JP5389306B1 - Charge control agent and toner using the same - Google Patents

Abstract

［一般式（１）中、Ｒ_１及びＲ_２は相互に同一でも異なってもよく、水素原子等を示し、Ｒ_３及びＲ_４は相互に同一でも異なってもよく、水素原子、炭素原子数１〜８の直鎖状若しくは分岐状のアルキル基等を示し、Ｒ_５及びＲ_６は相互に同一でも異なってもよく、置換基を有していてもよい炭素原子数５〜１０のシクロアルキル基、置換若しくは無置換の芳香族炭化水素基等を示す。］The present invention provides a charge control agent containing one or more thiophene dicarboxylic acid derivatives represented by the following general formula (1) as an active ingredient.
[Chemical 1]

[In the general formula (1), R ₁ and R ₂ may be the same or different from each other, each represents a hydrogen atom or the like, and R ₃ and R ₄ may be the same or different from each other, 1 to 8 linear or branched alkyl group or the like, and R ₅ and R ₆ may be the same or different from each other, and optionally substituted cycloalkyl having 5 to 10 carbon atoms. A group, a substituted or unsubstituted aromatic hydrocarbon group, and the like; ]

Description

  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 and fixed on paper or plastic film 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 general, a charge control agent is added to impart preferable charging characteristics (charging speed, charging level, charging stability, etc.), aging stability, environmental stability, and the like. By adding the charge control agent, the toner characteristics are greatly improved.

  Today, in this technical field, nigrosine dyes, azine dyes, copper phthalocyanine pigments, polymers having a quaternary ammonium salt or a quaternary ammonium salt in the side chain are known as positive triboelectric charge control agents. Known negative triboelectric charge control agents include metal complexes of monoazo dyes, metal complexes 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, 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 (for example, see Patent Documents 1 to 3) and aromatic dicarboxylic acid metal salt compounds (for example, see Patent Document 4) for negatively chargeable toners. ), Metal complex salts of anthranilic acid derivatives (for example, see Patent Documents 5 to 6), organoboron compounds (for example, see Patent Documents 7 to 8), biphenol compounds (for example, see Patent Document 9), calix (n) allene There exist a compound (for example, refer patent documents 10-15), cyclic phenol sulfide (for example, refer patent documents 16-18), etc. Further, for positively chargeable toners, there are quaternary ammonium salt compounds (for example, see Patent Documents 19 to 21).

Japanese Patent Publication No. 55-042752 JP 61-069073 A JP 61-221756 A JP-A-57-111541 JP 61-141453 A JP 62-094856 A U.S. Pat. No. 4,767,688 JP-A-1-3066861 JP 61-003149 A Japanese Patent No. 2568675 Japanese Patent No. 2899038 Japanese Patent No. 3359657 Japanese Patent No. 3313871 Japanese Patent No. 3325730 JP 2003-162100 A JP 2003-295522 A WO2007-111346 WO 2007-119797 Japanese Unexamined Patent Publication No. 57-119364 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 problematic with respect to waste regulations and are not necessarily safe. In addition, these charge control agents have a low charge-imparting effect that is required today, and the charge rising speed is insufficient, so that the initial copy image lacks clarity, or the copy image during continuous copying cannot be reproduced. There were drawbacks such as the quality being easily fluctuated and, furthermore, not being applicable 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.

  An 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 in order to achieve the above object, and has the following gist.

  That is, this invention provides the charge control agent which contains 1 type, or 2 or more types of the thiophene dicarboxylic acid derivative represented by General formula (1) as an active ingredient.

In the general formula (1), R ₁ and R ₂ may be the same as or different from each other, and are a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a cyano group, or trifluoromethyl. Group, nitro group, linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, and cycloalkyl group having 5 to 10 carbon atoms which may have a substituent A linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, 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 Fused polycyclic aromatic group or substitution Properly represents the unsubstituted aryloxy group, R ₃ and R ₄ may be the same or different, a hydrogen atom, a deuterium atom, a straight good 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 or branched group having 2 to 6 carbon atoms which may have a substituent A substituted 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 ₅ and R ₆ may be the same as each other May be different and optionally substituted cycloalkyl group having 5 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted heterocyclic group, or substituted or unsubstituted Of the condensed polycyclic aromatic group. R ₁ and R ₂ may be bonded to each other at adjacent groups to form a ring.

  The present invention also includes a charge control agent, a charge control agent containing one or more thiophene dicarboxylic acid derivatives represented by the general formula (1) as active ingredients, a colorant, and a binder resin. A toner is provided.

  The present invention further provides a polymerization containing a charge control agent containing one or more thiophene dicarboxylic 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 of the thiophene dicarboxylic acid derivatives represented by the above general formula (1) as an active ingredient has a high charge amount, and has no problem in waste regulation and is safe. Therefore, it can be suitably used for toner charge control. Accordingly, the present invention provides a charge control agent containing one or more thiophene dicarboxylic acid derivatives represented by the above general formula (1) as an active ingredient for controlling the charge of the toner, or the above general formula. It can also be said that the charge control agent containing one or more thiophene dicarboxylic 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 thiophene dicarboxylic 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 of the thiophene dicarboxylic acid derivatives represented by the general formula (1) as an active ingredient has a higher charge rising speed than a conventional charge control agent, 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 which concerns on this embodiment contains the 1 type (s) or 2 or more types of the thiophene dicarboxylic acid derivative represented by the said General formula (1) as an active ingredient. First, the thiophene dicarboxylic acid derivative represented by the general formula (1) will be described.

“A linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent” represented by R ₁ and R ₂ 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 the “8 linear or branched alkyl group”, “C 5 -C 10 cycloalkyl group” or “C 2 -C 6 linear or branched 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 group, n-heptyl group, isoheptyl group Group, n-octyl group, Sookuchiru 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, adjacent R ₁ and R ₂ is a thiophene ring In the case of bonding at matching positions, adjacent groups may be bonded to each other via a single bond, oxygen atom or sulfur atom 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 and R ₂ in the general formula (1), “the substituent is Preferred is a linear or branched alkyl group having 1 to 6 carbon atoms which may be present, and “a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent”. An “alkyl group” is more preferable. In the “cycloalkyl group having 5 to 10 carbon atoms which may have a substituent” represented by R ₁ and R ₂ in the general formula (1), the “having a substituent” Preferred is a cycloalkyl group having 5 to 6 carbon atoms. In the “linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent” represented by R ₁ and R ₂ in the general formula (1), “substitution” A “linear or branched alkenyl group having 2 to 4 carbon atoms which may have a group” is preferable.

“A linear or branched alkyl group having 1 to 8 carbon atoms having a substituent” represented by R ₁ and R ₂ in the general formula (1), “having 5 to 10 carbon atoms having a substituent” Specific examples of the “substituent” in the “cycloalkyl group” or “straight or branched alkenyl group having 2 to 6 carbon atoms” include a deuterium atom, a trifluoromethyl group, and a cyano 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, a 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, isooctyl group, etc. Or 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 Group, aralkyl group such as phenethyl group; aryloxy group such as phenyloxy group and tolyloxy group; arylalkyloxy group such as benzyloxy group and phenethyloxy group; phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group, Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as 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, 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 Group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalyl group, benzoimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, carbolinyl group, etc .; styryl group, naphthylvinyl group, etc. Aryl vinyl groups; acyl groups such as acetyl groups and benzoyl groups; dialkylamino groups such as dimethylamino groups and diethylamino groups; aromatic hydrocarbon groups such as diphenylamino groups and dinaphthylamino groups 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.

“A linear or branched alkyloxy group having 1 to 8 carbon atoms which may have a substituent” represented by R ₁ and R ₂ in the general formula (1) or “having a substituent In the "cycloalkyl group having 5 to 10 carbon atoms" which may be "linear or branched alkyloxy group having 1 to 8 carbon atoms" or "cycloalkyloxy group having 5 to 10 carbon atoms". Specifically, methyloxy group, ethyloxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, n-heptyl group. Oxy group, isoheptyloxy group, n-octyloxy group, isooctyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, B octyloxy group, 1-like adamantyl group and a 2-adamantyl group can be exemplified, if R ₁ and R ₂ are attached to adjacent positions of the thiophene ring, a single bond in adjacent groups to each other, They may be bonded to each other via 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 and R ₂ in the general formula (1), “substituent Is preferably a linear or branched alkyloxy group having 1 to 6 carbon atoms which may have a "straight or branched alkyl group having 1 to 4 carbon atoms which may have a substituent." And the like "is more preferable. In the “cycloalkyl group having 5 to 10 carbon atoms which may have a substituent” represented by R ₁ and R ₂ in the general formula (1), the “having a substituent”. An optionally substituted cycloalkyloxy group having 5 to 6 carbon atoms is preferable.

“A linear or branched alkyloxy group having 1 to 8 carbon atoms having a substituent” represented by R ₁ and R ₂ in the general formula (1) or “5 to 10 carbon atoms having a substituent” Specific examples of the “substituent” in the “cycloalkyloxy group of” include deuterium atom, trifluoromethyl group, cyano group, nitro group, hydroxyl group; halogen such as fluorine atom, chlorine atom, bromine atom and iodine atom 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 and isooctyl group; methyloxy group, ethyloxy group, C1-C8 linear or branched alkyloxy groups such as pyroxy groups; alkenyl groups such as allyl groups; aralkyl groups such as benzyl groups, naphthylmethyl groups, and phenethyl groups; phenyloxy groups, tolyloxy groups, etc. 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 , 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 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. Dialkylamino groups such as dimethylamino groups and diethylamino groups; disubstituted amino groups substituted with aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as diphenylamino groups and dinaphthylamino groups; 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.

“Substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted heterocyclic group” or “substituted or unsubstituted condensed polycyclic aromatic” represented by R ₁ and R ₂ in the general formula (1) As the “aromatic hydrocarbon group”, “heterocyclic group” or “fused polycyclic aromatic group” in the “group”, specifically, a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, an anthryl group, a 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, thiola Group, 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 And R ₁ and R ₂ are bonded to adjacent positions of the thiophene ring, the adjacent groups are bonded to each other through a single bond, oxygen atom or sulfur atom. May form a ring.

The “substituent” in the “substituted aromatic hydrocarbon group”, “substituted heterocyclic group” or “substituted condensed polycyclic aromatic group” represented by R ₁ and R ₂ in the general formula (1) is specifically 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, 1 carbon atom such as 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 -8 linear or branched alkyl groups; C5-C10 cycloalkyl groups such as cyclopentyl and cyclohexyl groups; vinyl groups, allyl groups, 2- Linear or branched alkenyl groups having 2 to 6 carbon atoms such as tenenyl group and 1-hexenyl group; linear or branched having 1 to 8 carbon atoms such as methyloxy group, ethyloxy group and propyloxy group Alkyloxy groups; cycloalkyloxy groups having 5 to 10 carbon atoms such as cyclopentyloxy group and cyclohexyloxy group; aralkyl groups such as benzyl group, naphthylmethyl group and phenethyl group; phenyloxy group, tolyloxy group and biphenylyl group 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 An aromatic hydrocarbon group such as a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a fluorenyl group, an indenyl group, a pyrenyl group, a perylenyl group, a fluoranthenyl group, a triphenylenyl group, or a condensed polycyclic aromatic group 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, 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 alkene And a group such as a disubstituted amino group substituted with a substituent selected from the above group, and these substituents may be further substituted with other substituents, such as a single bond, an oxygen atom Alternatively, they may be bonded to each other via a sulfur atom to form a ring.

As the “aryloxy group” in the “substituted or unsubstituted aryloxy group” represented by R ₁ and R ₂ in the general formula (1), specifically, a phenyloxy group, a tolyloxy group, a biphenylyloxy group, Tar phenylene Lil group, naphthyloxy group, anthryloxy group, phenanthryloxy group, fluorenyl group, indenyl group, pyrenyloxy group, etc. can be mentioned Perireniruokishi group, R ₁ and R ₂ are When bonded to adjacent positions of the thiophene ring, adjacent groups may be bonded to each other via a single bond, an oxygen atom or a sulfur atom to form a ring.

Specific examples of the “substituent” in the “substituted aryloxy group” represented by R ₁ and R ₂ in the general formula (1) include a deuterium atom, a cyano group, a trifluoromethyl group, a nitro group, and a hydroxyl group. Halogen atoms 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 and the like. -6 linear or branched alkenyl groups; linear or branched alkyloxy groups having 1 to 8 carbon atoms such as methyloxy, ethyloxy and propyloxy groups; cyclopentyloxy and cyclohexyloxy groups A cycloalkyloxy group having 5 to 10 carbon atoms such as aralkyl group such as benzyl group, naphthylmethyl group and phenethyl group; phenyloxy group, tolyloxy group, biphenylyloxy group, terphenylyloxy group, naphthyloxy group, Aryloxy groups such as anthryloxy group, phenanthryloxy group, fluorenyloxy group, indenyloxy group, pyrenyloxy group, perylenyloxy 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, 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 Group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalyl group, benzoimidazolyl group, pyrazolyl group, dibenzo Heterocyclic groups such as ranyl group, dibenzothienyl group and carbolinyl group; aryl vinyl groups such as styryl group and naphthyl vinyl group; acyl groups such as acetyl group and benzoyl group; dialkylamino groups such as dimethylamino group and diethylamino group; 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 Disubstituted by a substituent selected from an aralkyl group, a heterocyclic group or an alkenyl group Groups such as mino group, and these substituents may be further substituted by other substituents and bonded to each other through a single bond, oxygen atom or sulfur atom to form a ring. May be.

R ₁ and R ₂ in the general formula (1) are a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a linear or branched chain having 1 to 8 carbon atoms. An alkyl group, a cycloalkyl group having 5 to 10 carbon atoms, a linear or branched alkenyl group having 2 to 6 carbon atoms, a linear or branched alkyloxy group having 1 to 8 carbon atoms, A cycloalkyloxy group having 5 to 10 carbon atoms, an unsubstituted aromatic hydrocarbon group, an unsubstituted heterocyclic group, an unsubstituted condensed polycyclic aromatic group, or an unsubstituted aryloxy group is preferable. Adjacent groups may be bonded to each other to form a ring. R ₁ and R ₂ include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a linear or branched alkyl group having 1 to 8 carbon atoms, and 2 to 6 carbon atoms. A linear or branched alkenyl group or an unsubstituted aromatic hydrocarbon group is more preferable, and these groups may be bonded to each other to form a ring. R ₁ and R ₂ are more preferably a hydrogen atom.

“A linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent” represented by R ₃ and R ₄ 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”. 8 linear or branched alkyl group ”,“ cycloalkyl group having 5 to 10 carbon atoms ”or“ linear or branched alkenyl group having 2 to 6 carbon atoms ”includes the above R are the same groups as those given for ₁ and R _2, substituent which may be possessed by these groups is also similar to that shown with respect to R ₁ and R _2.

“Substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted heterocyclic group” or “substituted or unsubstituted condensed polycyclic aromatic” represented by R ₃ and R ₄ in the general formula (1) The “aromatic hydrocarbon group”, “heterocyclic group” or “fused polycyclic aromatic group” in the “group” is the same group as those described above with respect to R ₁ and R ₂ , and these groups Substituents that may have are the same as those shown for R ₁ and R ₂ .

As R ₃ and R ₄ in the general formula (1), a hydrogen atom, a deuterium atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, A linear or branched alkenyl group having 2 to 6 carbon atoms or an unsubstituted aromatic hydrocarbon group is preferable, and a hydrogen atom, a deuterium atom, or a linear or branched chain having 1 to 8 carbon atoms. Are more preferable, a hydrogen atom or a deuterium atom is still more preferable, and a hydrogen atom is still more preferable.

As the “cycloalkyl group having 5 to 10 carbon atoms” in the “cycloalkyl group having 5 to 10 carbon atoms which may have a substituent” represented by R ₅ and R ₆ in the general formula (1) Specific examples 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.

Specific examples of the “substituent” in the “cycloalkyl group having 5 to 10 carbon atoms having a substituent” represented by R ₅ and R ₆ in the general formula (1) include a deuterium atom and trifluoromethyl. Group, cyano 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 -Linear or branched chain having 1 to 8 carbon atoms such as -butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl 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; Aralkyl groups such as benzyl group, naphthylmethyl group and phenethyl group; aryloxy groups such as phenyloxy group and tolyloxy group; arylalkyloxy groups such as benzyloxy group and phenethyloxy group; phenyl group and biphenylyl group , Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as terphenylyl group, naphthyl group, anthracenyl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group; pyridyl group, Furanyl, pyranyl, thienyl, furyl, pyrrolyl, pyrrolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, pyridazinyl, pyrazinyl, piperi Zinyl, piperazinyl, thiolanyl, thianyl, quinolyl, isoquinolyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, benzoxazolyl, benzothiazolyl, quinoxalyl, benzoimidazolyl, pyrazolyl, dibenzo Heterocyclic groups such as furanyl group, dibenzothienyl group, carbolinyl group; aryl vinyl groups such as styryl group and naphthyl vinyl group; acyl groups such as acetyl group and benzoyl group; dialkylamino groups such as dimethylamino group and diethylamino group; Disubstituted amino groups substituted with aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as diphenylamino group and dinaphthylamino group; Diaralkylamino groups such as dibenzylamino group and diphenethylamino group; Dipyridylamino group , Jichi Disubstituted amino groups substituted by heterocyclic groups such as nylamino groups and dipiperidinylamino groups; dialkenylamino groups such as diallylamino groups; alkyl groups, aromatic hydrocarbon groups, condensed polycyclic aromatic groups, aralkyls And a group such as a disubstituted amino group substituted with a substituent selected from a group, a heterocyclic group or an alkenyl group, and these substituents may be further substituted with other substituents. May be bonded to each other through a single bond, an oxygen atom or a sulfur atom to form a ring.

As the “substituent” in the “cycloalkyl group having 5 to 10 carbon atoms having a substituent” represented by R ₅ and R ₆ in the general formula (1), a fluorine atom, a chlorine atom, a bromine atom, an iodine atom 1 or 2 selected from the group consisting of a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkyloxy group having 1 to 8 carbon atoms, and an alkenyl group It is preferably a seed or more, and includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a linear or branched alkyl group having 1 to 8 carbon atoms, and a linear or branched group having 1 to 8 carbon atoms. It is more preferable that it is 1 type or 2 types or more selected from the group which consists of a linear alkyloxy group, 1 type selected from the group which consists of a C1-C8 linear or branched alkyl group Or more preferably two or more There.

In the “cycloalkyl group having 5 to 10 carbon atoms which may have a substituent” represented by R ₅ and R ₆ in the general formula (1), “may have a substituent”. A cycloalkyl group having 5 to 8 carbon atoms "is preferable, and an" cycloalkyl group having 5 to 7 carbon atoms which may have a substituent "is more preferable, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, or A 4-tert-butylcyclohexyl group is more preferred.

“Substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted heterocyclic group” or “substituted or unsubstituted condensed polycyclic aromatic” represented by R ₅ and R ₆ in formula (1) The “group group” is the same group as that shown for R ₁ and R ₂ above, and the substituents that these groups may have are the same as those shown for R ₁ and R ₂ above. It is. Among these, an embodiment in which R ₅ is represented by the following general formula (1A-1) and R ₆ is represented by the following general formula (1A-2) is preferable.

