linear or branched alkyl groups, optionally substituted cycloalkyl groups having 5 to 10 carbon atoms, and optionally substituted straight chain having 2 to 6 carbon atoms A branched or branched alkenyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, or a 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 as or different from each other, and are a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom , Hydroxyl group, cyano group, A fluoromethyl group, a nitro group, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, and a cyclocarbon having 5 to 10 carbon atoms which may have a substituent; An alkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a linear or branched chain having 1 to 8 carbon atoms which may have a substituent Alkyloxy group, optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted A substituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group is shown. 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 are mutually adjacent groups. It may combine to form a ring.

In the pyridinedicarboxylic acid derivative represented by the general formula (1) and the pyridinedicarboxylic acid derivative represented by the general formula (1A-1), R ₆ and R ₇ may have a substituent. It may be a cycloalkyl group having 5 to 10 carbon atoms.

The present invention also provides a toner containing a charge control agent containing one or more pyridinedicarboxylic acid derivatives represented by the above general formula (1) as active ingredients, a colorant, and a binder resin. I will provide a.

The present invention further provides a polymerization comprising a charge control agent containing one or more pyridinedicarboxylic acid derivatives represented by the general formula (1) as an active ingredient, a colorant, and a binder resin. Provide toner.

The charge control agent containing one or more pyridinedicarboxylic acid derivatives represented by the above general formula (1) as an active ingredient has a high charge amount, and is safe and has no problem with waste regulations. Therefore, it can be suitably used for toner charge control. Therefore, the present invention relates to the use of a charge control agent containing one or more pyridinedicarboxylic acid derivatives represented by the above general formula (1) as an active ingredient for charge control of the toner, or the above general formula. It can also be said that the charge control agent containing one or more pyridinedicarboxylic acid derivatives represented by (1) as an active ingredient is applied to toner charge control. The toner may be a polymerized toner.

Furthermore, the present invention can also be referred to as a toner charge control method using a charge control agent containing one or more pyridinedicarboxylic acid derivatives represented by the general formula (1) as an active ingredient. Also in this case, the toner may be a polymerized toner.

In the present invention, the charge control agent containing one or more pyridinedicarboxylic acid derivatives represented by the general formula (1) as an active ingredient has a higher charge rising speed than conventional charge control agents, and has a high charge. And charging characteristics particularly excellent in stability over time and environmental stability. In addition, it does not contain heavy metals such as chromium, which is a concern for environmental problems, and is excellent in dispersibility and compound stability.

The charge control agent according to the present invention is excellent in charge control characteristics, environmental resistance, and durability, and has no fog, image density, dot reproducibility, fine line reproducibility when used for pulverized toner or polymerized toner. Can obtain a good image. The charge control agent is useful for an electrophotographic charge control agent that expresses sufficient triboelectric chargeability in the toner, particularly for a color toner, and further for a polymerized toner.

Hereinafter, embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

The charge control agent according to the present embodiment contains one or more pyridinedicarboxylic acid derivatives represented by the general formula (1) as an active ingredient. First, the pyridinedicarboxylic acid derivative represented by the general formula (1) will be described.

Represented by R ₁ , R ₂ and R ₃ (R ₁ to R ₃ ) in the general formula (1) “a linear or branched group having 1 to 8 carbon atoms which may have a substituent. Alkyl group "," optionally substituted cycloalkyl group having 5 to 10 carbon atoms "or" optionally substituted straight chain or branched chain group having 2 to 6 carbon atoms ". “Linear or branched alkyl group having 1 to 8 carbon atoms”, “Cycloalkyl group having 5 to 10 carbon atoms” or “Linear or branched chain having 2 to 6 carbon atoms” in “Alkenyl group” Specific examples of the alkenyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n -Hexyl, n-heptyl, isoheptyl Group, n- octyl group, isooctyl group, a cyclopentyl group, a cyclohexyl group, 1-adamantyl, 2-adamantyl, vinyl group, allyl group, etc. may be mentioned. Isopropenyl group and a 2-butenyl _{group, R} 1 ~ R ₃ may be adjacent to each other and bonded to each other via a single bond, oxygen atom or sulfur atom to form a ring.

“A linear or branched alkyl group having 1 to 8 carbon atoms having a substituent” represented by R ₁ to R ₃ in the general formula (1), “5 to 10 carbon atoms having a substituent” Specific examples of the “substituent” in the “cycloalkyl group” or “straight-chain or branched alkenyl group having 2 to 6 carbon atoms” include deuterium atom, trifluoromethyl group, cyano group Group, nitro group, hydroxyl group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group Straight chain having 1 to 8 carbon atoms such as n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, isoheptyl group, n-octyl group and isooctyl group Is a branched alkyl group; a linear or branched alkyloxy group having 1 to 8 carbon atoms such as a methyloxy group, an ethyloxy group or a propyloxy group; an alkenyl group such as an allyl group; a benzyl group or a naphthylmethyl group Aralkyl groups such as phenethyl group; aryloxy groups such as phenyloxy group and tolyloxy group; arylalkyloxy groups such as benzyloxy group and phenethyloxy group; phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group, phenanthryl Group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group and other aromatic hydrocarbon groups or condensed polycyclic aromatic groups; pyridyl group, furanyl group, pyranyl group, thienyl group, furyl group , Pyrrolyl group, pyrrolidini Group, imidazolyl group, imidazolinyl group, imidazolidinyl group, pyrazolyl group, pyrazolinyl group, pyrazolidinyl group, pyridazinyl group, pyrazinyl group, piperidinyl group, piperazinyl group, thiolanyl group, thianyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group , Heterocyclic groups such as indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalyl group, benzoimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, carbolinyl group; styryl group, naphthylvinyl group, etc. Aryl vinyl group; Acyl group such as acetyl group and benzoyl group; Dialkylamino group such as dimethylamino group and diethylamino group; Aromatic hydrocarbon group such as diphenylamino group and dinaphthylamino group Or a disubstituted amino group substituted with a condensed polycyclic aromatic group; a diaralkylamino group such as a dibenzylamino group or a diphenethylamino group; a dipyridylamino group, a dithienylamino group or a dipiperidinylamino group A disubstituted amino group substituted with a heterocyclic group; a dialkenylamino group such as a diallylamino group; an alkyl group, an aromatic hydrocarbon group, a condensed polycyclic aromatic group, an aralkyl group, a heterocyclic group or an alkenyl group; And a group such as a di-substituted amino group substituted with a substituent, and these substituents may be further substituted with other substituents, via a single bond, an oxygen atom or a sulfur atom. May be combined with each other to form a ring.

In the “linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent” represented by R ₁ to R ₃ in the general formula (1), “substituent A straight-chain or branched alkyl group having 1 to 4 carbon atoms which may have a "is preferable.
In the “cycloalkyl group having 5 to 10 carbon atoms which may have a substituent” represented by R ₁ to R ₃ in the general formula (1), the “having a substituent” An optionally substituted cycloalkyl group having 5 to 6 carbon atoms is preferable.
Further, in the “linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent” represented by R ₁ to R ₃ in the general formula (1), “ A “straight or branched alkenyl group having 2 to 4 carbon atoms which may have a substituent” is preferred.

“A linear or branched alkyloxy group having 1 to 8 carbon atoms which may have a substituent” represented by R ₁ to R ₃ in the general formula (1) or “having a substituent. The “linear or branched alkyloxy group having 1 to 8 carbon atoms” or “cycloalkyloxy group having 5 to 10 carbon atoms” in “optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms”. Are specifically methyloxy, ethyloxy, n-propyloxy, isopropyloxy, n-butyloxy, tert-butyloxy, n-pentyloxy, n-hexyloxy, n-heptyl Oxy group, isoheptyloxy group, n-octyloxy group, isooctyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclo Kuchiruokishi group, 1-like adamantyl group and a 2-adamantyl group can be exemplified, R 1 _~ R ₃ is a neighboring groups to each other, a single bond, and bonded to each other through an oxygen atom or a sulfur atom ring May be formed.

“A linear or branched alkyloxy group having 1 to 8 carbon atoms having a substituent” represented by R ₁ to R ₃ in the general formula (1) or “a carbon atom having 5 to 5 carbon atoms having a substituent” Specific examples of the “substituent” in “10 cycloalkyloxy groups” include deuterium atom, trifluoromethyl group, cyano group, nitro group, hydroxyl group; fluorine atom, chlorine atom, bromine atom, iodine atom, etc. Halogen atom: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group A linear or branched alkyl group having 1 to 8 carbon atoms such as isoheptyl group, n-octyl group, isooctyl group, etc .; methyloxy group, ethyloxy group, pro A linear or branched alkyloxy group having 1 to 8 carbon atoms such as a ruoxy group; an alkenyl group such as an allyl group; an aralkyl group such as a benzyl group, a naphthylmethyl group or a phenethyl group; a phenyloxy group or a tolyloxy group An aryloxy group such as benzyloxy group and phenethyloxy group; phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fullyl group Aromatic hydrocarbon group or condensed polycyclic aromatic group such as oranthenyl group and triphenylenyl group; pyridyl group, furanyl group, pyranyl group, thienyl group, furyl group, pyrrolyl group, pyrrolidinyl group, imidazolyl group, imidazolinyl group, imidazolidinyl group , Lazolyl, pyrazolinyl, pyrazolidinyl, pyridazinyl, pyrazinyl, piperidinyl, piperazinyl, thiolanyl, thianyl, quinolyl, isoquinolyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, benzoxazolyl Group, benzothiazolyl group, quinoxalyl group, benzoimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, carbolinyl group and other heterocyclic groups; styryl group, naphthylvinyl group and other aryl vinyl groups; acetyl group, benzoyl group, etc. Acyl group; Dialkylamino group such as dimethylamino group and diethylamino group; Disubstituted amino group substituted with aromatic hydrocarbon group or condensed polycyclic aromatic group such as diphenylamino group and dinaphthylamino group; Diaralkylamino groups such as amino groups and diphenethylamino groups; Disubstituted amino groups substituted with heterocyclic groups such as dipyridylamino groups, dithienylamino groups, and dipiperidinylamino groups; Dialkenyl groups such as diallylamino groups An amino group; a group such as an alkyl group, an aromatic hydrocarbon group, a condensed polycyclic aromatic group, an aralkyl group, a heterocyclic group or a disubstituted amino group substituted with a substituent selected from an alkenyl group. These substituents may be further substituted with other substituents, and may be bonded to each other through a single bond, an oxygen atom or a sulfur atom to form a ring.

In the “linear or branched alkyloxy group having 1 to 8 carbon atoms which may have a substituent” represented by R ₁ to R ₃ in the general formula (1), “A linear or branched alkyloxy group having 1 to 4 carbon atoms which may have a substituent” is preferable.
In the “cycloalkyloxy group having 5 to 10 carbon atoms which may have a substituent” represented by R ₁ to R ₃ in the general formula (1), “having a substituent An optionally substituted cycloalkyloxy group having 5 to 6 carbon atoms is preferable.

“Substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted heterocyclic group” represented by R ₁ to R ₃ in the general formula (1), or “substituted or unsubstituted condensed polycyclic aromatic” As the “aromatic hydrocarbon group”, “heterocyclic group” or “condensed polycyclic aromatic group” in the “group group”, specifically, phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthryl group, phenanthryl group , Fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, pyridyl group, furanyl group, pyranyl group, thienyl group, pyrrolidinyl group, imidazolyl group, imidazolinyl group, imidazolidinyl group, pyrazolyl group, pyrazolinyl group , Pyrazolidinyl group, pyridazinyl group, pyrazinyl group, piperidinyl group, piperazinyl group, thiolanyl , Thianyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalyl group, benzoimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, R ₁ to R ₃ may be bonded to each other through a single bond, an oxygen atom or a sulfur atom to form a ring.

