JP2020052373A - Charge control agent and toner using the same - Google Patents

Abstract

To provide: an electrophotography charge control agent capable of exhibiting sufficient triboelectric properties to a toner, especially used for color toner, used for polymer toner, capable of enhancing the rate of rise of electrification, excellent in charge amount, having electrification properties especially excellent in temporal stability and environmental stability and safe without having a problem even in waste control; a negative electrification toner for electrostatic charge image development using the charge control agent and having high electrification performance.SOLUTION: The charge control agent includes at least one kind of hexafluoropropane bis benzoic acid derivatives represented by the following general formula (1) as an active ingredient, and the toner includes the charge control agent.SELECTED DRAWING: None

Description

  The present invention relates to a charge control agent used in an image forming apparatus for visualizing an electrostatic latent image in fields such as electrophotography and electrostatic recording, and a negatively chargeable toner containing the charge control agent.

  In the 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 generating agent and a charge transporting agent. A visible image is obtained by developing with toner, transferring to paper or a plastic film, and fixing.

  The photoreceptor has a positive charging property and a negative charging property depending on its configuration, and when the printed portion is to be left as an electrostatic latent image by exposure, it is developed with a reverse-charging toner. When the development is performed, development is performed using the same-charging toner.

  The toner is composed of a binder resin, a colorant, and other additives. Generally, a charge control agent is added to impart desirable charging characteristics (charging speed, charging level, charging stability, etc.), aging stability, environmental stability, and the like. Addition of this charge control agent greatly improves the properties of the toner.

  Today, as a positive triboelectric charge controlling agent known in the art, a nigrosine dye, an azine dye, a copper phthalocyanine pigment, a quaternary ammonium salt, or a polymer having a quaternary ammonium salt in a side chain is known. ing. Known negative triboelectric charge controlling agents include metal complex salts of monoazo dyes, metal complex salts of salicylic acid, naphthoic acid, and dicarboxylic acid, copper phthalocyanine pigments, and resins containing acid components.

  In the case of a color toner expected to expand in the market in the future, a light-colored, preferably colorless, charge control agent that does not affect the hue is indispensable. These light-colored or colorless charge control agents include a metal complex salt compound of a hydroxybenzoic acid derivative (Patent Document 1), a metal salt compound of an aromatic dicarboxylic acid (Patent Document 2), and a metal of an anthranilic acid derivative for negatively charging toner. Complex salt compounds (Patent Document 3), organic boron compounds (Patent Document 4), biphenol compounds (Patent Document 5), calix (n) arene compounds (Patent Documents 6 and 7), cyclic phenol sulfides (Patent Document 8), and the like. is there. Further, there is a quaternary ammonium salt compound (Patent Document 9) and the like for a positively chargeable toner.

JP-A-61-221756 JP-A-57-111541 JP-A-62-094856 U.S. Pat. No. 4,767,688 JP-A-61-003149 Japanese Patent No. 3325730 JP 2003-162100 A WO2007-119797 JP-A-58-098742

  However, many of these charge control agents are complexes or salts of heavy metals such as chromium, which are problems with regard to waste regulations and are not necessarily safe. In addition, the initial copy image lacks sharpness due to the fact that it cannot be completely colorless, the charging effect required today is low, and the rising speed of charging is insufficient, and during continuous copying, The quality of the copied image tends to fluctuate, or the fluctuation range of the toner charging characteristics with respect to environmental conditions such as temperature and humidity is large, and the image quality is remarkably changed due to seasonal factors and the like. There has been a demand for a charge control agent which has drawbacks such as inability to be applied, has a high charge imparting effect, and can be applied to polymerized toner.

  The present invention has been made in order to solve the above-mentioned problems, and is useful as a charge control agent for electrophotography that expresses sufficient triboelectricity to a toner, particularly for a color toner, and further useful for a polymerized toner. Providing a safe charge control agent that enhances the rate of charge rise, has an excellent charge amount, has particularly excellent charge characteristics with aging stability and environmental stability, and has no problem with waste regulations. Is to do. It is another object of the present invention to provide a negatively chargeable toner for developing an electrostatic image having high charging performance using the charge control agent.

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

1. A charge control agent containing at least one hexafluoropropanebisbenzoic acid derivative represented by the following general formula (1) as an active ingredient.