In general formula (1A-1) and general formula (1A-2), R < ₇ >, R < ₈ >, R < ₉ >, R < ₁₀ >, R < ₁₁ >, R < ₁₂ >, R <_13> , R <_14> , R <_15> and R <_16> (R < ₇ >-). R ₁₆ ) may be the same as or different from each other, and each represents a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, cyano group, trifluoromethyl group, nitro group, or substituent. A linear or branched alkyl group having 1 to 8 carbon atoms which may have, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, and a substituent; A linear or branched alkenyl group having 2 to 6 carbon atoms, a linear or branched alkyloxy group having 1 to 8 carbon atoms which may have a substituent, and a substituent. Optionally having 5 to 10 carbon atoms Shi group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group. R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ , or R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , and R ₁₆ are bonded to each other to form a ring. May be. * Indicates a bond.

“C1-C8 linear or branched alkyl optionally having substituent (s)” represented by R _{7 to} R ₁₆ in general formula (1A-1) and general formula (1A-2) Group "," optionally substituted cycloalkyl group having 5 to 10 carbon atoms "," optionally substituted straight chain or branched alkenyl having 2 to 6 carbon atoms " Group "," optionally substituted linear or branched alkyloxy group having 1 to 8 carbon atoms "," optionally substituted cyclohexane having 5 to 10 carbon atoms ". "Alkyloxy group", "substituted or unsubstituted aromatic hydrocarbon group", "substituted or unsubstituted heterocyclic group", "substituted or unsubstituted condensed polycyclic aromatic group", or "substituted or unsubstituted "Aryloxy group" in "linear or branched having 1 to 8 carbon atoms" “Alkyl group”, “cycloalkyl group having 5 to 10 carbon atoms”, “linear or branched alkenyl group having 2 to 6 carbon atoms”, “linear or branched chain having 1 to 8 carbon atoms” As "alkyloxy group", "cycloalkyl group having 5 to 10 carbon atoms", "aromatic hydrocarbon group", "heterocyclic group", "condensed polycyclic aromatic group", or "aryloxy group" Are the same groups as those shown for R ₁ and R ₂ above, and the substituents that these groups may have are also the same as those shown for R ₁ and R ₂ above.

R _{7 to} R ₁₆ in the general formula (1A-1) and the general formula (1A-2) include a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a cyano group, Trifluoromethyl group, nitro group, linear or branched alkyl group having 1 to 8 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, linear or branched chain having 2 to 6 carbon atoms An alkenyl group, a linear or branched alkyloxy group having 1 to 8 carbon atoms, a cycloalkyloxy group having 5 to 10 carbon atoms, an unsubstituted aromatic hydrocarbon group, an unsubstituted heterocyclic group, no A substituted condensed polycyclic aromatic group or an unsubstituted aryloxy group is preferred, and a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, a straight chain having 1 to 8 carbon atoms or Branched A kill group, a linear or branched alkyloxy group having 1 to 8 carbon atoms, or an unsubstituted aromatic hydrocarbon group is more preferable, and a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, More preferred are a fluoromethyl group, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkyloxy group having 1 to 8 carbon atoms.

  Examples of the thiophene dicarboxylic acid derivative represented by the general formula (1) include the following general formula (2), the following general formula (2A), the following general formula (2A-1), the following general formula (2A-2), The following general formula (2A-3), the following general formula (2A-4), the following general formula (2B), the following general formula (2B-1), the following general formula (2B-2), or the following general formula (2B-3) The thiophene dicarboxylic acid derivative represented by this may be sufficient.

In the general formula (2), R ₁ and R ₂ 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, trifluoromethyl. Group, nitro group, linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, and cycloalkyl group having 5 to 10 carbon atoms which may have a substituent A linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, 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 Fused polycyclic aromatic group or substitution Properly represents the unsubstituted aryloxy group, R ₃ and R ₄ may be the same or different, a hydrogen atom, a deuterium atom, a straight good 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 or branched group having 2 to 6 carbon atoms which may have a substituent A substituted 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 ₅ and R ₆ may be the same as each other May be different and optionally substituted cycloalkyl group having 5 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted heterocyclic group, or substituted or unsubstituted Of the condensed polycyclic aromatic group. R ₁ and R ₂ may be bonded to each other at adjacent groups to form a ring.

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

In general formula (2A-1), R ₁ and R ₂ 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, carbon A linear or branched alkyl group having 1 to 8 atoms, a cycloalkyl group having 5 to 10 carbon atoms, a linear or branched alkenyl group having 2 to 6 carbon atoms, and 1 to 8 carbon atoms A linear or branched alkyloxy group, a cycloalkyloxy group having 5 to 10 carbon atoms, an unsubstituted aromatic hydrocarbon group, an unsubstituted heterocyclic group, an unsubstituted condensed polycyclic aromatic group, Or an unsubstituted aryloxy group, R ₃ and R ₄ may be the same or different from each other, and are a hydrogen atom, a deuterium atom, a linear or branched alkyl group having 1 to 8 carbon atoms, carbon A cycloalkyl group having 5 to 10 atoms Represents a linear or branched alkenyl group having 2 to 6 carbon atoms, or an unsubstituted aromatic hydrocarbon group, and R ₅ and R ₆ may be the same as or different from each other and have a substituent. And a cycloalkyl group having 5 to 10 carbon atoms which may be present. R ₁ and R ₂ may be bonded to each other at adjacent groups to form a ring.

一般式（２Ａ−２）中、Ｒ_１及びＲ_２は相互に同一でも異なってもよく、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ヒドロキシル基、炭素原子数１〜８の直鎖状若しくは分岐状のアルキル基、炭素原子数２〜６の直鎖状若しくは分岐状のアルケニル基又は無置換の芳香族炭化水素基を示し、Ｒ_３及びＲ_４は相互に同一でも異なってもよく、水素原子、重水素原子、又は炭素原子数１〜８の直鎖状若しくは分岐状のアルキル基を示し、Ｒ_５及びＲ_６は、置換基を有していてもよい炭素原子数５〜１０のシクロアルキル基を示す。また、Ｒ_１及びＲ_２は、隣り合う基同士で互いに結合して環を形成していてもよい。

In General Formula (2A-2), R ₁ and R ₂ may be the same or different from each other, and are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, or a straight chain having 1 to 8 carbon atoms. A chain or branched alkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms, or an unsubstituted aromatic hydrocarbon group, and R ₃ and R ₄ may be the same or different from each other. Well, it represents a hydrogen atom, a deuterium atom, or a linear or branched alkyl group having 1 to 8 carbon atoms, and R ₅ and R ₆ each have 5 to 5 carbon atoms which may have a substituent. 10 cycloalkyl groups are shown. R ₁ and R ₂ may be bonded to each other at adjacent groups to form a ring.

In general formula (2A-3), R ₁ and R ₂ may be the same or different from each other, and have a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, or a substituent. A linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkenyl group having 2 to 6 carbon atoms, or an unsubstituted aromatic hydrocarbon group, and R ₅ and R ₆ represents a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent. R ₁ and R ₂ may be bonded to each other at adjacent groups to form a ring.

In General Formula (2A-4), R ₅ and R ₆ represent an optionally substituted cycloalkyl group having 5 to 10 carbon atoms.

In general formula (2B), R ₁ and R ₂ 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, trifluoromethyl. Group, nitro group, linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, and cycloalkyl group having 5 to 10 carbon atoms which may have a substituent A linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, 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 Fused polycyclic aromatic groups, or Or show the unsubstituted aryloxy group, R ₃ and R ₄ may be the same or different, a hydrogen atom, a deuterium atom, which may have a substituent linear 1 to 8 carbon atoms Or a branched alkyl group, an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, and an optionally substituted straight chain or branched chain having 2 to 6 carbon atoms An 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 ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ may be the same or different from each other, and are a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, Cyano group, trifluoromethyl Group, nitro group, linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, and cycloalkyl group having 5 to 10 carbon atoms which may have a substituent A linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, 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 condensed polycyclic aromatic group or a substituted or unsubstituted aryloxy group is shown. R ₁ and R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ , and R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are bonded to each other through adjacent groups. May form a ring.

In General Formula (2B-1), R ₁ and R ₂ may be the same or different from each other, and are a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, or 1 carbon atom. -8 linear or branched alkyl group, cycloalkyl group having 5 to 10 carbon atoms, linear or branched alkenyl group having 2 to 6 carbon atoms, linear chain having 1 to 8 carbon atoms Or branched alkyloxy group, cycloalkyloxy group having 5 to 10 carbon atoms, unsubstituted aromatic hydrocarbon group, unsubstituted heterocyclic group, unsubstituted condensed polycyclic aromatic group, or unsubstituted R ₃ and R ₄ may be the same or different from each other, and are a hydrogen atom, a deuterium atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a carbon atom number of 5 -10 cycloalkyl groups, carbon atoms A linear or branched alkenyl group of 2 to 6, an unsubstituted aromatic hydrocarbon group, an unsubstituted heterocyclic group, or an unsubstituted condensed polycyclic aromatic group, R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ 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, trifluoromethyl group, nitro group, linear or branched alkyl group having 1 to 8 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, 2 to 6 carbon atoms A linear or branched alkenyl group, a linear or branched alkyloxy group having 1 to 8 carbon atoms, a cycloalkyloxy group having 5 to 10 carbon atoms, an unsubstituted aromatic hydrocarbon group, Unsubstituted heterocyclic group, unsubstituted If polycyclic aromatic group, or an unsubstituted aryloxy group. R ₁ and R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ , and R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are bonded to each other through adjacent groups. May form a ring.