Examples of the “substituent” in the “substituted aromatic hydrocarbon group”, “substituted heterocyclic group” or “substituted condensed polycyclic aromatic group” represented by R ₁ to R ₃ in the general formula (1) include Deuterium atom, cyano group, trifluoromethyl group, nitro group, hydroxyl group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyl group, ethyl group, n-propyl group, isopropyl group , N-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group, etc. A linear or branched alkyl group having 1 to 8 carbon atoms; a cycloalkyl group having 5 to 10 carbon atoms such as a cyclopentyl group and a cyclohexyl group; a vinyl group, an allyl group, Straight or branched alkenyl groups having 2 to 6 carbon atoms such as nyl and 1-hexenyl groups; straight or branched having 1 to 8 carbon atoms such as methyloxy, ethyloxy and propyloxy Alkyloxy groups having 5 to 10 carbon atoms such as cyclopentyloxy groups and cyclohexyloxy groups; aralkyl groups such as benzyl groups, naphthylmethyl groups and phenethyl groups; phenyloxy groups, tolyloxy groups and biphenylyl groups Aryloxy groups such as oxy group, terphenylyloxy group, naphthyloxy group, anthryloxy group, phenanthryloxy group, fluorenyloxy group, indenyloxy group, pyrenyloxy group, perylenyloxy group; benzyloxy group, Arylalkyloxy groups such as phenethyloxy groups Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as phenyl, biphenylyl, terphenylyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthenyl, triphenylenyl Group; pyridyl group, furanyl group, pyranyl group, thienyl group, furyl group, pyrrolyl group, pyrrolidinyl group, imidazolyl group, imidazolinyl group, imidazolidinyl group, pyrazolyl group, pyrazolinyl group, pyrazolidinyl group, pyridazinyl group, pyrazinyl group, piperidinyl group, Piperazinyl, thiolanyl, thianyl, quinolyl, isoquinolyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, benzoxazolyl, benzothiazolyl, quinoxalyl, Heterocyclic groups such as azoimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, carbolinyl; arylvinyl groups such as styryl and naphthylvinyl; acyl groups such as acetyl and benzoyl; dimethylamino Dialkylamino groups such as diethylamino groups; disubstituted amino groups substituted with aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as diphenylamino groups and dinaphthylamino groups; dibenzylamino groups and diphenethylamino groups A disubstituted amino group substituted with a heterocyclic group such as a dipyridylamino group, a dithienylamino group or a dipiperidinylamino group; a dialkenylamino group such as a diallylamino group; an alkyl group or an aromatic group Hydrocarbon group, condensed polycyclic aromatic group, aralkyl group, heterocyclic group or alkeni And a group such as a di-substituted amino group substituted with a substituent selected from the group, and these substituents may be further substituted with other substituents, such as a single bond, an oxygen atom or A ring may be formed by bonding to each other via a sulfur atom.

Specific examples of the “aryloxy group” in the “substituted or unsubstituted aryloxy group” represented by R ₁ to R ₃ in the general formula (1) include a phenyloxy group, a tolyloxy group, and a biphenylyloxy group. Terphenylyloxy group, naphthyloxy group, anthryloxy group, phenanthryloxy group, fluorenyloxy group, indenyloxy group, pyrenyloxy group, perylenyloxy group, and the like. R ₁ to R ₃ May be bonded to each other through a single bond, oxygen atom or sulfur atom to form a ring.

Specific examples of the “substituent” in the “substituted aryloxy group” represented by R ₁ to R ₃ in the general formula (1) include deuterium atom, cyano group, trifluoromethyl group, nitro group, hydroxyl group Group: halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, A linear or branched alkyl group having 1 to 8 carbon atoms such as an isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group; cyclopentyl group, cyclohexyl group A cycloalkyl group having 5 to 10 carbon atoms such as vinyl group, allyl group, 2-butenyl group, 1-hexenyl group, etc. A linear or branched alkenyl group of 1 to 8 carbon atoms such as a methyloxy group, an ethyloxy group or a propyloxy group; a cyclopentyloxy group, a cyclohexyloxy group or the like; A cycloalkyloxy group having 5 to 10 carbon atoms; an aralkyl group such as benzyl group, naphthylmethyl group, phenethyl group; phenyloxy group, tolyloxy group, biphenylyloxy group, terphenylyloxy group, naphthyloxy group, anthryl Aryloxy groups such as oxy group, phenanthryloxy group, fluorenyloxy group, indenyloxy group, pyrenyloxy group, perylenyloxy group; arylalkyloxy groups such as benzyloxy group, phenethyloxy group; phenyl group, biphenylyl group , Terphenylyl group Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as naphthyl group, anthracenyl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group; pyridyl group, furanyl group, pyranyl Group, thienyl group, furyl group, pyrrolyl group, pyrrolidinyl group, imidazolyl group, imidazolinyl group, imidazolidinyl group, pyrazolyl group, pyrazolinyl group, pyrazolidinyl group, pyridazinyl group, pyrazinyl group, piperidinyl group, piperazinyl group, thiolanyl group, thianyl group, Quinolyl, isoquinolyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, benzoxazolyl, benzothiazolyl, quinoxalyl, benzoimidazolyl, pyrazolyl, dibenzofura Heterocyclic groups such as nyl, dibenzothienyl and carbolinyl; arylvinyl groups such as styryl and naphthylvinyl; acyl groups such as acetyl and benzoyl; dialkylamino groups such as dimethylamino and diethylamino; diphenyl A disubstituted amino group substituted with an aromatic hydrocarbon group such as an amino group or a dinaphthylamino group or a condensed polycyclic aromatic group; a diaralkylamino group such as a dibenzylamino group or a diphenethylamino group; a dipyridylamino group; Disubstituted amino groups substituted by heterocyclic groups such as dithienylamino groups and dipiperidinylamino groups; Dialkenylamino groups such as diallylamino groups; alkyl groups, aromatic hydrocarbon groups, condensed polycyclic aromatic groups A disubstituted amino substituted with a substituent selected from an aralkyl group, a heterocyclic group or an alkenyl group These substituents may be further substituted with other substituents, and are bonded to each other through a single bond, oxygen atom or sulfur atom to form a ring. Also good.

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

“A linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent” represented by R ₄ and R ₅ in the general formula (1), “having a substituent In the “cycloalkyl group having 5 to 10 carbon atoms” or “the linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent”. Examples of “8 linear or branched alkyl group”, “C5-C10 cycloalkyl group” or “C2-C6 linear or branched alkenyl group” include the above R The groups are the same as those shown for ₁ to R ₃ , and the substituents that these groups may have are the same as those shown for R ₁ to R ₃ .

“Substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted heterocyclic group” or “substituted or unsubstituted condensed polycyclic aromatic” represented by R ₄ and R ₅ in the general formula (1) The “aromatic hydrocarbon group”, “heterocyclic group” or “condensed polycyclic aromatic group” in the “group” is the same group as those described above for R ₁ to R ₃ , and these groups Substituents that may have are the same as those described for R ₁ to R ₃ .

R ₄ and R ₅ in the general formula (1) are a hydrogen atom, a deuterium atom, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, or a substituted group. A cycloalkyl group having 5 to 10 carbon atoms which may have a group is preferable, and a straight chain or branched chain having 1 to 4 carbon atoms which may have a hydrogen atom, a deuterium atom, or a substituent. The alkyl group is more preferably a hydrogen atom or a deuterium atom.

“Cycloalkyl group having 5 to 10 carbon atoms” in “cycloalkyl group having 5 to 10 carbon atoms which may have a substituent” represented by R ₆ and R ₇ in formula (1) Specific examples thereof include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a 1-adamantyl group, and a 2-adamantyl group.

“Aromatic hydrocarbon group” in “substituted or unsubstituted aromatic hydrocarbon group” or “substituted or unsubstituted condensed polycyclic aromatic group” represented by R ₆ and R ₇ in general formula (1) Or, as the “fused polycyclic aromatic group”, specifically, phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthryl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group And a triphenylenyl group.

“C6-C10 substituted cycloalkyl group”, “substituted aromatic hydrocarbon group” or “substituted condensed polycyclic aromatic group represented by R ₆ and R ₇ in general formula (1) As the “substituent” in the above, specifically, deuterium atom, trifluoromethyl group, cyano group, nitro group, hydroxyl group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, isoheptyl, n- Straight or branched alkyl group having 1 to 8 carbon atoms such as octyl group, isooctyl group, etc .; carbon atom number such as methyloxy group, ethyloxy group, propyloxy group, etc. A linear or branched alkyloxy group of 8 to 8; an alkenyl group such as an allyl group; an aralkyl group such as a benzyl group, a naphthylmethyl group and a phenethyl group; an aryloxy group such as a phenyloxy group and a tolyloxy group; a benzyloxy group Arylalkyloxy groups such as phenethyloxy groups; phenyl groups, biphenylyl groups, terphenylyl groups, naphthyl groups, anthracenyl groups, phenanthryl groups, fluorenyl groups, indenyl groups, pyrenyl groups, perylenyl groups, fluoranthenyl groups, triphenylenyl groups, etc. Aromatic hydrocarbon group or condensed polycyclic aromatic group; pyridyl group, furanyl group, pyranyl group, thienyl group, furyl group, pyrrolyl group, pyrrolidinyl group, imidazolyl group, imidazolinyl group, imidazolidinyl group, pyrazolyl group, pyrazolinyl group, Pyrazolidinyl group, pyridazinyl group, pyrazinyl group, piperidinyl group, piperazinyl group, thiolanyl group, thianyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalyl Group, benzimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, carbolinyl group and other heterocyclic groups; styryl group, naphthylvinyl group and other aryl vinyl groups; acetyl group, benzoyl group and other acyl groups; dimethylamino group Dialkylamino groups such as diethylamino groups; disubstituted amino groups substituted with aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as diphenylamino groups and dinaphthylamino groups; dibenzylamino groups and diphenethylamino groups Diaralkylamino groups such as: Disubstituted amino groups substituted with heterocyclic groups such as dipyridylamino groups, dithienylamino groups, and dipiperidinylamino groups; Dialkenylamino groups such as diallylamino groups; And a group such as a disubstituted amino group substituted with a substituent selected from an aromatic hydrocarbon group, a condensed polycyclic aromatic group, an aralkyl group, a heterocyclic group, or an alkenyl group. Furthermore, they may be substituted with other substituents, and may be bonded to each other via a single bond, oxygen atom or sulfur atom to form a ring.

“C6-C10 substituted cycloalkyl group”, “substituted aromatic hydrocarbon group” or “substituted condensed polycyclic aromatic group represented by R ₆ and R ₇ in general formula (1) The “substituent” in “is a deuterium 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, the number of carbon atoms 1-8 linear or branched alkyloxy groups are preferred.

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

In the general formulas (1A-2) and (1A-3), R ₈ to R ₁₇ may be the same as or different from each other, and are a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine. An 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, or a substituent A good cycloalkyl group having 5 to 10 carbon atoms, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and a carbon atom which may have a substituent 1 to 8 linear or branched alkyloxy group, optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted Substituted heterocyclic groups, substituted or unsubstituted It shows a 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 are bonded to each other to form a ring. Also good. * Indicates a bond.

Represented by R ₈ to R ₁₇ in the general formula (1A-2) and the general formula (1A-3) “a linear or branched group having 1 to 8 carbon atoms which may have a substituent. Alkyl group "," optionally substituted cycloalkyl group having 5 to 10 carbon atoms "or" optionally substituted straight chain or branched chain group having 2 to 6 carbon atoms ". “Linear or branched alkyl group having 1 to 8 carbon atoms”, “Cycloalkyl group having 5 to 10 carbon atoms” or “Linear or branched chain having 2 to 6 carbon atoms” in “Alkenyl group” the alkenyl group "is a similar group to that shown with reference to the above R _{1 ~} R _3, substituent which may be possessed by these groups is also similar to that shown with respect to R 1 _~ R ₃ is there.

A “substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted heterocyclic group” represented by R ₈ to R ₁₇ in the general formula (1A-2) and the general formula (1A-3); As the “aromatic hydrocarbon group”, “heterocyclic group” or “fused polycyclic aromatic group” in the “substituted or unsubstituted condensed polycyclic aromatic group”, those shown for R ₁ to R ₃ above The substituents which these groups may have are the same as those shown for R ₁ to R ₃ .

The “aryloxy group” in the “substituted or unsubstituted aryloxy group” represented by R ₈ to R ₁₇ in the general formula (1A-2) and the general formula (1A-3) is the above R ₁ to The groups are the same as those shown for R ₃ , and the substituents that these groups may have are the same as those shown for R ₁ to R ₃ .

R ₈ to R _{17 in the} general formula (1A-2) and the general formula (1A-3) include a deuterium atom, a trifluoromethyl group, a cyano group, a nitro group, a hydroxyl group, a halogen atom, and one carbon atom. A linear or branched alkyl group having 8 to 8 carbon atoms or a linear or branched alkyloxy group having 1 to 8 carbon atoms is preferable.

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

In general formula (1A), R ₁ to R ₇ are as described above.

In general 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 general formula (1) according to this embodiment can be produced by a known method. For example, by reacting the corresponding dichloride of pyridinedicarboxylic acid and the alicyclic hydrocarbon, aromatic hydrocarbon or condensed polycyclic aromatic having the corresponding amino group in the presence of a base or the like, this embodiment The pyridinedicarboxylic acid derivative according to the above can be synthesized. It can also be synthesized by reacting the corresponding pyridinedicarboxylic acid with an alicyclic hydrocarbon, aromatic hydrocarbon or condensed polycyclic aromatic having a corresponding amino group in the presence of a dehydrating condensing agent.

Specific examples of preferable compounds among the pyridinedicarboxylic acid derivatives represented by the general formula (1) according to the present invention are shown below, but the present invention is not limited to these compounds.
In the following structural formula, hydrogen atoms are omitted. Further, even when stereoisomers exist, the planar structural formula is described.