[Wherein, R ^{1 to} R ¹⁸ may be the same or different from each other;
Hydrogen atom, deuterium atom, halogen atom, hydroxyl group, cyano group, trifluoromethyl group, nitro group,
A linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent,
A cycloalkyl group having 5 to 10 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 10 carbon atoms which may have a substituent,
A linear or branched alkyloxy group having 1 to 10 carbon atoms which may have a substituent,
A cycloalkyloxy group having 5 to 10 carbon atoms which may have a substituent,
An acyl group having 1-10 carbon atoms that may have a substituent,
An aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,
A heterocyclic group having 2 to 20 carbon atoms which may have a substituent,
A condensed polycyclic aromatic group having 10 to 30 carbon atoms which may have a substituent,
Or represents an aryloxy group having 6 to 20 carbon atoms which may have a substituent,
R ¹⁹ and R ²⁰ may be the same or different from each other;
Hydrogen atom, deuterium atom,
A linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent,
A cycloalkyl group having 5 to 10 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 10 carbon atoms which may have a substituent,
An acyl group having 1-10 carbon atoms that may have a substituent,
An aromatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent,
A heterocyclic group having 2 to 20 carbon atoms which may have a substituent,
Here, R ^{1 to} R ⁵ , R ^{6 to} R ¹⁰ , R ^{11 to} R ^14, and R ^{15 to} R ¹⁸ represent a condensed polycyclic aromatic group having 10 to 30 carbon atoms which may have a substituent. May be bonded to each other by adjacent groups to form a ring. ]

2. The charge control agent as described above, which contains at least one kind of a 4,4-hexafluoropropanebisbenzoic acid derivative represented by the following general formula (2) as an active ingredient.

[Wherein, R ^{1 to} R ¹⁸ may be the same or different from each other;
Hydrogen atom, deuterium atom, halogen atom, hydroxyl group, cyano group, trifluoromethyl group, nitro group,
A linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent,
A cycloalkyl group having 5 to 10 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 10 carbon atoms which may have a substituent,
A linear or branched alkyloxy group having 1 to 10 carbon atoms which may have a substituent,
A cycloalkyloxy group having 5 to 10 carbon atoms which may have a substituent,
An acyl group having 1-10 carbon atoms that may have a substituent,
An aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,
A heterocyclic group having 2 to 20 carbon atoms which may have a substituent,
A condensed polycyclic aromatic group having 10 to 30 carbon atoms which may have a substituent,
Or represents an aryloxy group having 6 to 20 carbon atoms which may have a substituent,
R ¹⁹ and R ²⁰ may be the same or different from each other;
Hydrogen atom, deuterium atom,
A linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent,
A cycloalkyl group having 5 to 10 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 10 carbon atoms which may have a substituent,
An acyl group having 1-10 carbon atoms that may have a substituent,
An aromatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent,
A heterocyclic group having 2 to 20 carbon atoms which may have a substituent,
Here, R ^{1 to} R ⁵ , R ^{6 to} R ¹⁰ , R ^{11 to} R ^14, and R ^{15 to} R ¹⁸ represent a condensed polycyclic aromatic group having 10 to 30 carbon atoms which may have a substituent. May be bonded to each other by adjacent groups to form a ring. ]

3. A toner comprising: a charge control agent containing at least one of the hexafluoropropanebisbenzoic acid derivatives described above as an active ingredient; a colorant; and a binder resin.

4. The polymerized toner as described above.

  In the present invention, the charge control agent containing, as an active ingredient, at least one of the hexafluoropropanebisbenzoic acid derivatives represented by the general formula (1) has a higher charge rising speed than conventional charge control agents and is excellent. It has a charge amount and has a charge characteristic particularly excellent in environmental stability. In addition, it does not contain heavy metals such as chromium, which are concerned about environmental issues, and is excellent in dispersibility and compound stability.

  The charge control agent used in the present invention has excellent charge control properties, environmental resistance, and durability.When used in a pulverized toner or a polymerized toner, there is no fog, image density, dot reproducibility, and fine line reproduction. An image having good properties can be obtained.