In general formula (2B-2), R ₁ and R ₂ may be the same or different from each other, and are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a straight chain having 1 to 8 carbon atoms. A chain or branched alkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms, or an unsubstituted aromatic hydrocarbon group, wherein R ₃ and R ₄ are the same or different from each other And represents a hydrogen atom, a deuterium atom, or a linear or branched alkyl group having 1 to 8 carbon atoms, and R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R _13. , R ₁₄ , R ₁₅ and R ₁₆ may be the same as or different from each other, and may be a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, a straight chain having 1 to 8 carbon atoms, Branched alkyl group, 1 carbon atom -8 linear or branched alkyloxy groups or unsubstituted aromatic hydrocarbon groups. R ₁ and R ₂ may be bonded to each other at adjacent groups to form a ring.

In General Formula (2B-3), R ₃ and R ₄ represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, and R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ may be the same or different from each other, and are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, a carbon atom. A linear or branched alkyl group having 1 to 8 carbon atoms or a linear or branched alkyloxy group having 1 to 8 carbon atoms is shown.

  The thiophene dicarboxylic acid derivative represented by the general formula (1) according to this embodiment can be produced by a known method. For example, the thiophene dicarboxylic acid derivative according to this embodiment can be synthesized by reacting the corresponding dithiolide of thiophene dicarboxylic acid with an alicyclic hydrocarbon having a corresponding amino group in the presence of a base or the like. it can. It can also be synthesized by reacting the corresponding thiophene dicarboxylic acid with the corresponding alicyclic hydrocarbon having an amino group in the presence of a dehydrating condensing agent.

  Specific examples of preferable compounds among the thiophene dicarboxylic acid derivatives represented by the general formula (1) according to this embodiment 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 size is preferably adjusted to 1.0 μm or less, and particularly preferably adjusted to a 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 of incorporating the charge control agent according to the present embodiment into the toner, a method of adding a charge control agent to a binder resin together with a colorant, kneading and pulverization (pulverized toner), or a polymerizable monomer A method in which a charge control agent is added to a monomer and polymerized to obtain a toner (polymerized toner), a method in which toner particles are added in advance (internal addition), and a toner particle surface prepared in advance. There is a method of adding (external addition) to. As a preferable addition amount of the charge control agent when internally added to the toner particles, the amount of the thiophene dicarboxylic acid derivative with respect to 100 parts by mass of the binder resin is preferably 0.1 to 10 parts by mass, and more preferably 0.2 to The amount is 5 parts by mass. In addition, when externally added to the toner particles, the amount of the thiophene dicarboxylic 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. In addition, when externally added to the toner particles, the charge control agent is preferably fixed mechanochemically on the surface of the toner particles.

  In this embodiment, the charge control agent containing the thiophene dicarboxylic 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 this embodiment, when the charge control agent according to this embodiment is used in combination with another charge control agent, the addition amount of the charge control agent other than the charge control agent according to this embodiment is 100 parts by mass of the binder resin. 0.1 to 10 parts by mass is preferable.

  As the binder resin used in the toner according to the exemplary embodiment, a known resin can be used, for example, a vinyl polymer such as a styrene monomer, an acrylate monomer, a methacrylate monomer, or the like. Polyester polymer; Polyol resin; Phenol resin; Silicone resin; Polyurethane resin; Polyurethane resin; Epoxy resin; Xylene resin; Terpene resin; Polycarbonate resin; petroleum resin and the like can be mentioned.

  Examples of the styrene monomer, acrylate monomer, and methacrylate monomer that form the vinyl polymer or copolymer are shown 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, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-dodecyl acrylate, and 2-ethyl acrylate. Examples include hexyl, stearyl acrylate, acrylic acid such as 2-chloroethyl acrylate, and phenyl acrylate, or esters thereof.

  Examples of methacrylate monomers include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, and 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 Monoesters 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 Unsaturated dibasic acid esters such as malic acid; (14) α, β-unsaturated acids such as crotonic acid and cinnamic acid; and (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.

  In addition, a diacrylate compound or a dimethacrylate compound linked by a chain containing an aromatic group and an ether bond is also exemplified. 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 this embodiment, as a polymerization initiator used for manufacture of a vinyl polymer or a copolymer, for example, 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, cycl Ketone peroxides such as hexanone peroxide, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydro Peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl Peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, diisopropylperoxydicarbonate, di-2-ethylhexylperoxy Carbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, diethoxyisopropyl peroxydicarbonate, bis (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl Peroxide, tert-butylperoxyacetate, tert-butylperoxyisobutyrate, tert-butylperoxy-2-ethylhexarate, tert-butylperoxylaurate, tert-butyloxybenzoate, tert- Butyl peroxyisopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, isoamyl peroxy-2-ethylhexanoate, di-t rt- butylperoxy to hexa hydro terephthalate, etc. tert- butylperoxy azelate and the like.

  When the binder resin is a styrene-acrylate resin, the molecular weight distribution by gel permeation chromatography (hereinafter abbreviated as GPC) soluble in the resin component tetrahydrofuran (hereinafter abbreviated as THF) has a molecular weight of 3,000. A resin having at least one peak in a region of ˜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 fixability, offset property and storage stability. 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-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 ether such as ethylene oxide and propylene oxide with bisphenol A.

  In order to crosslink the polyester resin, it is preferable to use a trivalent 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. Examples of the trivalent or higher polyvalent carboxylic acid component include trimellitic acid, pyromellitic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic 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.

  In the case where the binder resin is a polyester-based resin, at least one peak is present in the molecular weight region of 3,000 to 50,000 in the molecular weight distribution of the THF soluble component of the resin component, and the toner fixing property and offset resistance property are reduced. In terms of the THF-soluble component, a binder resin in which a component having a molecular weight of 100,000 or less is 60 to 100% is also preferable. Moreover, it is more preferable that at least one peak exists 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 said molecular weight is the number average molecular weight of standard polystyrene conversion measured with the HLC-8220GPC apparatus (made by Tosoh Corporation), for example.

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

  In the present embodiment, two or more of an amorphous polyester resin and a crystalline polyester resin may be mixed and 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 that includes a monomer component capable of reacting with both the 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.

  Moreover, when using together a polyester polymer, a vinyl polymer, and another binder resin, what has 60 mass% or more of resin whose acid value of the whole binder resin is 0.1 mgKOH / g-50 mgKOH / g. 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 is in accordance with 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. . The sample pulverized product 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, the amount of KOH solution used at this time is B (ml), and the acid value is calculated by the following formula (1). To do. 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 polymerized toner according to 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.

  Examples of 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, and 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 a fine powder of triiron tetroxide or γ-iron sesquioxide.

  Further, 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 heteroelements include elements 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 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 substance. Further, different elements can be precipitated on the particle surface by adjusting the pH after the production of the magnetic particles or adjusting the pH by adding a salt of each element.

  The usage-amount of the said magnetic body can be 10-200 mass parts of magnetic bodies with respect to 100 mass parts of binder resin, Preferably it is preferable to use 20-150 mass parts. The number average particle diameter of these magnetic materials is preferably 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.

  Further, the magnetic material preferably has magnetic properties when applied with 10K Oersted, such that the coercive force is 20 to 150 Oersted, the saturation magnetization is 50 to 200 emu / g, and the residual magnetization is 2 to 20 emu / g.

  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.

  Examples of the dye-based magenta colorant include 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 a copper phthalocyanine pigment 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 yellow lead, 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 according to the exemplary 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.

  A binder type carrier core in which magnetic powder is dispersed in a resin can also 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.

  As the resin, a styrene-methyl methacrylate copolymer, a mixture of a fluorine-containing resin and a styrene copolymer, or a silicone resin is preferable, and a silicone resin is 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 Examples thereof include a mixture with an acrylic acid-2-ethylhexyl-methyl methacrylate copolymer (copolymer mass ratio 20 to 60: 5 to 30:10:50).

  Examples of silicone resins include nitrogen-containing silicone resins and modified silicone resins produced by reacting nitrogen-containing silane coupling agents with silicone resins.

  As the magnetic material for the carrier core, oxides such as ferrite, iron-rich ferrite, magnetite, and γ-iron oxide, metals such as iron, cobalt, and 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 case of a 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. Is more preferable.

  The toner according to the exemplary 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, and sazol wax, and aliphatic hydrocarbon waxes such as oxidized polyethylene wax, and their block co-polymers. Polymers, Candelilla wax, Carnauba wax, Wax wax, Jowa wax and other plant waxes, Beeswax, Lanolin, Whale wax and other animal waxes, Ozokerite, Ceresin, Peterolatam and other mineral waxes, Montanate ester wax, Custer Examples thereof include waxes mainly composed of fatty acid esters such as waxes and those obtained by partially or fully deoxidizing fatty acid esters such as deoxidized carnauba wax.

  Examples of waxes include palmitic acid, stearic acid, montanic acid, saturated linear fatty acids such as linear alkyl carboxylic acids having a linear alkyl group, brassic acid, eleostearic acid, parinaric acid and the like. Saturated fatty acids, stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnauvir alcohol, seryl alcohol, melyl alcohol, saturated alcohols such as long-chain alkyl alcohol, polyhydric alcohols such as sorbitol, linoleic acid amide, olefinic acid amide, lauric acid Fatty acid amides such as amides, methylene biscapric acid amides, ethylene bis lauric acid amides, saturated fatty acid bis amides such as hexamethylene bis stearic acid amides, ethylene bis oleic acid amides, hexamethylene bis olein Unsaturated fatty acid amides such as amide, N, N′-dioleyl adipate amide, N, N′-dioleyl sepasin amide, m-xylene bis stearamide, N, N′-distearyl isophthalamide Aromatic bisamides such as, fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate, wax grafted with aliphatic hydrocarbon wax using vinyl monomers such as styrene and acrylate, Examples thereof include partial ester compounds of fatty acids such as behenic monoglyceride and polyhydric alcohols, and methyl ester compounds 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 polymerization of high molecular weight polyolefins, and polymerizations using catalysts such as Ziegler catalysts and metallocene catalysts under low pressures. 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, 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 functional groups Mixture of hydrocarbon wax having a 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 perspiration method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a solution liquid crystal deposition method, or low molecular weight solid fatty acids, 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.