In the present embodiment, the charge control agent is preferably used by adjusting the volume average particle diameter within the range of 0.1 μm to 20 μm, and particularly preferably adjusted within the range of 0.1 μm to 10 μm. If the volume average particle size is smaller than 0.1 μm, the amount of the charge control agent appearing on the toner surface tends to be extremely small, and the target charge control effect tends to be difficult to be obtained. It is not preferable because the charge control agent tends to increase and adverse effects such as in-machine contamination tend to occur.

When the charge control agent is used for the polymerized toner, the volume average particle diameter is preferably adjusted to 1.0 μm or less, particularly preferably adjusted to be in the range of 0.01 μm to 1.0 μm. . When the volume average particle size exceeds 1.0 μm, the particle size distribution of the finally obtained electrophotographic toner may be broadened or free particles may be generated, which may lead to a decrease in performance or reliability. On the other hand, when the average particle diameter is within the above range, there are no disadvantages, and the uneven distribution among the toners is reduced, the dispersion in the toner is improved, and the variation in performance and reliability is advantageous.

As a method for adding the charge control agent according to the present embodiment to the toner, a method of adding a kneading agent to the binder resin together with a colorant, kneading, and pulverization (pulverized toner), or charge control to a polymerizable monomer monomer A method of adding the agent and polymerizing the toner (polymerized toner), a method of adding the toner particles in advance (internal addition), a method of preparing the toner particles in advance, and adding the toner particles to the surface of the toner particles (external There is a method to add). The amount of the charge control agent that is preferably added to the toner particles is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the binder resin. The amount is 5 parts by mass. When externally added to the toner particles, the amount of the pyridinedicarboxylic acid derivative with respect to 100 parts by mass of the binder resin is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 2 parts by mass. is there. Further, it is preferable that the toner particles are fixed mechanochemically.

In this embodiment, the charge control agent containing the pyridinedicarboxylic acid derivative represented by the general formula (1) as an active ingredient can be used in combination with other known negatively chargeable charge control agents. Preferred charge control agents to be used in combination include azo iron complexes or complex salts, azo chromium complexes or complex salts, azo manganese complexes or complex salts, azo cobalt complexes or complex salts, azo zirconium complexes or complex salts, and chromium complexes of carboxylic acid derivatives. Or a complex salt, a zinc complex or complex salt of a carboxylic acid derivative, an aluminum complex or complex salt of a carboxylic acid derivative, and a zirconium complex or complex salt of a carboxylic acid derivative. The carboxylic acid derivative is preferably an aromatic hydroxycarboxylic acid, more preferably 3,5-di-tert-butylsalicylic acid. Furthermore, a boron complex or complex salt, a negatively chargeable resin type charge control agent and the like can be mentioned.

In the present embodiment, when the charge control agent according to the present embodiment is used in combination with another charge control agent, the amount of charge control other than the charge control agent according to the present embodiment is 100 parts by mass of the binder resin. The agent is preferably 0.1 to 10 parts by mass.

Any binder resin can be used as the binder resin used in the toner according to the exemplary embodiment. Vinyl polymers such as styrene monomers, acrylate monomers, methacrylate monomers, or copolymers composed of two or more of these monomers, polyester polymers, polyol resins, phenol resins, Examples include silicone resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, terpene resins, coumarone indene resins, polycarbonate resins, petroleum resins, and the like.

Examples of the styrene monomer, acrylate monomer, and methacrylate monomer that form the vinyl polymer or copolymer are illustrated below, but are not limited thereto.

Styrene monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-amylstyrene, p -Tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-chloro Examples thereof include styrene such as styrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene, or derivatives thereof.

Examples of acrylate monomers include acrylic acid or methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-dodecyl acrylate, 2-acrylate Examples thereof include acrylic acid such as ethylhexyl, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate or esters thereof.

Methacrylate monomers include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, 2-ethyl methacrylate. And methacrylic acid or esters thereof such as hexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.

Examples of other monomers that form the vinyl polymer or copolymer include the following (1) to (18). (1) Monoolefins such as ethylene, propylene, butylene and isobutylene; (2) Polyenes such as butadiene and isoprene; (3) Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; (4) Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; (5) Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; (6) Vinyl methyl ketone, vinyl hexyl ketone and methyl. Vinyl ketones such as isopropenyl ketone; (7) N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone; (8) vinyl naphthalenes; (9) acrylonitrile, methacrylate. Ronitrile, acrylic Acrylic acid or methacrylic acid derivatives such as amides; (10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; (11) maleic anhydride, citraconic acid Unsaturated dibasic acid anhydrides such as anhydride, itaconic anhydride, alkenyl succinic anhydride; (12) maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid Monoethyl esters of unsaturated dibasic acids such as monoethyl ester, citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester; (13) dimethylmaleic acid, dimethyl ester Unsaturated dibasic acid esters such as rufumaric acid; (14) α, β-unsaturated acids such as crotonic acid and cinnamic acid; (15) α, β-unsaturated acids such as crotonic acid anhydride and cinnamic anhydride (16) Carboxyl groups such as anhydrides of the α, β-unsaturated acids and lower fatty acids, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof Monomer; (17) acrylic acid or methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; (18) 4- (1-hydroxy-1-methylbutyl) styrene; Monomers having a hydroxy group such as 4- (1-hydroxy-1-methylhexyl) styrene -.

In the toner according to the exemplary embodiment, the vinyl polymer or copolymer of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the cross-linking agent include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene. Examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, or those obtained by replacing the acrylate of the above compound with methacrylate.

Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, Examples include propylene glycol diacrylate or those obtained by replacing acrylate of the above-mentioned compound with methacrylate.

Other examples include diacrylate compounds or dimethacrylate compounds linked by a chain containing an aromatic group and an ether bond. Examples of polyester diacrylates include trade name MANDA (manufactured by Nippon Kayaku Co., Ltd.).

Polyfunctional cross-linking agents include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and those obtained by replacing acrylates of the above compounds with methacrylate, Examples include lucyanurate and triallyl trimellitate.

These crosslinking agents can be used in an amount of preferably 0.01 to 10 parts by weight, particularly preferably 0.03 to 5 parts by weight, with respect to 100 parts by weight of other monomer components. Among these cross-linkable monomers, those that are preferably used in the toner resin from the viewpoint of fixability and anti-offset properties include one aromatic divinyl compound (especially divinylbenzene is preferred), one aromatic group and one ether bond. Examples thereof include diacrylate compounds linked by a linking chain. Among these, a combination of monomers that becomes a styrene copolymer or a styrene-acrylate copolymer is preferable.

In the present embodiment, examples of the polymerization initiator used for producing the vinyl polymer or copolymer include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate 1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo- 2 ', 4'-dimethyl-4'-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide Ketone peroxides such as oxide and cyclohexanone peroxide, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetra Methylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide, decanoyl To peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, diisopropyl peroxydicarbonate, di-2-ethyl Xyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, diethoxyisopropyl peroxydicarbonate, bis (3-methyl-3-methoxybutyl) peroxycarbonate, acetyl Cyclohexylsulfonyl peroxide, tert-butylperoxyacetate, tert-butylperoxyisobutyrate, tert-butylperoxy-2-ethylhexarate, tert-butylperoxylaurate, tert-butyloxybenzoe Tert-butylperoxyisopropyl carbonate, di-tert-butylperoxyisophthalate, tert-butylperoxyallyl carbonate, isoamylperoxy-2-ethylhexa Benzoate, di -tert- butyl peroxy the hexa hydro terephthalate, etc. tert- butylperoxy azelate and the like.

When the binder resin is a styrene-acrylate resin, the molecular weight distribution is 3,000 by molecular weight distribution by gel permeation chromatography (hereinafter abbreviated as GPC) soluble in the resin component tetrahydrofuran (hereinafter abbreviated as THF). A resin having at least one peak in a region of 50,000 to 50,000 (in terms of number average molecular weight) and having at least one peak in a region having a molecular weight of 100,000 or more is preferable in terms of fixing property, offset property and storage property. In addition, the THF-soluble component is preferably a binder resin in which a component having a molecular weight distribution of 100,000 or less is 50 to 90%. More preferably, it has a main peak in a region having a molecular weight of 5,000 to 30,000, and most preferably in a region having a molecular weight of 5,000 to 20,000.

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

Examples of the monomer constituting the polyester polymer include the following. Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1, Examples thereof include 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or diol obtained by polymerizing cyclic ethers such as ethylene oxide and propylene oxide with bisphenol A.

In order to crosslink the polyester resin, it is preferable to use a trihydric or higher alcohol together. Examples of the trihydric or higher polyhydric alcohol include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene It is done.

Examples of the acid component that forms the polyester polymer include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or anhydrides thereof, and alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid or the like. Unsaturated dibasic acids such as anhydride, maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc. And unsaturated dibasic acid anhydrides. Trivalent or higher polyvalent carboxylic acid components include trimellitic acid, pyromellitic acid, 2,5,7-naphthalene tricarboxylic acid, 1,2,4-naphthalene tricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxy) methane, 1,2,7,8-octanetetracarboxylic acid, empol trimer Body acids, or anhydrides thereof, partial lower alkyl esters, and the like.

When the binder resin is a polyester resin, the molecular weight distribution of the THF-soluble component of the resin component has at least one peak in the molecular weight region of 3,000 to 50,000, which indicates toner fixability and offset resistance. In view of the above, the THF-soluble component is preferably a binder resin in which a component having a molecular weight of 100,000 or less is 60 to 100%. More preferably, at least one peak is present in a region having a molecular weight of 5,000 to 20,000.

In this 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 number average molecular weight in terms of standard polystyrene measured with an HLC-8220 GPC apparatus (manufactured by Tosoh Corporation).

When the binder resin is a polyester resin, the acid value is preferably 0.1 mgKOH / g to 100 mgKOH / g, more preferably 0.1 mgKOH / g to 70 mgKOH / g, and 0.1 mgKOH / g. More preferably, it is ˜50 mg KOH / g.

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

In the present embodiment, a mixture of two or more of an amorphous polyester resin and a crystalline polyester resin may be used. In this case, it is preferable to select the material in consideration of the compatibility of each.

As the amorphous polyester resin, those synthesized from a polyvalent carboxylic acid component, preferably an aromatic polyvalent carboxylic acid and a polyhydric alcohol component, are suitably used.

As the crystalline polyester resin, one synthesized from a divalent carboxylic acid component, preferably an aliphatic dicarboxylic acid and a dihydric alcohol component, is suitably used.

As the binder resin that can be used in the toner according to the exemplary embodiment, a resin including a monomer component capable of reacting with both of these resin components in the vinyl polymer component and / or the polyester resin component can also be used. Examples of monomers that can react with the vinyl polymer among the monomers constituting the polyester resin component include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Examples of the monomer constituting the vinyl polymer component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

Further, when a polyester polymer, a vinyl polymer and another binder resin are used in combination, the total binder resin has a resin having an acid value of 0.1 mgKOH / g to 50 mgKOH / g of 60% by mass or more. preferable.

In this embodiment, the acid value of the binder resin component of the toner composition is determined by the following method, and the basic operation conforms to JIS K-0070.
(1) The sample is used by removing additives other than the binder resin (polymer component) in advance, or the acid value and content of components other than the binder resin and the crosslinked binder resin are obtained in advance. . A crushed sample of 0.5 to 2.0 g is precisely weighed, and the weight of the polymer component is defined as Wg. For example, when the acid value of the binder resin is measured from the toner, the acid value and content of the colorant or magnetic material are separately measured, and the acid value of the binder resin is obtained by calculation.
(2) A sample is put into a 300 (ml) beaker, and a mixed solution 150 (ml) of toluene / ethanol (volume ratio 4/1) is added and dissolved.
(3) Titrate with an ethanol solution of 0.1 mol / L KOH using a potentiometric titrator.
(4) The amount of KOH solution used at this time is S (ml), a blank is measured at the same time, and the amount of KOH solution used at this time is B (ml), which is calculated by the following equation (1). However, f is a factor of KOH concentration.
Acid value (mgKOH / g) = [(SB) × f × 5.61] / W (1)

The toner binder resin and the composition containing the binder resin have a glass transition temperature (Tg) of preferably 35 to 80 ° C., particularly preferably 40 to 75 ° C. from the viewpoint of toner storage stability. When Tg is lower than 35 ° C., the toner is likely to deteriorate in a high temperature atmosphere, and offset is likely to occur during fixing. On the other hand, when Tg exceeds 80 ° C., fixability tends to be lowered.

In the polymerization toner of this embodiment, a binder resin having a softening point in the range of 80 to 140 ° C. is preferably used. When the softening point of the binder resin is less than 80 ° C., the toner and the image stability of the toner after fixing and storage may be deteriorated. On the other hand, when the softening point exceeds 140 ° C., the low-temperature fixability may be deteriorated.

Magnetic materials that can be used in the present embodiment include (1) magnetic iron oxides such as magnetite, maghemite, and ferrite, and iron oxides containing other metal oxides, (2) metals such as iron, cobalt, and nickel, or Alloys of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and (3) Examples thereof include a mixture thereof.

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. Or two or more types can be used in combination. A particularly suitable magnetic substance is fine powder of iron trioxide or γ-iron trioxide.