  The hexafluoropropanebisbenzoic acid derivative represented by the general formula (1) used in the present invention can be produced by a known method. For example, by reacting the corresponding dichloride of hexafluoropropanebisbenzoic acid with the corresponding aromatic hydrocarbon or condensed polycyclic aromatic having an amino group such as aniline in the presence of a base or the like, the present invention The hexafluoropropanebisbenzoic acid derivative to be used can be synthesized. Further, it can be synthesized by reacting the corresponding hexafluoropropanebisbenzoic acid with the corresponding aromatic hydrocarbon having an amino group such as aniline or a condensed polycyclic aromatic in the presence of a dehydrating condensing agent.

  Specific examples of the hexafluoropropanebisbenzoic acid derivative represented by the general formula (1) used in the present invention are shown below, but the present invention is not limited to these compounds. In the following structural formulas, some of the hydrogen atoms and alkyl groups are omitted. Also, a mixture of two or more stereoisomers may be used.

"A linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent", represented by R ^{1 to} R ¹⁸ in the general formula (1), A cycloalkyl group having 5 to 10 carbon atoms which may be substituted or a linear or branched alkenyl group having 2 to 10 carbon atoms which may have a substituent " Specific examples of "a linear or branched alkyl group having 10 carbon atoms", "a cycloalkyl group having 5 to 10 carbon atoms" or "a linear or branched alkenyl group having 2 to 10 carbon atoms" are specifically described. , Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, isoheptyl Group, n-octyl There may be mentioned isooctyl group, a cyclopentyl group, a cyclohexyl group, 1-adamantyl, 2-adamantyl, vinyl, allyl, etc. isopropenyl group and a 2-butenyl group.

As a “linear or branched alkyloxy group having 1 to 10 carbon atoms” or a “cycloalkyloxy group having 5 to 10 carbon atoms” represented by R ^{1 to} R ¹⁸ in the general formula (1) Are specifically a methyloxy group, an ethyloxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, a t-butyloxy group, an n-pentyloxy group, an n-hexyloxy group, an n-heptyloxy group , Isoheptyloxy group, n-octyloxy group, isooctyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, 1-adamantyloxy group and 2-adamantyloxy group. Can be.

The “acyl group having 1 to 10 carbon atoms” in the “optionally substituted acyl group having 1 to 10 carbon atoms” represented by R ^{1 to} R ¹⁸ in the general formula (1) includes Specific examples include a formyl group, an acetyl group, a polopionyl group, an acrylyl group, a benzoyl group, and an acylamino group.

“Optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms” represented by R ^{1 to} R ¹⁸ in formula (1), “optionally substituted substituent” "Aromatic hydrocarbon group having 6 to 20 carbon atoms" in "heterocyclic group having 2 to 20 carbon atoms" or "condensed polycyclic aromatic group having 10 to 30 carbon atoms which may have a substituent""," Heterocyclic group having 2 to 20 carbon atoms "or" condensed polycyclic aromatic group having 10 to 30 carbon atoms "specifically includes phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthryl Group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, pyridyl group, furanyl group, pyranyl group, thiophenyl group, pyrrolidinyl group, imidazolyl group, imidazolini 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, benzothiophenyl group, indolyl group, carbazolyl Group, benzoxazolyl group, benzothiazolyl group, quinoxalyl group, benzimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothiophenyl group, and carbolinyl group.

“Aryloxy group having 6 to 20 carbon atoms” in “optionally substituted aryloxy group having 6 to 20 carbon atoms” represented by R ^{1 to} R ¹⁸ in the general formula (1) As specifically, phenoxy group, tolyloxy group, biphenylyloxy group, terphenylyloxy group, naphthyloxy group, anthryloxy group, phenanthryloxy group, fluorenyloxy group, indenyloxy group, And a pyrenyloxy group and a perylenyloxy group.