  The types of wax having plasticizing action include, for example, wax having a low melting point, wax having a branched structure on the molecular structure, or wax having a structure having a polar group, and wax having a releasing action has a high melting point. With regard to the structure of the wax and molecule, a wax having a linear structure or a nonpolar 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 expressed. 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, and 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 according to the exemplary 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 preferably.

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

  In the present embodiment, the DSC measurement of wax or toner is preferably 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 according to the exemplary embodiment. The fluidity improver improves the fluidity of the toner (becomes easy to flow) when added to the toner surface. For example, fluororesin powder such as carbon black, vinylidene fluoride fine powder, polytetrafluoroethylene fine powder, fine powder silica such as wet process silica, dry process silica, fine powder unoxidized titanium, fine powder unalumina, silane cup Examples include treated silica, treated titanium oxide, and treated alumina that have been surface-treated with a ring agent, a titanium coupling agent, or silicone oil. Among these, fine powder silica, fine powder unoxidized titanium, and fine powder unalumina are preferable, and treated silica obtained by subjecting these to surface treatment 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 preferred fine powder silica is a fine powder produced by vapor phase oxidation of a silicon halide inclusion, and is so-called dry process 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) -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 is 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 the organosilicon compound 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, chloromethyldimethylchlorosilane , 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, and more preferably 5 nm to 50 nm. Specific surface area by nitrogen adsorption of preferably not less than 30 m ² / g as measured by BET method, that of 60m ² / g~400m ² / g is more preferable. The surface-treated fine powder is preferably not less than ^{20m 2 / g, 40m 2 /} g~300m 2 / g is more preferable. 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 according to the exemplary embodiment includes various types of metal soaps for the purpose of protecting the photoconductor / carrier, improving the cleaning property, adjusting the thermal characteristics / electrical characteristics / physical characteristics, adjusting the resistance, adjusting the softening point, and improving the fixing rate. , Fluorosurfactant, dioctyl phthalate, tin oxide, zinc oxide, carbon black, antimony oxide, etc., or inorganic fine powders such as titanium oxide, aluminum oxide, alumina, etc. are added as necessary. can do. 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 according to the exemplary 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. Therefore, in the toner according to the present 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 as compared with the fresh toner. On the other hand, when the waste toner from the toner for developing an electrostatic charge image according to 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 The difference between the fresh toner and the waste toner can be further reduced by producing the toner by a method in which a binder resin is used and a large amount of polyolefin is added thereto.

  The toner according to the exemplary 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, a core material and a shell material, which are obtained by mixing a predetermined material with a monomer that constitutes the binder resin to form an emulsified or suspended emulsion, and then polymerizing it. 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 exemplary 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 uniformly mixed. 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.

  Further, the toner according to the exemplary 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 a suitable 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 manufactured 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 photoconductor, 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. Styrenic 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 acetate 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 such as vinyl methyl ether and vinyl isobutyl ether Ether like; vinyl methyl ketone, polyvinyl hexyl ketone, vinyl ketones such as vinyl isopropyl ketone.

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

  Commercially available dispersants may be used as they are, but in order to obtain dispersed particles having a fine 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.

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

  The circularity (Ci) is measured using a flow type 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 at a dispersion concentration of 5000 to 20000 particles / μL.

  The average circularity value is preferably 0.955 to 0.995, 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 exemplary embodiment, in the case of measurement using a laser particle size distribution measuring device such as a micron sizer (for example, manufactured by Seishin Enterprise Co., Ltd.) The particle diameter of the toner 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 less than 4 μm, the toner fluidity is lowered, the chargeability of each particle is likely to be lowered, and the charge distribution is widened, so that fogging on the background or toner spillage from the developing device is likely to occur. 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 diameter is defined as volume D16% and the particle diameter corresponding to 50% cumulative is defined as volume D84%, the particle diameter corresponding to 84% cumulative volume D is calculated as (D84% / D16%) 1/2. The volume average particle size distribution index (GSDv) is preferably 1.15 to 1.30, and 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 high particle size uniformity (volume average particle size / number average particle size of 1.00 to 1.30) are preferable.

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. It is more preferable that it is 5-3.0 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). Preferably 0.2 to 0.6 g / cm ³ in the case of non-magnetic toner, in the case of the magnetic toner depends on the kind and content of the magnetic powder preferably 0.2 to 2.0 g / cm ^3.

In the case of the toner according to the present embodiment, the true specific gravity in the case of the non-magnetic toner is preferably 0.9 to 1.2 g / cm ³ , and in the case of the magnetic toner, it depends on the kind and content of the magnetic powder but is 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 this 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 100 to 350. Preferably there is.

In the present embodiment, SF-1 and SF-2 indicating the shape factor of the toner are, for example, toner particles enlarged 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. Perform shape factor calculation. 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. The closer the particle is to a sphere, the closer to 100, and the longer the particle, the larger the numerical value. SF-2 represents the unevenness of the particle. The closer the particle is to a sphere, the closer to 100, and the more complex the particle shape, the larger the numerical value.

The volume resistivity of the toner according to the exemplary embodiment 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 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.), the value is defined as a value after 1 hour when a DC voltage of 100 V is continuously applied.

The dielectric loss tangent of the toner according to the exemplary embodiment is preferably 1.0 × 10 ^{−3 to} 15.0 × 10 ⁻³ in the case of a non-magnetic toner, and the type and content of magnetic powder in the case of a magnetic toner. Depending on the amount, it is preferably 2 × 10 ⁻³ to 30 × 10 ⁻³ . In this case, the dielectric loss tangent of the toner 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 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 Izod impact value of the toner according to the exemplary embodiment is preferably 0.1 to 30 kg · cm / cm. In this case, the Izod impact value of the toner 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 melt index (MI value) of the toner according to the exemplary embodiment is preferably 10 to 150 g / 10 min. The melt index (MI value) of the toner in this case is measured according to JIS standard K-7210 (Method A). In this case, the measurement temperature is 125 ° C. and the load is 10 kg.

The melting start temperature of the toner according to the exemplary embodiment 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. -500C) and is defined as a 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.

  The glass transition temperature (Tg) of the toner according to the exemplary embodiment 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 DSC measurement of the toner according to the exemplary embodiment, it is preferable that the peak top temperature of the maximum peak exists in the region of 70 to 120 ° C. of the observed endothermic peak.

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

  The solvent dissolution residue of the toner according to the exemplary embodiment is preferably 0 to 30% by mass as a THF insoluble content, 0 to 40% by mass as an ethyl acetate insoluble content, and 0 to 30% by mass as a chloroform insoluble content. 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 exemplary embodiment can be used in a one-component development method that 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 this 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 magnetic material or glass beads described above is used as 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 along with the rotation of the developing roller, contacts the electrostatic charge latent image holding member or is opposed to the latent image latent image in a non-contact state, and develops and visualizes 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.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, these do not limit this invention at all. In the following examples, all “parts” represent “parts by mass”.

  The thiophene dicarboxylic acid derivative represented by the general formula (1) was purified by column chromatography, adsorption purification using silica gel, activated carbon, activated clay, etc., recrystallization using a solvent or crystallization method. The compound was identified by NMR analysis.

[Synthesis Example 1-1]
(Synthesis of Exemplified Compound 1-2)
To a reaction vessel purged with nitrogen, 6.08 g (71.38 mmol) of cyclopentylamine, 7.40 g (73.12 mmol) of triethylamine and 200 ml of dioxane were added, and then 2,5-thiophenedicarboxylic acid dichloride 7 while stirring. A solution of .28 g (34.82 mmol) in dioxane was added dropwise, and the mixture was heated and stirred at 35 ° C. for 7.5 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 9.37 g of white crystals (yield 87.8%).

The structure of the white crystals obtained was identified using NMR. ^The following 22 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).
δ (ppm) = 8.12 (2H), 7.67 (2H), 4.16 (2H), 1.88 (4H), 1.69 (4H), 1.53 (8H).

[Synthesis Example 1-2]
(Synthesis of Exemplified Compound 1-3)
To a reaction vessel purged with nitrogen, 4.86 g (49.04 mmol) of cyclohexylamine, 5.08 g (50.23 mmol) of triethylamine and 200 ml of dioxane were added, and then 2,5-thiophenedicarboxylic acid dichloride 5 with stirring. After adding dropwise 100 ml of a 0.000 g (23.92 mmol) dioxane solution, the mixture was heated and stirred at 35 ° C. for 7 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 7.29 g (yield 91.1%) of white crystals.

The structure of the white crystals obtained was identified using NMR. ^The following 26 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).
δ (ppm) = 8.23 (2H), 7.71 (2H), 3.69 (2H), 1.72-1.80 (8H), 1.60 (2H), 1.27-1. 32 (8H), 1.11 (2H).

[Synthesis Example 1-3]
(Synthesis of Exemplified Compound 1-4)
To a reaction vessel purged with nitrogen, 5.55 g (49.04 mmol) of 2-methylcyclohexylamine, 5.08 g (50.23 mmol) of triethylamine and 200 ml of dioxane were added, and then 2,5-thiophenedicarboxylic acid was stirred. After dropwise addition of 100 ml of a dioxane solution of 5.00 g (23.92 mmol) of acid dichloride, the mixture was heated and stirred at 60 ° C. for 5.5 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 8.05 g of white crystals (yield 92.8%).