Also, magnetic iron oxides such as magnetite, maghemite, and ferrite containing different elements, or a mixture thereof can be used. Examples of different elements include lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, sulfur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, gallium, etc. Can be given. Preferred heterogeneous elements are selected from magnesium, aluminum, silicon, phosphorus, or zirconium. The foreign element may be incorporated into the iron oxide crystal lattice, may be incorporated into the iron oxide as an oxide, or may exist as an oxide or hydroxide on the surface. Is preferably contained as an oxide.

The aforementioned different elements can be incorporated into the particles by adjusting the pH by mixing salts of the different elements at the time of producing the magnetic material. Moreover, it can be made to deposit on the particle | grain surface by adjusting pH after magnetic body particle | grain production | generation, or adding salt of each element and adjusting pH.

The amount of the magnetic substance used can be 10 to 200 parts by mass, preferably 20 to 150 parts by mass, with respect to 100 parts by mass of the binder resin. These magnetic materials preferably have a number average particle diameter of 0.1 μm to 2 μm, and more preferably 0.1 μm to 0.5 μm. The number average particle diameter can be obtained by measuring a photograph taken with a transmission electron microscope with a digitizer or the like.

Also, the magnetic material preferably has a magnetic property of 10 to 150 oersted, a saturation magnetization of 50 to 200 emu / g, and a residual magnetization of 2 to 20 emu / g when applied with 10K oersted.

The magnetic material can also be used as a colorant. In the case of a black toner, the colorant according to this embodiment includes black or blue dye or pigment particles. Examples of black or blue pigments include carbon black, aniline black, acetylene black, phthalocyanine blue, and indanthrene blue. Examples of black or blue dyes include azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes.

When used as a color toner, examples of the colorant include the following. As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dyes, lake dyes, naphthol dyes, benzimidazolone compounds, thioindigo compounds, and perylene compounds can be used. Specifically, examples of pigment-based magenta colorants include C.I. I. 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, C.I. I. Pigment violet 19, C.I. I. Vat red 1, 2, 10, 13, 15, 23, 29, 35 and the like.
Although the pigment may be used alone, it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together.

As dye-based magenta colorants, C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. I, disperse thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as Desperperiolet 1, C.I. I. Basic red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I. I. Examples include basic dyes such as basic violet 1,3,7,10,14,15,21,25,26,27,28.

As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinones, basic dye lake compounds can be used. Specifically, examples of the pigment-based cyan colorant include C.I. I. Pigment blue 2, 3, 15, 16, 17, C.I. I. Bat Blue 6, C.I. I. Examples include Acid Blue 45 or copper phthalocyanine pigments in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.

As the yellow colorant, condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds can be used. Specifically, yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 83, C.I. I. Bat yellow 1, 3, 20 and the like.

Examples of the orange pigment include red chrome yellow, molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, benzidine orange G, indanthrene brilliant orange RK, and indanthrene brilliant orange GK. Examples of purple pigments include manganese purple, fast violet B, and methyl violet lake. Examples of the green pigment include chromium oxide, chrome green, pigment green, malachite green lake, final yellow green G, and the like. Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.
The amount of the colorant used is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

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

The resin-coated carrier is composed of carrier core particles and a coating material that is a resin that coats (coats) the surface of the carrier core particles. Examples of the resin used for the coating material include styrene-acrylate resins such as styrene-acrylic acid ester copolymers and styrene-methacrylic acid ester copolymers, acrylic acid ester copolymers, and methacrylic acid ester copolymers. Fluorine-containing resins such as acrylate resins, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resins, polyester resins, polyamide resins, polyvinyl butyral, and aminoacrylate resins are preferred. In addition, a resin that can be used as a coating material for a carrier such as an ionomer resin or a polyphenylene sulfide resin can be used. These resins can be used alone or in combination.

Also, a binder type carrier core in which magnetic powder is dispersed in a resin can be used. In a resin-coated carrier, as a method for coating the surface of the carrier core with at least a resin coating material, the resin is dissolved or suspended in a solvent, and is applied to the carrier core for adhesion, or simply mixed in a powder state. Applicable methods are applicable. The ratio of the resin coating material to the resin-coated carrier may be appropriately determined, but is preferably 0.01 to 5% by mass, more preferably 0.1 to 1% by mass with respect to the resin-coated carrier.

Examples of use in which a magnetic material is coated with a coating agent of two or more kinds of mixtures include (1) dimethyldichlorosilane and dimethyl silicon oil (mass ratio 1: 5) with respect to 100 parts by mass of fine titanium oxide powder. Those treated with 12 parts by mass of the mixture, and (2) those treated with 20 parts by mass of the mixture of dimethyldichlorosilane and dimethylsilicone oil (mass ratio 1: 5) with respect to 100 parts by mass of the silica fine powder.

Among the above resins, styrene-methyl methacrylate copolymer, a mixture of fluorine-containing resin and styrene-based copolymer, or silicone resin is preferable, and silicone resin is particularly preferable.

Examples of the mixture of the fluorine-containing resin and the styrene copolymer include, for example, a mixture of polyvinylidene fluoride and a styrene-methyl methacrylate copolymer, a mixture of polytetrafluoroethylene and a styrene-methyl methacrylate copolymer, Vinylidene fluoride-tetrafluoroethylene copolymer (copolymer mass ratio 10:90 to 90:10), styrene-2-ethylhexyl acrylate copolymer (copolymer mass ratio 10:90 to 90:10) and styrene And a mixture with an acrylic acid-2-ethylhexyl-methyl methacrylate copolymer (copolymer mass ratio 20 to 60: 5 to 30:10:50).

Examples of the silicone resin include nitrogen-containing silicone resins and modified silicone resins produced by reacting a nitrogen-containing silane coupling agent with a silicone resin.

As the magnetic material for the carrier core, ferrite, iron-rich ferrite, magnetite, oxides such as γ-iron oxide, metals such as iron, cobalt, nickel, or alloys thereof can be used. Examples of elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, and vanadium. . Preferred magnetic materials include copper-zinc-iron-based ferrites mainly composed of copper, zinc and iron components, and manganese-magnesium-iron-based ferrites mainly composed of manganese, magnesium and iron components.

The resistance value of the carrier is preferably adjusted to 10 ⁶ Ω · cm to 10 ¹⁰ Ω · cm by adjusting the degree of unevenness on the surface of the carrier and the amount of resin to be coated. The particle size of the carrier can be 4 μm to 200 μm, preferably 10 μm to 150 μm, more preferably 20 μm to 100 μm. In particular, the resin-coated carrier preferably has a 50% particle size of 20 μm to 70 μm.

In the two-component developer, it is preferable to use 1 to 200 parts by mass of the toner according to this embodiment with respect to 100 parts by mass of the carrier, and 2 to 50 parts by mass of toner with respect to 100 parts by mass of the carrier. It is more preferable.

The toner of this embodiment may further contain a wax. In the present embodiment, the following wax is used. For example, oxides of aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax, sazol wax, aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or blocks thereof Copolymers, plant waxes such as candelilla wax, carnauba wax, wood wax, jojoba wax, animal waxes such as beeswax, lanolin, whale wax, mineral waxes such as ozokerite, ceresin, petrolatum, montanate ester wax, Examples thereof include waxes mainly composed of fatty acid esters such as caster wax and those obtained by partially or fully deoxidizing fatty acid esters such as deoxidized carnauba wax.

Examples of waxes are further saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or linear alkyl carboxylic acids having a linear alkyl group, prandidic acid, eleostearic acid, valinalic acid, etc. Unsaturated fatty acids, stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnaupyl alcohol, seryl alcohol, mesyl alcohol, saturated alcohols such as long-chain alkyl alcohols, polyhydric alcohols such as sorbitol, linoleic acid amides, olefinic acid amides , Fatty acid amides such as lauric acid amide, methylene biscapric acid amide, ethylene bis lauric acid amide, saturated fatty acid bisamides such as hexamethylene bis stearic acid amide, ethylene bis oleic acid amide, hexamethyle Unsaturated fatty acid amides such as bisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sepasic acid amide, m-xylene bisstearic acid amide, N, N′-distearyl Grafting onto aromatic bisamides such as isophthalic acid amide, fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate, and aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylate Wax, a partial ester compound of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol, and a methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

Preferred waxes include polyolefins obtained by radical polymerization of olefins under high pressure, polyolefins obtained by purifying low molecular weight by-products obtained during the polymerization of high molecular weight polyolefins, and polymerization using a catalyst such as a Ziegler catalyst or a metallocene catalyst under low pressure. Polyolefin, polyolefin polymerized using radiation, electromagnetic wave or light, low molecular weight polyolefin obtained by thermal decomposition of high molecular weight polyolefin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, Jintole method, hydrocol method, age method, etc. Synthetic hydrocarbon waxes synthesized by the above, synthetic waxes having a compound having one carbon atom as monomers, hydrocarbon waxes having functional groups such as hydroxyl groups or carboxyl groups, hydrocarbon waxes and government Mixture of hydrocarbon wax having a group, styrene these waxes as a matrix, maleic acid esters, acrylates, methacrylates, graft modified wax with vinyl monomers such as maleic anhydride.

In addition, these waxes have a sharp molecular weight distribution using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a solution liquid crystal deposition method, or a low molecular weight solid fatty acid, a low A molecular weight solid alcohol, a low molecular weight solid compound or other impurities are preferably used.

The wax used in the present embodiment preferably has a melting point of 50 to 140 ° C., more preferably 70 to 120 ° C., in order to balance the fixability and the offset resistance. If it is less than 50 degreeC, there exists a tendency for blocking resistance to fall, and if it exceeds 140 degreeC, it will become difficult to express an offset-proof effect.

Further, by using two or more different types of waxes in combination, the plasticizing action and the releasing action which are the actions of the wax can be expressed simultaneously.
Examples of the type of wax having a plasticizing action include a wax having a low melting point, a wax having a branched structure on the molecular structure, or a wax having a structure having a polar group. As for the wax having a high molecular weight, a linear wax or a non-polar wax having no functional group can be mentioned. Examples of use include a combination in which the difference in melting point between two or more different waxes is 10 ° C. to 100 ° C., a combination of polyolefin and graft-modified polyolefin, and the like.

When two types of wax are selected, in the case of a wax having a similar structure, a wax having a relatively low melting point exhibits a plasticizing action, and a wax having a high melting point exhibits a releasing action. At this time, when the difference in melting point is 10 to 100 ° C., functional separation is effectively exhibited. If it is less than 10 ° C., the function separation effect is difficult to appear, and if it exceeds 100 ° C., the function is not easily emphasized by interaction. In this case, the melting point of at least one of the waxes is preferably 70 to 120 ° C., more preferably 70 to 100 ° C. When the melting point is in this range, the function separation effect tends to be easily exhibited.

In addition, the wax is relatively branched, has a polar group such as a functional group, or is modified with a component different from the main component to exert a plastic action, and has a more linear structure, A non-polar one having no functional group or an unmodified straight one exhibits a releasing action. Preferred combinations of waxes include polyethylene homopolymers or copolymers based on ethylene and polyolefin homopolymers or copolymers based on olefins other than ethylene; combinations of polyolefins and graft modified polyolefins; alcohol waxes, fatty acid waxes or A combination of ester wax and hydrocarbon wax; a combination of Fischer-Tropsch wax or polyolefin wax and paraffin wax or microcrystal wax; a combination of Fischer-Tropsch wax and polyolefin wax; a combination of paraffin wax and microcrystal wax; a carnauba wax; Candelilla wax, rice wax or montan wax and carbonized water The combination of the system wax and the like.

In any case, the endothermic peak observed in the DSC measurement of the toner preferably has a maximum peak peak top temperature in the region of 70 to 110 ° C., and has a maximum peak peak top temperature in the region of 70 to 110 ° C. It is more preferable. This makes it easy to balance toner storage and fixing properties.

In the toner of the present embodiment, the total content of these waxes is preferably 0.2 to 20 parts by mass, and preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin. More preferred.

In this embodiment, the melting point of the wax is the peak top temperature of the endothermic peak of the wax measured by DSC.

In this embodiment, it is preferable that the DSC measurement of wax or toner is performed with a highly accurate internal heat input compensation type differential scanning calorimeter. The measurement method is performed according to ASTM D3418-82. In the present embodiment, a DSC curve is used that is measured when the temperature is raised at a temperature rate of 10 ° C./min after once raising and lowering the temperature and taking a previous history.

A fluidity improver may be added to the toner of this embodiment. The fluidity improver improves the fluidity of the toner (becomes easy to flow) when added to the toner surface. For example, fluorocarbon resin powder such as carbon black, vinylidene fluoride fine powder, polytetrafluoroethylene fine powder, wet process silica, fine powder silica such as dry process silica, fine powder unoxidized titanium, fine powder unalumina, and silane Examples include treated silica, treated titanium oxide, and treated alumina that have been surface-treated with a coupling agent, a titanium coupling agent, or silicone oil. Of these, finely divided silica, finely powdered titanium oxide, and finely powdered unalumina are preferable, and treated silica obtained by surface-treating these with a silane coupling agent or silicone oil is more preferable. The particle size of the fluidity improver is preferably 0.001 μm to 2 μm, more preferably 0.002 μm to 0.2 μm, as an average primary particle size.