"A linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent", represented by R ^{1 to} R ¹⁸ in the general formula (1), An optionally substituted cycloalkyl group having 5 to 10 carbon atoms ", an" optionally substituted linear or branched alkenyl group having 2 to 10 carbon atoms "," having a substituent A linear or branched alkyloxy group having 1 to 10 carbon atoms which may be substituted, a cycloalkyloxy group having 5 to 10 carbon atoms which may have a substituent, An acyl group having 1 to 10 carbon atoms which may have ", an" aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent ", and Good heterocyclic group having 2 to 20 carbon atoms "," condensation having 10 to 30 carbon atoms which may have a substituent " Specific examples of the “substituent” in the “cyclic aromatic group” or the “optionally substituted aryloxy group having 6 to 20 carbon atoms” include a deuterium atom, a trifluoromethyl group, a cyano group , A nitro group, a hydroxyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom;
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, isoheptyl group A straight-chain or branched alkyl group having 1 to 8 carbon atoms, such as n-octyl group, isooctyl group;
A cycloalkyl group having 5 to 10 carbon atoms such as a cyclopentyl group and a cyclohexyl group;
A linear or branched alkyloxy group having 1 to 8 carbon atoms such as a methoxy group, an ethoxy group and a propyloxy group;
A cycloalkyloxy group having 5 to 10 carbon atoms such as a cyclopentyloxy group and a cyclohexyloxy group;
A linear or branched alkoxy group having 1 to 8 carbon atoms such as a methoxy group, an ethoxy group and a propyloxy group;
A linear or branched alkenyl group having 2 to 6 carbon atoms such as a vinyl group, an allyl group, a 2-butenyl group, and a 1-hexenyl group;
Aralkyl groups such as benzyl, naphthylmethyl and phenethyl;
Arylalkoxy groups such as benzyloxy group and phenethyloxy group;
Aryloxy groups such as benzyloxy group and phenethyloxy group;
Phenoxy group, tolyloxy group, biphenylyloxy group, terphenylyloxy group, naphthyloxy group, anthryloxy group, phenanthryloxy group, fluorenyloxy group, indenyloxy group, pyrenyloxy group, perylenyloxy group, etc. An aryloxy group;
Aromatic hydrocarbon group such as phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group or 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, thianyl, quinolyl, isoquinolyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, benzoxazolyl, benzothiazolyl, quinoxalyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzofuranyl, dibenzo A heterocyclic group such as a thienyl group or a carbolinyl group;
Arylvinyl groups such as styryl groups and naphthylvinyl groups;
Acyl groups such as acetyl and benzoyl;
A dialkylamino group such as a dimethylamino group and a diethylamino group;
A disubstituted amino group substituted with an aromatic hydrocarbon group such as a diphenylamino group or a dinaphthylamino group or a condensed polycyclic aromatic group;
A diaralkylamino group such as a dibenzylamino group or a diphenethylamino group;
A disubstituted amino group substituted with a heterocyclic group such as a dipyridylamino group, a dithienylamino group, a dipiperidinylamino group;
A dialkenylamino group such as a diallylamino group;
Alkyl groups, aromatic hydrocarbon groups, condensed polycyclic aromatic groups, aralkyl groups, heterocyclic groups or disubstituted amino groups substituted with a substituent selected from an alkenyl group, and the like. May be further substituted by another substituent, and may be bonded to each other via a single bond, an oxygen atom or a sulfur atom to form a ring.

In the general formula (1), R ^{1 to} R ⁵ , R ^{6 to} R ¹⁰ , R ^{11 to} R ^14, and R ^{15 to} R ¹⁸ represent the same substituents as described above. May be bonded to each other via an oxygen atom or a sulfur atom to form a ring.

R ¹⁹ in the general formula ^(1), represented by R ²⁰ "linear or branched alkyl group optionally having 1 to 10 carbon atoms which may have a substituent" has "substituent A cycloalkyl group having 5 to 10 carbon atoms which may be substituted or a linear or branched alkenyl group having 2 to 10 carbon atoms which may have a substituent " Examples of the “straight or branched alkyl group having 10 carbon atoms”, “cycloalkyl group having 5 to 10 carbon atoms” or “linear or branched alkenyl group having 2 to 10 carbon atoms” include a general formula ( 1) a “linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent” represented by R ^{1 to} R ¹⁸ in “1), Good cycloalkyl group having 5 to 10 carbon atoms "or" having a substituent A "linear or branched alkyl group having 1 to 10 carbon atoms" in "a linear or branched alkenyl group having 2 to 10 carbon atoms", a "cycloalkyl group having 5 to 10 carbon atoms""Or" linear or branched alkenyl group having 2 to 10 carbon atoms ".

The “acyl group having 1 to 10 carbon atoms” in the “optionally substituted acyl group having 1 to 10 carbon atoms” represented by R ¹⁹ and R ²⁰ in the general formula (1) includes An “acyl group having 1 to 10 carbon atoms” in the “acyl group having 1 to 10 carbon atoms that may have a substituent” represented by R ^{1 to} R ¹⁸ in the general formula (1); The same can be given.