The structure of the white crystals obtained was identified using NMR. ^The following 30 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).
δ (ppm) = 8.28-8.31 (2H), 7.73-7.89 (2H), 4.01 (2H), 1.00-1.76 (18H), 0.83-0 .85 (6H).

[Synthesis Example 1-4]
(Synthesis of Exemplified Compound 1-5)
To a reaction vessel purged with nitrogen, 5.55 g (49.04 mmol) of 4-methylcyclohexylamine, 5.08 g (50.23 mmol) of triethylamine and 200 ml of dioxane were added, and then 2,5-thiophenedicarboxylic acid was stirred. After adding dropwise 100 ml of dioxane solution of 5.00 g (23.92 mmol) of acid dichloride, the mixture was heated and stirred at 60 ° C. 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 8.26 g of white crystals (yield 95.3%).

The structure of the white crystals obtained was identified using NMR. ^The following 30 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).
δ (ppm) = 8.18-8.34 (2H), 7.71-7.80 (2H), 3.63-3.83 (2H), 1.29-1.82 (18H), 0 .86-1.05 (6H).

[Synthesis Example 1-5]
(Synthesis of Exemplified Compound 1-6)
To a reaction vessel purged with nitrogen, 4,93 g (23.6 mmol) of 2,5-thiophenedicarboxylic acid dichloride and 200 ml of dioxane were added, and then 8.8 ml (49.0) of 4-tert-butylcyclohexylamine with stirring. Mmol) and 50 ml of a dioxane solution of 7.7 ml (55 mmol) of triethylamine were added dropwise, followed by heating and stirring at 50 ° C. for 7.5 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 10.37 g (yield 98.4%) of white crystals.

The structure of the white crystals obtained was identified using NMR. ^The following 42 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).
δ (ppm) = 7.76-7.77 (2H), 7.66-7.71 (2H), 1.76-1.92 (6H), 1.25-1.55 (10H), 0 .98-1.14 (4H), 0.86 (18H).

[Synthesis Example 1-6]
(Synthesis of Exemplified Compound 1-7)
To a reaction vessel purged with nitrogen, 5.19 g (24.8 mmol) of 2,5-thiophenedicarboxylic acid dichloride and 200 ml of dioxane were added, and then 50 ml of a dioxane solution of 14 ml (110 mmol) of cycloheptylamine was added dropwise with stirring. Then, the mixture was heated and stirred at 50 ° C. for 7.5 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 8.73 g (yield 97.1%) of white crystals.

The structure of the white crystals obtained was identified using NMR. ^The following 30 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).
δ (ppm) = 7.94-7.97 (2H), 7.65 (2H), 3.87-3.98 (2H), 1.39-1.91 (24H).

[Synthesis Example 1-7]
(Synthesis of Exemplified Compound 1-8)
To a reaction vessel purged with nitrogen, 6.86 g (53.94 mmol) of cyclooctylamine, 5.59 g (55.25 mmol) of triethylamine and 200 ml of dioxane were added, and then 2,5-thiophenedicarboxylic acid dichloride was stirred. After dropwise addition of 100 ml of a 5.50 g (26.31 mmol) dioxane solution, the mixture was heated and stirred at 60 ° C. for 5.5 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 9.69 g of white crystals (yield 94.3%).

The structure of the white crystals obtained was identified using NMR. ^The following 34 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).
δ (ppm) = 8.35-8.38 (2H), 7.74 (2H), 3.95 (2H), 1.52-1.70 (28H).

[Example 1-8]
(Manufacture 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, thiophene dicarboxylic acid derivative synthesized in Synthesis Example 1-4 (Exemplary Compound 1- 5) 1 part, 5 parts of carbon black (Mitsubishi Chemical Co., Ltd., trade name MA-100) and 3 parts of low molecular weight polypropylene (Sanyo Kasei Co., Ltd., trade name Biscol 550P) 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)
The non-magnetic toner 1-1 is mixed and shaken at a ratio of 4: 100 parts by mass (toner: carrier) with a non-coated ferrite carrier (trade name F-150, manufactured by Powder Tech Co., Ltd.) to negatively charge the toner. Thereafter, the charge amount was measured with a blow-off powder charge amount measuring device. As a result, the charge amount was −41.5 μc / g.

  Similarly, the charge amount was also evaluated when mixed with a silicon-coated ferrite carrier (trade name F96-150, manufactured by Powdertech). As a result, the charge amount was −28.3 μc / g.

[Example 1-9]
(Production and evaluation of non-magnetic toner 1-2)
Example except that the thiophene dicarboxylic acid derivative (Exemplified Compound 1-5) synthesized in Synthesis Example 1-4 was replaced with the thiophene dicarboxylic acid derivative (Exemplified Compound 1-6) synthesized in Synthetic Example 1-5 Nonmagnetic toner 1-2 was prepared in the same manner as in 1-8, 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 (trade name F-150, manufactured by Powder Tech Co., Ltd.) was −40.8 μc / g. Similarly, the charge amount when mixed with a silicon-coated ferrite carrier (product name: F96-150, manufactured by Powdertech Co., Ltd.) was −27.6 μc / g.

[Example 1-10]
(Production and evaluation of non-magnetic toner 1-3)
Example except that the thiophene dicarboxylic acid derivative (Exemplary Compound 1-5) synthesized in Synthesis Example 1-4 was replaced with the thiophene dicarboxylic acid derivative (Exemplary Compound 1-4) synthesized in Synthetic Example 1-3. Nonmagnetic toner 1-3 was prepared in the same manner as in 1-8, 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 (trade name F-150, manufactured by Powder Tech Co., Ltd.) was -39.7 μc / g. Similarly, the charge amount when mixed with a silicon-coated ferrite carrier (product name: F96-150, manufactured by Powdertech Co., Ltd.) was −27.1 μc / g.

[Comparative Example 1-1]
(Production and evaluation of comparative non-magnetic toner 1-1)
Comparative nonmagnetic toner in the same manner as in Example 1-8, except that the thiophene dicarboxylic acid derivative (Exemplary Compound 1-5) synthesized in Synthesis Example 1-4 was replaced with a salt of 3,5-tert-butylsalicylic acid and zinc. 1-1 was prepared, and the charge amount was evaluated by a blow-off powder charge amount measuring device. As a result, the amount of charge when mixed with a non-coated ferrite carrier (trade name F-150, manufactured by Powder Tech Co., Ltd.) was −23.0 μc / g. Similarly, the charge amount when mixed with a silicon-coated ferrite carrier (trade name F96-150, manufactured by Powdertech Co., Ltd.) was -15.0 μc / g.

[Example 1-11]
(Preparation of resin dispersion)
80 parts of a polyester resin (Mitsubishi Rayon Co., Ltd., DIACRON ER-561), 320 parts of ethyl acetate, and 32 parts of isopropyl alcohol are mixed, and a homogenizer (Made Co., Ltd., foamless mixer NGM-0.5TB) is used. While stirring at 5,000 to 10,000 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)
Sodium dodecylbenzenesulfonate 0.2 part, sorbon T-20 (manufactured by Toho Chemical Co., Ltd.) 0.2 part, and ion-exchanged water 17.6 parts are mixed and dissolved, and thiophene synthesized in Synthesis Example 1-4. 2.0 parts of a dicarboxylic acid derivative (Exemplary Compound 1-5) and zirconia beads (bead particle diameter 0.65 mmφ, equivalent to 15 ml) were added, and paint conditioner (UNION NJ (USA), Red Devil, Inc.) was added. 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 dispersing with a homogenizer (IKA Japan, Ultra Tarrax T-25), 0.125 part of polyaluminum chloride was added, the 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 at 400 to 700 rpm using a stirrer, 8.0 parts of a 5% by mass aqueous sodium hydroxide solution was added, and stirring was continued until the volume average particle diameter of the toner 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 size 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. 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 −45.4 μc / g.

[Comparative Example 1-2]
A toner was prepared under the same conditions as in Example 1-11 except that the operation of adding the charge control agent dispersion was omitted, and the saturation charge amount was measured. As a result, the saturation charge amount was −20.5 μC / g.

[Synthesis Example 2-1]
(Synthesis of Exemplified Compound 2-2)
To a reaction vessel purged with nitrogen, 5.00 g (23.9 mmol) of 2,5-thiophenedicarboxylic acid dichloride, 5.08 g (50.2 mmol) of triethylamine and 200 ml of dioxane were added, and while stirring, 4.56 g of aniline ( 41.0 mmol) of dioxane solution was added dropwise, and the mixture was further stirred for 4.5 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 7.30 g (yield 94.7%) of white crystals.

The structure of the white crystals obtained was identified using NMR. ^The following 14 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).
δ (ppm) = 10.40 (2H), 8.06 (2H), 7.75-7.76 (4H), 7.37-7.40 (4H), 7.13-7.15 (2H ).

[Synthesis Example 2-2]
(Synthesis of Exemplified Compound 2-3)
To a reaction vessel purged with nitrogen, 5.00 g (23.9 mmol) of 2,5-thiophenedicarboxylic acid dichloride, 5.08 g (50.2 mmol) of triethylamine and 200 ml of dioxane were added, and o-toluidine 5. After adding 100 ml of a 25 g (49.0 mmol) dioxane solution dropwise, the mixture was heated and stirred at 30 ° C. for 10 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 7.68 g of white crystals (yield 91.6%).

The structure of the white crystals obtained was identified using NMR. ^The following 18 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).
δ (ppm) = 10.01 (2H), 8.05 (2H), 7.33-7.35 (2H), 7.29-7.30 (2H), 7.19-7.25 (4H) ), 2.25 (6H).