A preferable fine powder silica is a fine powder produced by vapor phase oxidation of a silicon halide inclusion, and is called so-called dry silica or fumed silica.

Examples of commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include those sold under the following trade names. AEROSIL (manufactured by Nippon Aerosil Co., Ltd., the same shall apply hereinafter) -130, -300, -380, -TT600, -MOX170, -MOX80, -COK84: Ca-O-SiL (manufactured by CABOT Corp., hereinafter the same shall apply) -M-5 , -MS-7, -MS-75, -HS-5, -EH-5, Wacker HDK (manufactured by WACKER-CHEMIEGMBH Co., Ltd., the same shall apply hereinafter) -N20 V15, -N20E, -T30, -T40: D-CFineSi1ica (Manufactured by Dow Corning): Franco1 (manufactured by Franci1).

Furthermore, a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of a silicon halogen compound is more preferable. As the treated silica fine powder, it is particularly preferable to treat the silica fine powder so that the degree of hydrophobicity measured by a methanol titration test shows a value of 30 to 80%. The hydrophobizing treatment can be performed, for example, by a method of chemically or physically treating with an organosilicon compound that reacts or physically adsorbs with silica fine powder. Among these, a method of treating silica fine powder produced by vapor phase oxidation of a silicon halogen compound with an organosilicon compound is preferable.

Examples of organosilicon compounds include hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, vinylmethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, dimethylvinylchlorosilane, Divinylchlorosilane, γ-methacryloxypropyltrimethoxysilane, hexamethyldisilane, trimethylsilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α -Chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchloro Run, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane , Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 siloxane units per molecule, each of which is located at the end Examples thereof include dimethylpolysiloxane containing 0 to 1 hydroxyl group bonded to. Furthermore, silicone oils such as dimethyl silicone oil can be mentioned. These are used individually by 1 type or in mixture of 2 or more types.

The fluidity improver preferably has a number average particle diameter of 5 nm to 100 nm, more preferably 5 nm to 50 nm. The specific surface area by nitrogen adsorption measured by the BET method is preferably 30 m ² / g or more, more preferably 60 to 400 m ² / g. The surface-treated fine powder is preferably 20 m ² / g or more, more preferably 40 to 300 m ² / g. The application amount of these fine powders is preferably 0.03 to 8 parts by mass with respect to 100 parts by mass of the toner particles.

The toner of the present embodiment includes various types of metal soaps for the purpose of protecting the photoconductor / carrier, improving cleaning properties, adjusting thermal characteristics / electrical characteristics / physical characteristics, adjusting resistance, adjusting softening point, improving fixing rate, etc. Add fluorosurfactant, dioctyl phthalate, tin oxide, zinc oxide, carbon black, antimony oxide, etc., or inorganic fine powders such as titanium oxide, aluminum oxide, alumina, etc. as necessary. be able to. These inorganic fine powders may be hydrophobized as necessary. Also, lubricants such as polytetrafluoroethylene, zinc stearate, and polyvinylidene fluoride, abrasives such as cesium oxide, silicon carbide, and strontium titanate, anti-caking agents, and white particles and black particles that are opposite in polarity to the toner particles A small amount can be used as a developability improver.

These additives include silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, and other organosilicon compounds for the purpose of charge control. It is also preferable to treat with a treating agent or various treating agents.

In this embodiment, the charge control agent is sufficiently mixed and stirred together with the additive and toner as described above by a mixer such as a Henschel mixer, a ball mill, a nauter mixer, a V-type mixer, a W-type mixer, or a super mixer. Further, the target electrostatic charge developing toner can be obtained by uniformly externally treating the toner particle surface.

The toner of this embodiment is thermally stable and does not undergo thermal changes during the electrophotographic process, and can maintain stable charging characteristics. Further, since it is uniformly dispersed in any binder resin, the charge distribution of the fresh toner is very uniform. For this reason, in the toner of this embodiment, even in the untransferred and recovered toner (waste toner), almost no change is observed in the saturated triboelectric charge amount and the charge distribution compared to the fresh toner. On the other hand, when the waste toner from the electrostatic image developing toner of this embodiment is reused, a method of selecting a polyester resin containing an aliphatic diol as a binder resin, a metal-crosslinked styrene-acrylate copolymer is used. By producing a toner by using a binder resin and adding a large amount of polyolefin to the binder resin, the difference between the fresh toner and the waste toner can be further reduced.

The toner according to the present embodiment can be manufactured by a known manufacturing method. As an example of the production method, the above-mentioned toner constituent materials such as a binder resin, a charge control agent, and a colorant are sufficiently mixed by a mixer such as a ball mill, and the resulting mixture is well kneaded by a heating and kneading apparatus such as a hot roll kneader. A method (pulverization method) obtained by solidifying by cooling, classification after pulverization is preferable.

It can also be produced by a method obtained by dissolving the mixture in a solvent and atomizing, drying, and classifying by spraying. Furthermore, a so-called toner production method comprising a core material and a shell material by a polymerization method in which a predetermined material is mixed with a monomer to constitute a binder resin to form an emulsion or suspension and then polymerized to obtain a toner. The microcapsule toner can also be manufactured by a method in which a predetermined material is contained in the core material, the shell material, or both. Furthermore, the toner according to the exemplary embodiment can be manufactured by sufficiently mixing a desired additive and toner particles with a mixer such as a Henschel mixer as necessary.

The toner manufacturing method according to the present embodiment using the pulverization method will be described in more detail. First, a binder resin, a colorant, a charge control agent, and other necessary additives are mixed uniformly. For mixing, a known stirrer such as a Henschel mixer, a super mixer, or a ball mill can be used. The obtained mixture is hot-melt kneaded using a closed kneader or a single-screw or twin-screw extruder. After cooling, the kneaded product is coarsely pulverized using a crusher or a hammer mill, and further finely pulverized by a pulverizer such as a jet mill or a high-speed rotor rotary mill. Further, classification is performed to a predetermined particle size using an air classifier, for example, an inertia class elbow jet utilizing the Coanda effect, a cyclone (centrifugal) class microplex, a DS separator, and the like. Further, when the external additive is treated on the toner surface, the toner and the external additive are agitated and mixed with a high-speed agitator such as a Henschel mixer or a super mixer.

In addition, the toner according to the present embodiment can be manufactured by a suspension polymerization method or an emulsion polymerization method. In the suspension polymerization method, first, a polymerizable monomer, a colorant, a polymerization initiator, a charge control agent and, if necessary, a crosslinking agent, a dispersion stabilizer and other additives are uniformly dissolved or dispersed. A monomer composition is prepared. Thereafter, the monomer composition and the dispersion stabilizer are mixed into an appropriate stirrer or disperser such as a homomixer, a homogenizer, an atomizer, a microfluidizer, a one-component fluid nozzle, a gas-liquid fluid in a continuous phase (for example, an aqueous phase). Disperse using a nozzle, electric emulsifier or the like. Preferably, granulation is performed by adjusting the stirring speed, temperature, and time so that the droplets of the polymerizable monomer composition have a desired toner particle size. At the same time, the polymerization reaction is carried out at 40 to 90 ° C. to obtain toner particles having a desired particle size. The obtained toner particles are washed, filtered, and dried. For the external addition treatment after the production of the toner particles, the method described above can be used.

When produced by the emulsion polymerization method, the average particle diameter is extremely small, 0.1 μm to 1.0 μm, although it is excellent in uniformity compared to the particles obtained by the suspension polymerization method described above. It can also be produced by a so-called seed polymerization method in which particles are grown by post-addition of a polymerizable monomer, or a method in which emulsified particles are coalesced and fused to an appropriate average particle size.

Since the production by these polymerization methods does not go through the pulverization step, it is not necessary to impart brittleness to the toner particles, and furthermore, it is possible to use a large amount of a low softening point substance that was difficult to use by the conventional pulverization method. The selection range of can be expanded. The release agent or colorant, which is a hydrophobic material, is difficult to be exposed on the surface of the toner particles, so that contamination of the toner carrying member, the photoreceptor, the transfer roller, and the fixing device can be reduced.

By producing the toner according to this embodiment by a polymerization method, characteristics such as image reproducibility, transferability, and color reproducibility can be further improved. In addition, the toner particle size can be reduced in order to deal with minute dots, and a toner having a sharp particle size distribution can be obtained relatively easily.

Examples of the polymerizable monomer used when the toner according to the exemplary embodiment is manufactured by a polymerization method include vinyl polymerizable monomers capable of radical polymerization. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

Monofunctional polymerizable monomers include styrene, α-methyl styrene, β-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene, pn-butyl. Styrene polymerizable monomers such as styrene, p-tert-butylstyrene, pn-hexylstyrene, p-phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl Acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, benzyl acrylate, dimethyl phosphate methyl acrylate, dibutyl phosphate ethyl Acrylate polymerizable monomers such as acrylate and 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, Methacrylate-based polymerizable monomers such as n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, diethyl phosphate methacrylate, dibutyl phosphate ethyl methacrylate; unsaturated aliphatic monocarboxylic acid esters; vinyl acetate, propionic acid Vinyl esters such as vinyl and vinyl benzoate; Vinyl resins such as vinyl methyl ether and vinyl isobutyl ether Ethers; vinyl methyl ketone, vinyl hexyl ketone, vinyl ketones such as vinyl isopropyl ketone.

A known polymerization initiator such as an organic peroxide can be used as the polymerization initiator used when the toner according to the present embodiment is produced by the polymerization method. Examples of the water-soluble initiator include ammonium persulfate, potassium persulfate, 2, 2'-azobis (N, N'-dimethyleneisobutyroamidine) hydrochloride, 2,2'-azobis (2-aminodipropane) hydrochloride, azobis (isobutylamidine) hydrochloride, 2,2'-azo Examples thereof include sodium bisisobutyronitrile sulfonate, ferrous sulfate, and hydrogen peroxide.

The polymerization initiator is preferably added in an amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer, and may be used alone or in combination. Examples of the dispersant used in the production of the polymerized toner include inorganic calcium oxides such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, aluminum hydroxide, and metasilicate. Examples thereof include calcium acid, calcium sulfate, barium sulfate, bentonite, silica, and alumina. Examples of the organic compound include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch and the like. These dispersants are preferably used in an amount of 0.2 to 2.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

These commercially available dispersants may be used as they are, but in order to obtain dispersed particles having a fine and uniform particle size, the inorganic compound can be produced in a dispersion medium under high-speed stirring.

The toner obtained by the polymerization method tends to have a small degree of unevenness of the toner particles compared to the toner by the pulverization method without any special treatment and is indefinite, so that the contact between the electrostatic latent image carrier and the toner The area is increased and the toner adhesion is increased. As a result, there is less in-machine contamination, and a higher image density and a higher quality image can be easily obtained.

Also in the toner by the pulverization method, the toner particles are dispersed in water and heated by a hot water bath method, a heat treatment method in which the toner particles pass through a hot air current, or a mechanical impact method in which mechanical energy is applied and processed. The degree of unevenness on the toner surface can be reduced. Effective devices for reducing the degree of unevenness include a mechano-fusion system (manufactured by Hosokawa Micron Co., Ltd.) applying dry mechanochemical method, an I-type jet mill, and a hybridizer that is a mixing device having a rotor and a liner (Nara Machinery) Manufactured by Seisakusho Co., Ltd.) and a Henschel mixer which is a mixer having high-speed stirring blades.

As one of the values indicating the degree of unevenness of the toner particles, the average circularity can be given. The average circularity (C) is the total number of particles obtained by calculating the circularity (Ci) by the following formula (2) and further measuring the total roundness of all the particles measured as shown by the following formula (3). It means the value divided by (m).

The circularity (Ci) is measured using a flow particle image analyzer (for example, FPIA-1000 manufactured by Toa Medical Electronics Co., Ltd.). As a measurement method, a dispersion in which about 5 mg of toner is dispersed in 10 ml of water in which about 0.1 mg of a nonionic surfactant is dissolved is prepared, and ultrasonic waves (20 kHz, 50 W) are irradiated to the dispersion for 5 minutes. The circularity distribution of particles having an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm is measured using the flow type particle image analyzer with a dispersion concentration of 5000 to 20000 particles / μL.

The value of the average circularity is preferably 0.955 to 0.995, and more preferably 0.960 to 0.985. When the toner particles are adjusted so that the average circularity becomes this value, the phenomenon that the transfer residual toner increases is less likely to occur, and retransfer tends not to occur.