[Synthesis Example 2-3]
(Synthesis of Exemplified Compound 2-4)
To a reaction vessel purged with nitrogen, 5.20 g (24.9 mmol) of 2,5-thiophenedicarboxylic acid dichloride and 150 ml of dioxane were added, and 5.60 g (52.2 mmol) of m-toluidine and 5. After dropwise addition of 30 ml of 51 g (54.5 mmol) of dioxane solution, the mixture was heated and stirred at 40 ° C. for 15 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 8.02 g of white crystals (yield 92.0%).

The structure of the white crystals obtained was identified using NMR. ^The following 18 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).
δ (ppm) = 10.32 (2H), 8.04 (2H), 7.54-7.27 (4H), 7.24-7.27 (2H), 6.95-6.96 (2H) ) 2.32 (6H).

[Synthesis Example 2-4]
(Synthesis of Exemplified Compound 2-7)
To a reaction vessel purged with nitrogen, 5.00 g (23.9 mmol) of 2,5-thiophenedicarboxylic acid dichloride, 5.08 g (50.2 mmol) of triethylamine and 200 ml of dioxane were added, and while stirring, 4-chloroaniline 6 .26 g (49.0 mmol) of dioxane solution (100 ml) was added dropwise, followed by heating and stirring at 30 ° C. for 7.5 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 8.64 g of white crystals (yield 92.3%).

The structure of the white crystals obtained was identified using NMR. ^The following 12 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).
[delta] (ppm) = 10.47 (2H), 8.03 (2H), 7.77-7.78 (4H), 7.42-7.44 (4H).

[Synthesis Example 2-5]
(Synthesis of Exemplified Compound 2-8)
To a reaction vessel purged with nitrogen, 5.00 g (23.9 mmol) of 2,5-thiophenedicarboxylic acid dichloride, 5.08 g (50.2 mmol) of triethylamine and 200 ml of dioxane were added, and m-anisidine 6. After dropwise addition of 100 ml of 04 g (49.0 mmol) of dioxane solution, the mixture was heated and stirred at 30 ° C. for 7 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 8.74 g (yield 95.5%) of white crystals.

The structure of the white crystals obtained was identified using NMR. ^The following 18 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).
δ (ppm) = 10.38 (2H), 8.06 (2H), 7.44 (2H), 7.34-7.35 (2H), 7.27-7.30 (2H), 6. 72-6.73 (2H), 3.77 (6H).

[Synthesis Example 2-6]
(Synthesis of Exemplified Compound 2-9)
To a nitrogen-substituted reaction vessel, 5.00 g (23.9 mmol) of 2,5-thiophenedicarboxylic acid dichloride, 5.08 g (50.2 mmol) of triethylamine and 200 ml of dioxane were added, and 2-tert-butyl was stirred. After adding dropwise 100 ml of a dioxane solution of 7.32 g (49.0 mmol) of aniline, the mixture was heated and stirred at 30 ° C. for 7 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 9.64 g (yield 92.7%) of white crystals.

The structure of the white crystals obtained was identified using NMR. ^The following 30 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).
δ (ppm) = 9.73 (2H), 7.90 (2H), 7.45-7.46 (2H), 7.22-7.28 (4H), 7.13-7.14 (2H) ), 1.35 (18H).

[Synthesis Example 2-7]
(Synthesis of Exemplified Compound 2-10)
To a reaction vessel purged with nitrogen, 5.00 g (23.9 mmol) of 2,5-thiophenedicarboxylic acid dichloride, 5.08 g (50.2 mmol) of triethylamine, and 200 ml of dioxane were added and heated. 100 ml of a dioxane solution of 7.90 g (49.0 mmol) of (trifluoromethyl) aniline was added dropwise at 50 ° C. The mixture was further heated and stirred at 98 ° C. for 40 hours. After standing overnight, the reaction solution was added to 400 ml of diluted hydrochloric acid with stirring. Extraction with ethyl acetate was performed, and the organic layer was washed twice with aqueous sodium bicarbonate and twice with water, then dehydrated with anhydrous magnesium sulfate, and the solvent was removed by concentration under reduced pressure to remove the residue. Obtained. The crude product precipitated by adding cyclohexane to the residue and triturating was collected by filtration. By drying under reduced pressure at 60 ° C., 2.31 g of light yellow crystals (yield 21.1%) was obtained.

The structure of the white crystals obtained was identified using NMR. ^The following 12 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).
δ (ppm) = 10.41 (2H), 8.00 (2H), 7.83-7.84 (2H), 7.76-7.78 (2H), 7.57-7.60 (4H) ).

[Synthesis Example 2-8]
(Synthesis of Exemplary Compound 2-11)
To a reaction vessel purged with nitrogen, 5.00 g (23.9 mmol) of 2,5-thiophenedicarboxylic acid dichloride, 5.08 g (50.2 mmol) of triethylamine and 200 ml of dioxane were added, and N-methyl-m was stirred. -Toluidine (5.94 g, 49.0 mmol) in dioxane (100 ml) was added dropwise, followed by heating and stirring at 30 ° C for 7.5 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 8.27 g (yield 91.4%) of white crystals.

The structure of the white crystals obtained was identified using NMR. ^The following 22 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).
δ (ppm) = 7.26-7.29 (2H), 7.19-7.20 (2H), 7.11 (2H), 7.02-7.04 (2H), 6.33 (2H) ), 3.25 (6H), 2.28 (6H).

[Example 2-9]
(Manufacture of non-magnetic toner 2-1)
Styrene-acrylate copolymer resin (Mitsui Chemicals, trade name CPR-100, acid value 0.1 mg KOH / g) 91 parts, thiophene dicarboxylic acid derivative synthesized in Synthesis Example 2-6 (Exemplary Compound 2- 9) 1 part, 5 parts of carbon black (Mitsubishi Chemical Co., Ltd., trade name MA-100) and 3 parts of low molecular weight polypropylene (Sanyo Kasei Co., Ltd., trade name Biscol 550P) are heated and mixed at 130 ° C. (biaxial) The mixture was melt mixed by an extrusion kneader. The cooled mixture was roughly pulverized with a hammer mill, then finely pulverized with a jet mill, and classified to obtain a nonmagnetic toner having a volume average particle size of 9 ± 0.5 μm.

(Evaluation of non-magnetic toner 2-1)
The nonmagnetic toner 2-1 is mixed and shaken at a ratio of 4: 100 parts by mass (toner: carrier) with a non-coated ferrite carrier (product name: F-150, manufactured by Powder Tech Co., Ltd.) to negatively charge the toner. Thereafter, the charge amount was measured with a blow-off powder charge amount measuring device. As a result, the charge amount was −35.2 μc / g.

  Similarly, the charge amount was also evaluated when mixed with a silicon-coated ferrite carrier (trade name F96-150, manufactured by Powdertech). As a result, the charge amount was −23.5 μc / g.

[Comparative Example 2-1]
(Production and evaluation of comparative non-magnetic toner 2-1)
Except that the thiophene dicarboxylic acid derivative (Exemplary Compound 2-9) synthesized in Synthesis Example 2-6 was replaced with a salt of 3,5-tert-butylsalicylic acid and zinc, the same method as in Example 2-9 Comparative non-magnetic toner 2-1 was prepared, and the charge amount was evaluated by a blow-off powder charge amount measuring device. As a result, the amount of charge when mixed with a non-coated ferrite carrier (trade name F-150, manufactured by Powder Tech Co., Ltd.) was −23.0 μc / g. Similarly, the charge amount when mixed with a silicon-coated ferrite carrier (trade name F96-150, manufactured by Powdertech Co., Ltd.) was -15.0 μc / g.

[Example 2-10]
(Preparation of resin dispersion)
80 parts of a polyester resin (Mitsubishi Rayon Co., Ltd., DIACRON ER-561), 320 parts of ethyl acetate, and 32 parts of isopropyl alcohol are mixed, and a homogenizer (Made Co., Ltd., foamless mixer NGM-0.5TB) is used. While stirring at 5,000 to 10,000 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 thiophene synthesized in Synthesis Example 2-6 2.0 parts of a dicarboxylic acid derivative (Exemplary Compound 2-9) 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 dispersing with a homogenizer (IKA Japan, Ultra Tarrax T-25), 0.125 part of polyaluminum chloride was added, the 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 at 400 to 700 rpm using a stirrer, 8.0 parts of a 5% by mass aqueous sodium hydroxide solution was added, and stirring was continued until the volume average particle diameter of the toner 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 size 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 (trade name F96-150, manufactured by Powdertech) were mixed and shaken to charge the toner negatively, and then blow-off powder. The saturation charge amount was measured in an atmosphere at a temperature of 25 ° C. and a humidity of 50% with a body charge amount measuring device. As a result, the saturated charge amount was -37.4 μc / g.

[Comparative Example 2-2]
A toner was prepared under the same conditions as in Example 2-10, except that the operation of adding the charge control agent dispersion was omitted, and the saturation charge amount was measured. As a result, the saturation charge amount was −20.5 μC / g.

  As is clear from the above results, it was found that the polymerized toner containing the thiophene dicarboxylic acid derivative represented by the general formula (1) of the present invention as an active ingredient exhibits excellent charging performance.

  That is, by using a charge control agent containing the thiophene dicarboxylic acid derivative represented by the general formula (1) of the present invention as an active ingredient, high charge performance can be imparted to the polymerized toner.

  The thiophene dicarboxylic 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 (16)

The charge control agent which contains 1 type, or 2 or more types of the thiophene dicarboxylic acid derivative represented by the following general formula (1) as an active ingredient.