In the case of the toner according to the present embodiment, in the case of using a laser particle size distribution measuring machine such as a micron sizer (for example, manufactured by Seishin Enterprise Co., Ltd.) The toner particle diameter is preferably in the range of 2 μm to 15 μm, more preferably in the range of 3 μm to 12 μm in terms of volume average particle diameter. When the average particle size exceeds 15 μm, the resolution or sharpness tends to be dull, and when the average particle size is less than 2 μm, the resolution is good, but the problem of high cost due to the deterioration of the yield during toner production, Or there is a tendency for health problems such as toner scattering and skin penetration in the machine.

On the other hand, in the case of the 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 size is smaller than 4 μm, the toner fluidity is lowered, the chargeability of each particle is liable to be lowered, and the charge distribution is widened. Become. On the other hand, if it is smaller than 4 μm, the cleaning property may be extremely difficult. If the volume average particle size is larger than 9 μm, the resolution decreases, so that sufficient image quality cannot be obtained, and it may be difficult to satisfy recent high image quality requirements.

In addition, the polymerized toner according to the present embodiment draws a cumulative distribution from the smaller diameter side for each of the volume and the number in the divided particle size range (channel) measured by the following method. When the particle size to be defined is defined as volume D16%, the particle size to be accumulated 50% is defined as volume D50%, and the particle size to be accumulated 84% is defined as volume D84%, it is calculated from (D84% / D16%) 1/2. The volume average particle size distribution index (GSDv) is preferably 1.15 to 1.30, more preferably 1.15 to 1.25.

Regarding the toner particle size distribution, in the case of the toner according to the present embodiment, the particle content of 2 μm or less is 10 to 90% on the number basis, for example, by particle size measurement using a Coulter counter (TA-II manufactured by Coulter Co., Ltd.). Preferably, the content of particles of 12.7 μm or more is more preferably 0 to 30% on a volume basis.
Further, those having a high particle size uniformity (volume average particle size / number average particle size of 1.00 to 1.30) are desirable.

In the case of the electrostatic charge developing toner according to the exemplary embodiment, the specific surface area of the toner is preferably 1.2 to 5.0 m ² / g in BET specific surface area measurement using nitrogen as a desorption gas. More preferably, it is 1.5 to 3.0 m ² / g. The specific surface area is measured using, for example, a BET specific surface area measuring apparatus (for example, FlowSorb II2300, manufactured by Shimadzu Corporation), desorbing the adsorbed gas on the toner surface at 50 ° C. for 30 minutes, and then rapidly cooling with liquid nitrogen. The gas is re-adsorbed and then heated again to 50 ° C., which is defined as a value obtained from the degassing amount at this time.

In the case of the toner according to the exemplary embodiment, the apparent specific gravity (bulk density) was measured using, for example, a powder tester (for example, manufactured by Hosokawa Micron Corporation). In the case of a non-magnetic toner, 0.2 to 0.6 g / cm ³ is preferable, and in the case of a magnetic toner, 0.2 to 2.0 g / cm ³ is preferable depending on the kind and content of the magnetic powder.

In the case of the toner according to this 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 kind and content of the magnetic powder, but 0.9 ˜4.0 g / cm ³ is preferred. The true specific gravity of the toner is calculated as follows. 1.000 g of toner is precisely weighed, put into a 10 mmφ tablet molding machine, and compression molded while applying a pressure of 200 kgf / cm ² under vacuum. The height of this cylindrical molded product is measured with a micrometer, and the true specific gravity is calculated from this.

The fluidity of the toner is defined by, for example, a flow repose angle and a static repose angle by a repose angle measuring device (for example, manufactured by Tsutsui Rika Co., Ltd.). The flow angle of repose is preferably 5 to 45 degrees in the case of the electrostatic charge developing toner using the charge control agent according to the present embodiment. The rest angle of repose is preferably 10 to 50 degrees.
In the toner according to the exemplary embodiment, the average value of the shape factor (SF-1) in the case of the pulverized toner is preferably 100 to 400, and the average value of the shape factor 2 (SF-2) is preferably 100 to 350.

In the present embodiment, SF-1 and SF-2 indicating the shape factor of the toner are, for example, toner particles magnified 1000 times using an optical microscope (for example, BH-2 manufactured by Olympus Corporation) equipped with a CCD camera. The group is sampled to be about 30 in one field of view, and the obtained image is transferred to an image analyzer (for example, Luzex FS manufactured by Nireco Co., Ltd.), and the same operation is repeated until there are about 1000 toner particles. The shape factor was calculated. The shape factor (SF-1) and the shape factor 2 (SF-2) are calculated by the following equations.
SF-1 = ((ML ² × π) / 4A) × 100
(In the formula, ML represents the maximum particle length, and A represents the projected area of one particle.)
SF-2 = (PM ² / 4Aπ) × 100
(In the formula, PM represents the perimeter of the particle, and A represents the projected area of one particle.)

SF-1 represents the distortion of the particle, and the closer the particle is to a sphere, the closer to 100, and the longer the particle, the larger the value. SF-2 represents the unevenness of the particle. The closer the particle is to a sphere, the closer to 100, and the more complicated the particle shape, the larger the value.

In the toner according to this embodiment, the volume resistivity of the toner is preferably 1 × 10 ¹² to 1 × 10 ¹⁶ Ω · cm in the case of a non-magnetic toner, and the type and content of the magnetic powder in the case of a magnetic toner. However, it is preferably 1 × 10 ⁸ to 1 × 10 ¹⁶ Ω · cm. In this case, the toner volume resistivity is obtained by compression-molding toner particles to produce a disk-shaped test piece having a diameter of 50 mm and a thickness of 2 mm, and setting this on a solid electrode (for example, SE-70 manufactured by Ando Electric Co., Ltd.). Using a high insulation resistance meter (for example, 4339A manufactured by Hewlett-Packard Co., Ltd.), it is defined as a value after 1 hour when a DC voltage of 100 V is continuously applied.

The toner according to this embodiment preferably has a dielectric loss tangent of 1.0 × 10 ⁻³ to 15.0 × 10 ⁻³ in the case of non-magnetic toner, and the kind of magnetic powder in the case of magnetic toner. Depending on the content, those of 2 × 10 ⁻³ to 30 × 10 ⁻³ are preferable. In this case, the dielectric loss tangent of the toner is obtained by compression-molding the toner particles to produce a disk-shaped test piece having a diameter of 50 mm and a thickness of 2 mm, setting this on an electrode for solid, and an LCR meter (for example, Hewlett-Packard) It is defined as a dielectric loss tangent value (Tanδ) obtained when measured at a measurement frequency of 1 KHz and a peak-to-peak voltage of 0.1 KV using 4284A).

The toner according to the exemplary embodiment preferably has an Izod impact value of the toner of 0.1 to 30 kg · cm / cm. The Izod impact value of the toner in this case is measured in accordance with JIS standard K-7110 (hard plastic impact test method) by thermally melting toner particles to produce a plate-like test piece.

The toner according to the present embodiment preferably has a toner melt index (MI value) of 10 to 150 g / 10 min. The melt index (MI value) of the toner in this case is measured according to JIS standard K-7210 (Method A). In this case, the measurement temperature is 125 ° C. and the load is 10 kg.

In the toner according to this embodiment, the melting start temperature of the toner is preferably 80 to 180 ° C., and the 4 mm drop temperature is preferably 90 to 220 ° C. In this case, the toner melting start temperature is obtained by compressing and molding toner particles to produce a cylindrical test piece having a diameter of 10 mm and a thickness of 20 mm, which is then used as a thermal melting characteristic measuring device such as a flow tester (for example, CFT manufactured by Shimadzu Corporation). -500C) and is defined as the value at which melting starts and the piston starts to descend when measured at a load of 20 kgf / cm ² . In the same measurement, the temperature when the piston drops by 4 mm is defined as the 4 mm drop temperature.

In the toner according to the exemplary embodiment, the glass transition temperature (Tg) of the toner is preferably 35 to 80 ° C., and more preferably 40 to 75 ° C. The glass transition temperature of the toner in this case is measured using a differential thermal analysis (hereinafter abbreviated as DSC) apparatus, and the peak value of the phase change that appears when the temperature is raised at a constant temperature, rapidly cooled, and then reheated. Define what you want more. When the Tg of the toner is lower than 35 ° C., the offset resistance and the storage stability tend to decrease, and when it exceeds 80 ° C., the fixing strength of the image tends to decrease.
In the endothermic peak observed in the DSC measurement of the toner according to the exemplary embodiment, it is preferable that the peak top temperature of the maximum peak is in the region of 70 to 120 ° C.

In the toner according to the exemplary embodiment, the melt viscosity of the toner is preferably 1000 to 50000 poise, and more preferably 1500 to 38000 poise. In this case, the toner melt viscosity is obtained by compressing and molding toner particles to prepare a cylindrical test piece having a diameter of 10 mm and a thickness of 20 mm, and using this, for example, a flow tester (CFT-500C manufactured by Shimadzu Corporation). It is defined as a value when measured at a load of 20 kgf / cm ² .

The solvent-soluble residue of the toner according to the exemplary embodiment is preferably 0 to 30% by mass as a THF-insoluble component, 0 to 40% by mass as an ethyl acetate-insoluble component, and 0 to 30% by mass as a chloroform-insoluble component. The solvent-dissolved residue here is obtained by uniformly dissolving / dispersing 1 g of toner in 100 ml of each solvent of THF, ethyl acetate and chloroform, pressure-filtering the solution / dispersion, drying the filtrate, and quantifying. From this value, the ratio of insoluble matter in the organic solvent in the toner is calculated.

The toner according to the present embodiment can be used in a one-component development method which is one of image forming methods. The one-component developing method is a method for developing a latent image by supplying a thinned toner to a latent image carrier. The toner thinning usually includes a toner conveying member, a toner layer thickness regulating member and a toner replenishing auxiliary member, and the replenishing auxiliary member and the toner conveying member, and the toner layer thickness regulating member and the toner conveying member are in contact with each other. It is performed using the device.

The case where the toner according to the present embodiment is applied to the two-component development method will be specifically described. The two-component development method is a method using toner and a carrier (having a role as a charge imparting material and a toner conveying material), and the above-described magnetic material and glass beads are used for the carrier. The developer (toner and carrier) is agitated by the agitating member, generates a predetermined amount of charge, and is conveyed to the development site by a magnet roller or the like. On the magnet roller, a developer is held on the roller surface by magnetic force, and a magnetic brush whose layer is regulated to an appropriate height by a developer regulating plate or the like is formed. The developer moves on the roller as the developing roller rotates, and is brought into contact with the electrostatic charge latent image holding member or opposed in a non-contact state at a constant interval to develop and visualize the latent image. In the case of development in a non-contact state, it is usually possible to obtain a driving force for the toner to fly through a space at a constant interval by generating a direct current electric field between the developer and the latent image holding member. It can also be applied to a method of superimposing alternating current in order to develop an image.

Furthermore, the charge control agent used in the present embodiment is also suitable as a charge control agent (charge enhancer) in a coating for electrostatic powder coating. That is, the coating material for electrostatic coating using this charge enhancer is excellent in environmental resistance, storage stability, in particular thermal stability and durability, has a coating efficiency of 100%, and is a thick film free from coating film defects. Can be formed.

Hereinafter, the present invention will be described in more detail based on examples, but these do not limit the present invention in any way. In the following examples, all “parts” represent “parts by mass”.

Purification of the pyridinedicarboxylic acid derivative represented by the general formula (1) was performed by purification using column chromatography, adsorption purification using silica gel, activated carbon, activated clay, recrystallization using a solvent, or crystallization. The compound was identified by NMR analysis.

[Synthesis Example 1-1] (Synthesis of Exemplified Compound 1-2)
To a reaction vessel purged with nitrogen, 8.0 g (86.3 mmol) of aniline, 8.7 g (86.3 mmol) of triethylamine and 50 ml of dioxane were added, and 8.0 g (2,6-pyridinedicarboxylic acid dichloride) was added while stirring. 39.2 mmol) of dioxane solution was added dropwise, and the mixture was further stirred for 5 hours. After standing overnight, the reaction solution was added to 400 ml of diluted hydrochloric acid with stirring. The precipitated crude product was collected by filtration, washed with water, and then dried under reduced pressure at 60 ° C. to obtain 12.05 g (yield 97.2%) of white crystals.

The structure of the white crystals obtained was identified using NMR. ^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 Exemplified Compound 1-3)
To a reaction vessel purged with nitrogen, 5.5 g (51.5 mmol) of o-toluidine, 5.2 g (51.5 mmol) of triethylamine and 100 ml of dioxane were added, and 2,6-pyridinedicarboxylic acid dichloride 5. After adding 50 g of 0 g (24.5 mmol) dioxane solution dropwise, the mixture was further stirred for 6 hours. After standing overnight, the reaction solution was added to 500 ml of diluted hydrochloric acid with stirring. The precipitated crude product was collected by filtration, washed with water, and then dried under reduced pressure at 60 ° C. to obtain 7.71 g of white crystals (yield 90.7%).