[In General Formula (1), R ₁ and R ₂ may be the same as or different from each other, and include a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, cyano group, trifluoro group. A methyl group, a nitro group, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, or a cycloalkyl having 5 to 10 carbon atoms which may have a substituent A linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, 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 condensed polycyclic aromatic group of Or show the unsubstituted aryloxy group, R ₃ and R ₄ may be the same or different, a hydrogen atom, a deuterium atom, which may have a substituent linear 1 to 8 carbon atoms Or a branched alkyl group, an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, and an optionally substituted straight chain or branched chain having 2 to 6 carbon atoms An 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 ₅ and R ₆ are the same or different from each other The cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted group; A condensed polycyclic aromatic group is shown. R ₁ and R ₂ may be bonded to each other at adjacent groups to form a ring. ] A charge control agent containing one or more thiophene dicarboxylic acid derivatives represented by the following general formula (2) as an active ingredient.

[In the general formula (2), R ₁ and R ₂ 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, trifluoro group. A methyl group, a nitro group, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, or a cycloalkyl having 5 to 10 carbon atoms which may have a substituent A linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, 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 condensed polycyclic aromatic group of Or show the unsubstituted aryloxy group, R ₃ and R ₄ may be the same or different, a hydrogen atom, a deuterium atom, which may have a substituent linear 1 to 8 carbon atoms Or a branched alkyl group, an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, and an optionally substituted straight chain or branched chain having 2 to 6 carbon atoms An 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 ₅ and R ₆ are the same or different from each other The cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted group; A condensed polycyclic aromatic group is shown. R ₁ and R ₂ may be bonded to each other at adjacent groups to form a ring. ] The charge control agent which contains the 1 type (s) or 2 or more types of the thiophene dicarboxylic acid derivative represented by the following general formula (2A) as an active ingredient.

[In General Formula (2A), R ₁ and R ₂ may be the same as or different from each other, and include a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, cyano group, trifluoro group. A methyl group, a nitro group, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, or a cycloalkyl having 5 to 10 carbon atoms which may have a substituent A linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, 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 condensed polycyclic aromatic group of Indicates substituted or unsubstituted aryloxy group, R ₃ and R ₄ may be the same or different, a hydrogen atom, a deuterium atom, a straight good 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 or branched group having 2 to 6 carbon atoms which may have a substituent A substituted 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 ₅ and R ₆ may be the same as each other It may be different and represents a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent. R ₁ and R ₂ may be bonded to each other at adjacent groups to form a ring. ] The charge control agent which contains 1 type, or 2 or more types of the thiophene dicarboxylic acid derivative represented by the following general formula (2A-1) as an active ingredient.

[In General Formula (2A-1), R ₁ and R ₂ may be the same 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, a cyano group, C1-C8 linear or branched alkyl group, C5-C10 cycloalkyl group, C2-C6 linear or branched alkenyl group, C1-C1 8 linear or branched alkyloxy groups, cycloalkyloxy groups having 5 to 10 carbon atoms, unsubstituted aromatic hydrocarbon groups, unsubstituted heterocyclic groups, unsubstituted condensed polycyclic aromatic groups Or an unsubstituted aryloxy group, R ₃ and R ₄ may be the same or different from each other, and are a hydrogen atom, a deuterium atom, a linear or branched alkyl group having 1 to 8 carbon atoms, C 5 -C 10 cycloalkyl Group, a linear or branched alkenyl group having 2 to 6 carbon atoms, or an unsubstituted aromatic hydrocarbon group, R ₅ and R ₆ may be the same or different from each other and have a substituent. And an optionally substituted cycloalkyl group having 5 to 10 carbon atoms. R ₁ and R ₂ may be bonded to each other at adjacent groups to form a ring. ] The charge control agent which contains 1 type, or 2 or more types of the thiophene dicarboxylic acid derivative represented by the following general formula (2A-2) as an active ingredient.

[In General Formula (2A-2), R ₁ and R ₂ may be the same or different from each other, and are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, or a carbon atom having 1 to 8 carbon atoms. A linear or branched alkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms, or an unsubstituted aromatic hydrocarbon group, wherein R ₃ and R ₄ are the same or different from each other; And represents a hydrogen atom, a deuterium atom, or a linear or branched alkyl group having 1 to 8 carbon atoms, and R ₅ and R ₆ each have 5 carbon atoms which may have a substituent. -10 cycloalkyl groups. R ₁ and R ₂ may be bonded to each other at adjacent groups to form a ring. ] The charge control agent which contains the 1 type (s) or 2 or more types of the thiophene dicarboxylic acid derivative represented by the following general formula (2A-3) as an active ingredient.

[In General Formula (2A-3), R ₁ and R ₂ may be the same or different from each other, and are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, or a carbon atom having 1 to 8 carbon atoms. A linear or branched alkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms, or an unsubstituted aromatic hydrocarbon group, R ₅ and R ₆ have a substituent. And a cycloalkyl group having 5 to 10 carbon atoms which may be present. R ₁ and R ₂ may be bonded to each other at adjacent groups to form a ring. ] The charge control agent which contains the 1 type (s) or 2 or more types of the thiophene dicarboxylic acid derivative represented by the following general formula (2A-4) as an active ingredient.

[In General Formula (2A-4), R ₅ and R ₆ represent a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent. ] The substituents in R ₅ and R ₆ are a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a linear or branched alkyl group having 1 to 8 carbon atoms, and a straight chain having 1 to 8 carbon atoms. The charge control agent according to any one of claims 3 to 7, which is one or more selected from the group consisting of a chain-like or branched alkyloxy group and an alkenyl group. The substituent in R ₅ and R ₆ is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a linear or branched alkyl group having 1 to 8 carbon atoms, and a linear shape having 1 to 8 carbon atoms. Or the charge control agent as described in any one of Claims 3-7 which is 1 type, or 2 or more types selected from the group which consists of a branched alkyloxy group. Substituent in R ₅ and R _6, is one or more selected from the group consisting of straight-chain or branched alkyl group having 1 to 8 carbon atoms, any one of claims 3-7 The charge control agent according to one item. A charge control agent containing one or more thiophene dicarboxylic acid derivatives represented by the following general formula (2B) as an active ingredient.

[In General Formula (2B), R ₁ and R ₂ may be the same as or different from each other, and include a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, cyano group, trifluoro group. A methyl group, a nitro group, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, or a cycloalkyl having 5 to 10 carbon atoms which may have a substituent A linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, 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 condensed polycyclic aromatic group of Indicates substituted or unsubstituted aryloxy group, R ₃ and R ₄ may be the same or different, a hydrogen atom, a deuterium atom, a straight good 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 or branched group having 2 to 6 carbon atoms which may have a substituent An 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 ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ may be the same or different from each other, and are a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydroxyl group. , Cyano group, trifluorome Group, nitro group, linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, and cycloalkyl having 5 to 10 carbon atoms which may have a substituent A linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, 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 condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group. R ₁ and R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ , and R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are bonded to each other through adjacent groups. May form a ring. ] The charge control agent which contains 1 type, or 2 or more types of the thiophene dicarboxylic acid derivative represented by the following general formula (2B-1) as an active ingredient.

[In General Formula (2B-1), R ₁ and R ₂ may be the same 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 the number of carbon atoms. Straight chain or branched alkyl group having 1 to 8 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, straight chain or branched alkenyl group having 2 to 6 carbon atoms, straight chain having 1 to 8 carbon atoms A linear or branched alkyloxy group, a cycloalkyloxy group having 5 to 10 carbon atoms, an unsubstituted aromatic hydrocarbon group, an unsubstituted heterocyclic group, an unsubstituted condensed polycyclic aromatic group, or nothing A substituted aryloxy group, wherein R ₃ and R ₄ may be the same or different from each other; a hydrogen atom, a deuterium atom, a linear or branched alkyl group having 1 to 8 carbon atoms, and the number of carbon atoms; 5-10 cycloalkyl groups, carbon atoms A linear or branched alkenyl group having 2 to 6 atoms, an unsubstituted aromatic hydrocarbon group, an unsubstituted heterocyclic group, or an unsubstituted condensed polycyclic aromatic group; R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ 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, trifluoromethyl group, nitro group, linear or branched alkyl group having 1 to 8 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, 2 to 2 carbon atoms 6 linear or branched alkenyl groups, linear or branched alkyloxy groups having 1 to 8 carbon atoms, cycloalkyloxy groups having 5 to 10 carbon atoms, and unsubstituted aromatic hydrocarbon groups , Unsubstituted heterocyclic group, unsubstituted Condensed polycyclic aromatic group, or an unsubstituted aryloxy group. R ₁ and R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ , and R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are bonded to each other through adjacent groups. May form a ring. ] The charge control agent which contains the 1 type (s) or 2 or more types of the thiophene dicarboxylic acid derivative represented by the following general formula (2B-2) as an active ingredient.

[In General Formula (2B-2), R ₁ and R ₂ may be the same or different from each other, and are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, or a carbon atom having 1 to 8 carbon atoms. A linear or branched alkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms, or an unsubstituted aromatic hydrocarbon group, wherein R ₃ and R ₄ are the same or different from each other And represents a hydrogen atom, a deuterium atom, or a linear or branched alkyl group having 1 to 8 carbon atoms, and R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ may be the same or different from each other, and are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, or a straight chain having 1 to 8 carbon atoms. Or branched alkyl group, carbon atom number 1 to 8 linear or branched alkyloxy groups or unsubstituted aromatic hydrocarbon groups. R ₁ and R ₂ may be bonded to each other at adjacent groups to form a ring. ] The charge control agent which contains 1 type, or 2 or more types of the thiophene dicarboxylic acid derivative represented by the following general formula (2B-3) as an active ingredient.

[In General Formula (2B-3), R ₃ and R ₄ represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, and R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ may be the same or different from each other, and are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, a carbon A linear or branched alkyl group having 1 to 8 atoms or a linear or branched alkyloxy group having 1 to 8 carbon atoms is shown. ]   A toner containing the charge control agent according to any one of claims 1 to 14, a colorant, and a binder resin.   A polymerized toner containing the charge control agent according to any one of claims 1 to 14, a colorant, and a binder resin.