The structure of the white crystals obtained was identified using NMR. ^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 Compound 1-4)
To a reaction vessel purged with nitrogen, 5.5 g (51.5 mmol) of m-toluidine, 5.2 g (51.5 mmol) of triethylamine and 100 ml of dioxane were added, and 2,6-pyridinedicarboxylic acid dichloride was added while stirring. After adding 50 g of 0 g (24.5 mmol) dioxane solution dropwise, the mixture was further stirred for 7 hours. After standing overnight, the reaction solution was added to 500 ml of diluted hydrochloric acid with stirring. The precipitated crude product was collected by filtration, washed with water, and then dried under reduced pressure at 60 ° C. to obtain 7.90 g of white crystals (yield 92.9%).

The structure of the white crystals obtained was identified using NMR. ^The following 19 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).
δ (ppm) = 19.66 (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)
To a reaction vessel purged with nitrogen, 9.2 g (86.3 mmol) of p-toluidine, 8.7 g (86.3 mmol) of triethylamine and 50 ml of dioxane were added, and 2,6-pyridinedicarboxylic acid dichloride 8. 50 ml of a dioxane solution of 0 g (39.2 mmol) was added dropwise, 50 ml of dioxane was added, and the mixture was further stirred for 5 hours. After standing overnight, the reaction solution was added to 400 ml of diluted hydrochloric acid with stirring. The precipitated crude product was collected by filtration, washed with water, and dried under reduced pressure at 60 ° C. to obtain 11.62 g (yield 86.1%) of white crystals.

The structure of the white crystals obtained was identified using NMR. ^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 Exemplified Compound 1-6)
To a reaction vessel purged with nitrogen, 12.9 g (86.3 mmol) of 4-tert-butylaniline, 8.7 g (86.3 mmol) of triethylamine, and 50 ml of dioxane were added, and 2,6-pyridinedicarboxylic acid was stirred. After dropwise addition of 50 ml of dioxane 8.0 g (39.2 mmol) in dioxane, the mixture was further stirred for 6 hours. After standing overnight, the reaction solution was added to 400 ml of diluted hydrochloric acid with stirring. The precipitated crude product was collected by filtration, washed with water, and then dried under reduced pressure at 60 ° C. to obtain 15.78 g (yield 93.9%) of white crystals.

The structure of the white crystals obtained was identified using NMR. ^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)
To a reaction vessel purged with nitrogen, 6.6 g (51.5 mmol) of m-chloroaniline, 5.2 g (51.5 mmol) of triethylamine, and 100 ml of dioxane were added, and 2,6-pyridinedicarboxylic acid dichloride 5 was added while stirring. After dropwise addition of 50 ml of 0.0 g (24.5 mmol) of dioxane, the mixture was further stirred for 6 hours. After standing overnight, the reaction solution was added to 500 ml of diluted hydrochloric acid with stirring. The precipitated crude product was collected by filtration, washed with water, and then dried under reduced pressure at 60 ° C. to obtain 8.76 g of white crystals (yield 92.2%).

The structure of the white crystals obtained was identified using NMR. ^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 Exemplified Compound 1-8)
To a reaction vessel purged with nitrogen, 6.3 g (51.5 mmol) of m-anisidine, 5.2 g (51.5 mmol) of triethylamine and 100 ml of dioxane were added, and 2,6-pyridinedicarboxylic acid dichloride 5. After adding 50 g of 0 g (24.5 mmol) dioxane solution dropwise, the mixture was further stirred for 6 hours. After standing overnight, the reaction solution was added to 500 ml of diluted hydrochloric acid with stirring. The precipitated crude product was collected by filtration, washed with water, and then dried under reduced pressure at 60 ° C. to obtain 8.28 g (yield 90.0%) of white crystals.

The structure of the white crystals obtained was identified using NMR. ^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 Exemplified Compound 1-9)
To a reaction vessel purged with nitrogen, 7.7 g (51.5 mmol) of 2-tert-butylaniline, 5.2 g (51.5 mmol) of triethylamine and 100 ml of dioxane were added, and 2,6-pyridinedicarboxylic acid was stirred. After adding 50 ml of a dioxane solution of 5.0 g (24.5 mmol) of dichloride dropwise, the mixture was further stirred for 6.5 hours. After standing overnight, the reaction solution was added to 500 ml of diluted hydrochloric acid with stirring. Ethyl acetate was added and an organic layer was collected by performing a liquid separation operation. The organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous sodium sulfate, and concentrated to give a crude product. The crude product was purified by column chromatography [carrier: silica gel, eluent: ethyl acetate] to obtain 10.5 g of amorphous crystals (yield 100%).

The structure of the obtained amorphous crystal was identified using NMR. ^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 Exemplified Compound 1-10)
To a reaction vessel purged with nitrogen, 8.3 g (51.5 mmol) of 2- (trifluoromethyl) aniline, 5.2 g (51.5 mmol) of triethylamine, and 100 ml of dioxane were added, and 2,6-pyridine was stirred. After dropwise addition of 50 ml of a dioxane solution of 5.0 g (24.5 mmol) of dicarboxylic acid dichloride, the mixture was further stirred for 6 hours. After standing overnight, the reaction solution was added to 500 ml of diluted hydrochloric acid with stirring. The precipitated crude product was collected by filtration, washed with water, and then dried under reduced pressure at 60 ° C. to obtain 9.33 g of white crystals (yield 84.1%).

The structure of the white crystals obtained was identified using NMR. ^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]
(Production of non-magnetic toner 1-1)
Styrene-acrylate copolymer resin (manufactured by Mitsui Chemicals, trade name CPR-100, acid value 0.1 mg KOH / g) 91 parts, pyridinedicarboxylic acid derivative synthesized in Synthesis Example 1-3 (Exemplary Compound 1- 4) 1 part, 5 parts of carbon black (trade name MA-100, manufactured by Mitsubishi Chemical Corporation) and 3 parts of low molecular weight polypropylene (trade name, Biscol 550P, manufactured by Sanyo Chemical Co., Ltd.) are heated and mixed at 130 ° C. (biaxial) The mixture was melt mixed by an extrusion kneader. The cooled mixture was coarsely pulverized with a hammer mill, then finely pulverized with a jet mill, and classified to obtain a nonmagnetic toner 1-1 having a volume average particle size of 9 ± 0.5 μm.

(Evaluation of non-magnetic toner 1-1)
After the non-magnetic toner 1-1 was mixed and shaken at a ratio of 4 to 100 parts by mass (toner: carrier) with a non-coated ferrite carrier (F-150 manufactured by Powder Tech Co., Ltd.), the toner was negatively charged. The charge amount was measured with a blow-off powder charge amount measuring device. As a result, it was −36.6 μc / g.

Similarly, the charge amount was also evaluated when mixed with a silicon-coated ferrite carrier (F96-150 manufactured by Powdertech). As a result, it was −23.7 μc / g.

[Example 1-11]
(Production and evaluation of non-magnetic toner 1-2)
Except that the pyridinedicarboxylic acid derivative synthesized in Synthesis Example 1-3 (Exemplary Compound 1-4) was replaced with the pyridinedicarboxylic acid derivative synthesized in Synthesis Example 1-5 (Exemplary Compound 1-6), Example Nonmagnetic toner 1-2 was prepared in the same manner as in 1-10, and the charge amount was evaluated by a blow-off powder charge amount measuring device. As a result, the charge amount when mixed with a non-coated ferrite carrier (F-150 manufactured by Powdertech Co., Ltd.) was −32.3 μc / g. Similarly, the charge amount when mixed with a silicon-coated ferrite carrier (F96-150 manufactured by Powdertech Co., Ltd.) was −22.5 μc / g.
[Comparative Example 1-1]
(Production and evaluation of comparative non-magnetic toner 1-1)
Except that the pyridinedicarboxylic acid derivative (Exemplary Compound 1-4) synthesized in Synthesis Example 1-3 was replaced with a salt of 3,5-tert-butylsalicylic acid and zinc, the same method as Example 1-10 was used. A comparative nonmagnetic toner 1-1 was prepared, and the charge amount was evaluated by a blow-off powder charge amount measuring device. As a result, the charge amount when mixed with a non-coated ferrite carrier (F-150 manufactured by Powdertech Co., Ltd.) was −23.0 μc / g. Similarly, the charge amount when mixed with a silicon-coated ferrite carrier (F96-150 manufactured by Powdertech) was -15.0 μc / g.

[Synthesis Example 2-1] (Synthesis of Exemplified Compound 2-2)
To a reaction vessel purged with nitrogen, 5.0 g (51.5 mmol) of cyclohexylamine, 5.2 g (51.5 mmol) of triethylamine, and 100 ml of dioxane were added and 5.0 g of 2,6-pyridinedicarboxylic acid dichloride was stirred. After adding 50 ml of a dioxane solution (24.5 mmol) dropwise, the mixture was further stirred for 6 hours. After standing overnight, the reaction solution was added to 500 ml of water with stirring. Hydrochloric acid was added to adjust the pH of the solution to 3, and the mixture was further stirred for 1 hour. The precipitated crude product was collected by filtration, washed with water, and then dried under reduced pressure at 60 ° C. to obtain 7.16 g (yield 88.4%) of white crystals.

The structure of the white crystals obtained was identified using NMR. ^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 Exemplary Compound 2-3)
To a reaction vessel purged with nitrogen, 8.0 g (51.5 mmol) of 4-tert-butylcyclohexylamine, 5.2 g (51.5 mmol) of triethylamine and 100 ml of dioxane were added, and 2,6-pyridinedicarboxylic acid was stirred. After adding 50 ml of dioxane solution of 5.0 g (24.5 mmol) of acid dichloride dropwise, the mixture was further stirred for 6 hours. After standing overnight, the reaction solution was added to 500 ml of water with stirring. Hydrochloric acid was added to adjust the pH of the solution to 3, and the mixture was further stirred for 1 hour. Extraction operation using ethyl acetate was performed, the organic layer was washed with aqueous sodium bicarbonate, dehydrated using anhydrous magnesium sulfate, and then the solvent was distilled off by concentration under reduced pressure to obtain a residue. After recrystallization using a mixed solvent of ethyl acetate and hexane, drying under reduced pressure at 60 ° C. gave 3.16 g (yield 29.3%) of white crystals as a mixture of stereoisomers.

The structure of the white crystals obtained was identified using NMR. ^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)
To a reaction vessel purged with nitrogen, 4.4 g (51.5 mmol) of cyclopentylamine, 5.2 g (51.5 mmol) of triethylamine, and 100 ml of dioxane were added, and 2,6-pyridinedicarboxylic acid dichloride 5 was then stirred. After dropwise addition of 50 ml of 0.0 g (24.5 mmol) of dioxane, the mixture was further stirred for 6 hours. After standing overnight, the reaction solution was added to 500 ml of water with stirring. Hydrochloric acid was added to adjust the pH of the solution to 3, and the mixture was further stirred for 1 hour. The precipitated crude product was collected by filtration, washed with water, and then dried under reduced pressure at 60 ° C. to obtain 6.14 g (yield 84.1%) of white crystals.

The structure of the white crystals obtained was identified using NMR. ^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)
To a reaction vessel purged with nitrogen, 5.8 g (51.5 mmol) of cycloheptylamine, 5.2 g (51.5 mmol) of triethylamine and 100 ml of dioxane were added, and then 2,6-pyridinedicarboxylic acid dichloride was stirred. After dropwise addition of 50 ml of 5.0 g (24.5 mmol) of dioxane, the mixture was further stirred for 6 hours. After standing overnight, the reaction solution was added to 500 ml of water with stirring. Hydrochloric acid was added to adjust the pH of the solution to 3, and the mixture was further stirred for 1 hour. The precipitated crude product was collected by filtration, washed with water, and then dried under reduced pressure at 60 ° C. to obtain 7.89 g of white crystals (yield 89.7%).

The structure of the white crystals obtained was identified using NMR. ^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)
Styrene-acrylate copolymer resin (manufactured by Mitsui Chemicals, trade name CPR-100, acid value 0.1 mg KOH / g) 91 parts, pyridine dicarboxylic acid derivative synthesized in Synthesis Example 2-2 (Exemplary Compound 2- 3) 1 part, 5 parts of carbon black (trade name MA-100, manufactured by Mitsubishi Chemical Corporation) and 3 parts of low molecular weight polypropylene (trade name, Biscol 550P, manufactured by Sanyo Chemical Co., Ltd.) are heated and mixed at 130 ° C. (biaxial The mixture was melt mixed by an extrusion kneader. The cooled mixture was coarsely pulverized with a hammer mill, then finely pulverized with a jet mill, and classified to obtain a nonmagnetic toner 2-1 having a volume average particle size of 9 ± 0.5 μm.

(Evaluation of non-magnetic toner 2-1)
After non-magnetic toner 2-1 was mixed and shaken at a ratio of 4 to 100 parts by mass (toner: carrier) with a non-coated ferrite carrier (F-150 manufactured by Powdertech Co., Ltd.), the toner was negatively charged. The charge amount was measured with a blow-off powder charge amount measuring device. As a result, it was −38.2 μc / g.

Similarly, the charge amount was also evaluated when mixed with a silicon-coated ferrite carrier (F96-150 manufactured by Powdertech). As a result, it was −25.3 μc / g.

[Comparative Example 2-1]
(Production and evaluation of comparative non-magnetic toner 2-1)
Except that the pyridinedicarboxylic acid derivative (Exemplary Compound 2-3) synthesized in Synthesis Example 2-2 was replaced with a salt of 3,5-tert-butylsalicylic acid and zinc, the same method as in Example 2-5 was used. Comparative non-magnetic toner 2-1 was prepared, and the charge amount was evaluated with a blow-off powder charge amount measuring device. As a result, the charge amount when mixed with a non-coated ferrite carrier (F-150 manufactured by Powdertech Co., Ltd.) was −23.0 μc / g. Similarly, the charge amount when mixed with a silicon-coated ferrite carrier (F96-150 manufactured by Powdertech) was -15.0 μc / g.

As is clear from the above results, it was found that the toner using the charge control agent containing the pyridinedicarboxylic acid derivative represented by the general formula (1) of the present invention as an active ingredient has a high charge amount.

[Example 1-12]
(Preparation of resin dispersion)
Mix 80 parts of polyester resin (Made by Mitsubishi Rayon Co., Ltd., DIACRON ER-561), 320 parts of ethyl acetate and 32 parts of isopropyl alcohol, and use a homogenizer (Megaku Co., Ltd., foamless mixer NGM-0.5TB). While stirring at 5000 to 10000 rpm, an appropriate amount of 0.1% by mass of ammonia water was added dropwise for phase inversion emulsification, and the solvent was removed while reducing the pressure with an evaporator to obtain a resin dispersion. The volume average particle diameter of the resin particles in this dispersion was 0.2 μm (the resin particle concentration was adjusted to 20% by mass with ion-exchanged water).

(Preparation of charge control agent dispersion)
0.2 parts of sodium dodecylbenzenesulfonate, 0.2 part of sorbon T-20 (manufactured by Toho Chemical Co., Ltd.) and 17.6 parts of ion-exchanged water are mixed and dissolved, and pyridine synthesized in Synthesis Example 1-3 2.0 parts of a dicarboxylic acid derivative (Exemplary Compound 1-4) and zirconia beads (bead particle diameter 0.65 mmφ, equivalent to 15 ml) were added, and paint conditioner (made by UNION NJ (USA), Red Devil) No. 5400-5L) for 3 hours. The zirconia beads were removed using a sieve and adjusted with ion-exchanged water to obtain a 10% by mass charge control agent dispersion.

(Preparation of polymerization toner)
125 parts of the resin dispersion, 1.0 part of a 20% by weight sodium dodecylbenzenesulfonate aqueous solution and 125 parts of ion-exchanged water are added to a reaction vessel equipped with a thermometer, pH meter, and stirrer, and the liquid temperature is controlled at 30 ° C. While stirring, the mixture was stirred at 150 rpm for 30 minutes. A 1% by mass aqueous nitric acid solution was added to adjust the pH to 3.0, and the mixture was further stirred for 5 minutes. While being dispersed with a homogenizer (manufactured by IKA Japan, Ultra Turrax T-25), 0.125 part of polyaluminum chloride was added, the temperature of the solution was raised to 50 ° C., and the mixture was further dispersed for 30 minutes. After adding 62.5 parts of the resin dispersion and 4.0 parts of the charge control agent dispersion, a 1% by mass aqueous nitric acid solution was added to adjust the pH to 3.0, and the mixture was further dispersed for 30 minutes. While stirring with a stirrer at 400 to 700 rpm, 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 reached 9.5 μm. After the liquid temperature was raised to 75 ° C., the mixture was further stirred for 2 hours, and after confirming that the volume average particle diameter was 6.0 μm and the particle shape was spheroidized, it was rapidly cooled using ice water. The sample was collected by filtration and dispersed and washed with ion exchange water. Dispersion washing was repeated until the electric conductivity of the filtrate after dispersion became 20 μS / cm or less. Thereafter, the toner particles were obtained by drying with a dryer at 40 ° C.
The obtained toner was sieved with a 166 mesh (aperture 90 μm) sieve to obtain an evaluation toner.

(Evaluation)
2 parts of the obtained toner for evaluation and 100 parts of a silicon-coated ferrite carrier (F96-150 manufactured by Powdertech Co., Ltd.) were mixed and shaken to charge the toner negatively. The saturation charge amount was measured in an atmosphere of a temperature of 25 ° C. and a humidity of 50% with a measuring device. As a result, the saturated charge amount was -38.9 μc / g.

[Comparative Example 1-2]
For comparison, a toner was prepared under the same conditions as in Example 1-12 except that the operation of adding the charge control agent dispersion was omitted, and the saturation charge amount was measured. As a result, the saturated charge amount was −20.5 μC / g.

[Example 2-6]
(Preparation of resin dispersion)
Mix 80 parts of polyester resin (Made by Mitsubishi Rayon Co., Ltd., DIACRON ER-561), 320 parts of ethyl acetate and 32 parts of isopropyl alcohol, and use a homogenizer (Megaku Co., Ltd., foamless mixer NGM-0.5TB). While stirring at 5000 to 10000 rpm, an appropriate amount of 0.1% by mass of ammonia water was added dropwise for phase inversion emulsification, and the solvent was removed while reducing the pressure with an evaporator to obtain a resin dispersion. The volume average particle diameter of the resin particles in this dispersion was 0.2 μm (the resin particle concentration was adjusted to 20% by mass with ion-exchanged water).

(Preparation of charge control agent dispersion)
0.2 parts of sodium dodecylbenzenesulfonate, 0.2 part of sorbon T-20 (manufactured by Toho Chemical Co., Ltd.) and 17.6 parts of ion-exchanged water are mixed and dissolved, and pyridine synthesized in Synthesis Example 2-2. 2.0 parts of a dicarboxylic acid derivative (Exemplified Compound 2-3) and zirconia beads (bead particle size 0.65 mmφ, equivalent to 15 ml) were added, and paint conditioner (made by UNION NJ (USA), Red Devil) No. 5400-5L) for 3 hours. The zirconia beads were removed using a sieve and adjusted with ion-exchanged water to obtain a 10% by mass charge control agent dispersion.

(Preparation of polymerization toner)
125 parts of the resin dispersion, 1.0 part of a 20% by weight sodium dodecylbenzenesulfonate aqueous solution and 125 parts of ion-exchanged water are added to a reaction vessel equipped with a thermometer, pH meter, and stirrer, and the liquid temperature is controlled at 30 ° C. While stirring, the mixture was stirred at 150 rpm for 30 minutes. A 1% by mass aqueous nitric acid solution was added to adjust the pH to 3.0, and the mixture was further stirred for 5 minutes. While being dispersed with a homogenizer (manufactured by IKA Japan, Ultra Tarrax T-25), 0.125 part of polyaluminum chloride was added, the liquid temperature was raised to 50 ° C., and the mixture was further dispersed for 30 minutes. After adding 62.5 parts of the resin dispersion and 4.0 parts of the charge control agent dispersion, a 1% by mass aqueous nitric acid solution was added to adjust the pH to 3.0, and the mixture was further dispersed for 30 minutes. While stirring with a stirrer at 400 to 700 rpm, 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 reached 9.5 μm. After the liquid temperature was raised to 75 ° C., the mixture was further stirred for 2 hours, and after confirming that the volume average particle diameter was 6.0 μm and the particle shape was spheroidized, it was rapidly cooled using ice water. The sample was collected by filtration and dispersed and washed with ion exchange water. Dispersion washing was repeated until the electric conductivity of the filtrate after dispersion became 20 μS / cm or less. Thereafter, the toner particles were obtained by drying with a dryer at 40 ° C.
The obtained toner was sieved with a 166 mesh (aperture 90 μm) sieve to obtain an evaluation toner.

(Evaluation)
2 parts of the obtained toner for evaluation and 100 parts of a silicon-coated ferrite carrier (F96-150 manufactured by Powdertech) were mixed and shaken to charge the toner negatively, and then the charge amount of blow-off powder was charged. The saturation charge amount was measured in an atmosphere of a temperature of 25 ° C. and a humidity of 50% with a measuring device. As a result, the saturated charge amount was −40.5 μc / g.

[Comparative Example 2-2]
For comparison, a toner was prepared under the same conditions as in Example 2-6, except that the operation of adding the charge control agent dispersion was omitted, and the saturation charge amount was measured. As a result, the saturated charge amount was −20.5 μC / g.

As is apparent from the above results, it was found 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.
That is, high charge performance can be imparted to the polymerized toner by using a charge control agent containing the pyridinedicarboxylic acid derivative represented by the general formula (1) of the present invention as an active ingredient.

The pyridinedicarboxylic acid derivative represented by the general formula (1) according to the present invention has excellent charging performance, and the charge control agent containing the compound as an active ingredient is clearly higher than the conventional charge control agent. Has charging performance. The charge control agent is optimal for color toners, particularly for polymerized toners. Furthermore, the charge control agent is extremely useful because it does not contain heavy metals such as chromium compounds, which are concerned with environmental problems.

Claims

A charge control agent containing one or more pyridinedicarboxylic acid derivatives represented by the following general formula (1) as an active ingredient.

[In General Formula (1), R 1 , R 2 and R 3 may be the same or different from each other, and are a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, cyano group. , A trifluoromethyl group, a nitro group, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, and a carbon atom having 5 to 10 carbon atoms which may have a substituent A cycloalkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and a linear chain having 1 to 8 carbon atoms which may have a substituent Or a branched alkyloxy group, an optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, substituted Or an unsubstituted condensed polycyclic aromatic group, Or a substituted or unsubstituted aryloxy group, R 4 and R 5 may be the same as or different from each other, and may have a hydrogen atom, a deuterium atom, or a substituent having 1 to 8 carbon atoms. A linear or branched alkyl group, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, a straight chain having 2 to 6 carbon atoms which may have a substituent, or A branched alkenyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, wherein R 6 and R 7 are the same as each other Or a cycloalkyl group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted condensed polycyclic aromatic group which may have a substituent. Show. Here, R 1 , R 2 and R 3 may be bonded to each other at adjacent groups to form a ring. ]
The charge control agent according to claim 1, wherein the pyridinedicarboxylic acid derivative represented by the general formula (1) is a compound represented by the following general formula (1A).

[In General Formula (1A), R 1 , R 2 and R 3 may be the same as or different from each other, and include a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, and 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, and a carbon atom having 5 to 10 carbon atoms which may have a substituent A cycloalkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and a linear chain having 1 to 8 carbon atoms which may have a substituent Or a branched alkyloxy group, an optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, substituted Or unsubstituted condensed polycyclic aromatic group Or a substituted or unsubstituted aryloxy group, R 4 and R 5 may be the same or different from each other, and may have a hydrogen atom, a deuterium atom, or a carbon atom having 1 to 8 carbon atoms which may have a substituent. A linear or branched alkyl group, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, or a linear chain having 2 to 6 carbon atoms which may have a substituent Or a branched alkenyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, and R 6 and R 7 are mutually The cycloalkyl group having 5 to 10 carbon atoms, which may be the same or different, and optionally substituted, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted condensed polycyclic aromatic group Indicates. Here, R 1 , R 2 and R 3 may be bonded to each other at adjacent groups to form a ring. ]
The charge control agent according to claim 1, wherein the pyridinedicarboxylic acid derivative represented by the general formula (1) is a compound represented by the following general formula (1A-1).

[In the general formula (1A-1), R 1 , R 2 and R 3 may be the same or different from each other, and are a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, 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, and a carbon atom which may have a substituent of 5 A cycloalkyl group having 10 to 10 carbon atoms, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and a straight chain having 1 to 8 carbon atoms which may have a substituent. A linear or branched alkyloxy group, an optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group Substituted or unsubstituted condensed polycyclic aromatic Represents a group or a substituted or unsubstituted aryloxy group, R 4 and R 5 may be the same or different from each other, and may have a hydrogen atom, a deuterium atom, or a carbon atom which may have a substituent; A linear or branched alkyl group having 8 to 8 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, and a straight chain having 2 to 6 carbon atoms which may have a substituent. A chain or branched alkenyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, or a 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 from each other, and are a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine Atoms, hydroxyl groups, cyano groups, A trifluoromethyl group, a nitro group, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, and a carbon atom having 5 to 10 carbon atoms which may have a substituent A cycloalkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a straight chain having 1 to 8 carbon atoms which may have a substituent, or A branched alkyloxy group, an optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, substituted or An unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group is shown. 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 are mutually adjacent groups. It may combine to form a ring. ]
The charge control agent according to claim 1 or 2, wherein R 6 and R 7 are cycloalkyl groups having 5 to 10 carbon atoms which may have a substituent.
A toner containing the charge control agent according to any one of claims 1 to 4, a colorant, and a binder resin.
A polymerized toner containing the charge control agent according to any one of claims 1 to 4, a colorant, and a binder resin.