Formula (1) "aromatic hydrocarbon group having carbon atoms which may have a substituent having 6 to 20" to R ^19, R ²⁰ in expressed in, or may have a "substituent "Aromatic hydrocarbon group having 6 to 20 carbon atoms" in "heterocyclic group having 2 to 20 carbon atoms" or "condensed polycyclic aromatic group having 10 to 30 carbon atoms which may have a substituent""," Optionally substituted heterocyclic group having 2 to 20 carbon atoms "or" optionally substituted condensed polycyclic aromatic group having 10 to 30 carbon atoms " An "optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms" represented by R ^{1 to} R ¹⁸ in the general formula (1), In a "good heterocyclic group having 2 to 20 carbon atoms" or "a condensed polycyclic aromatic group having 10 to 30 carbon atoms which may have a substituent" An aromatic hydrocarbon group having 6 to 20 carbon atoms ", a" heterocyclic group having 2 to 20 carbon atoms which may have a substituent "or" a carbon atom having 10 carbon atoms which may have a substituent " To 30 condensed polycyclic aromatic groups ".

R ¹⁹ in the general formula ^(1), represented by R ²⁰ "linear or branched alkyl group optionally having 1 to 10 carbon atoms which may have a substituent" has "substituent An optionally substituted cycloalkyl group having 5 to 10 carbon atoms, an "optionally substituted linear or branched alkenyl group having 2 to 6 carbon atoms", "having a substituent An optionally substituted acyl group having 1 to 10 carbon atoms, an "optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms", and an "optionally substituted carbon group" As the “substituent” in the “heterocyclic group having 2 to 20 atoms” or the “optionally substituted condensed polycyclic aromatic group having 10 to 30 carbon atoms”, the general formula (1) R ¹ is represented by to R ¹⁸ 'have a substituent having 1 to 10 carbon atoms which may atoms straight-chain or branched alkyl Group "," optionally substituted cycloalkyl group having 5 to 10 carbon atoms "," optionally substituted linear or branched alkenyl having 2 to 10 carbon atoms " Group "," a linear or branched alkyloxy group having 1 to 10 carbon atoms which may have a substituent ", and" a cycloalkyl having 5 to 10 carbon atoms which may have a substituent ". An "alkyloxy group", an "optionally substituted acyl group having 1 to 10 carbon atoms", an "optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms", "Optionally substituted heterocyclic group having 2 to 20 carbon atoms", "optionally substituted fused polycyclic aromatic group having 10 to 30 carbon atoms" or "substituent The same as the “substituent” in the “aryloxy group having 6 to 20 carbon atoms that may have” You can gel, these substituents may further be substituted by other substituents, a single bond or via an oxygen atom or a sulfur atom bonded to each other to form a ring.

In the general formula (1), R ¹ and R ¹⁹ or R ⁵ and R ¹⁹ , R ⁶ and R ²⁰ or R ¹⁰ and R ²⁰ are directly or via a substituent, via a single bond, an oxygen atom or a sulfur atom. May combine with each other to form a ring.

In the general formula (1), R ^{1 to} R ⁵ and R ^{6 to} R ¹⁰ are preferably a halogen atom, and R ^{11 to} R ²⁰ are preferably a hydrogen atom.

  The general formula (1) is preferably represented by the general formula (2).

“A linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent” represented by R ^{1 to} R ¹⁸ in the general formula (2), “having a substituent A cycloalkyl group having 5 to 10 carbon atoms which may be substituted or a linear or branched alkenyl group having 2 to 10 carbon atoms which may have a substituent " Examples of the “10 linear or branched alkyl group”, “a cycloalkyl group having 5 to 10 carbon atoms” or “a linear or branched alkenyl group having 2 to 10 carbon atoms” are those represented by the general formula "A linear or branched alkyl group having 1 to 10 carbon atoms, which may have a substituent", represented by R ^{1 to} R ¹⁸ in (1), Or a cycloalkyl group having 5 to 10 carbon atoms "or" having a substituent "A linear or branched alkenyl group having 2 to 10 carbon atoms which may be substituted", "a linear or branched alkyl group having 1 to 10 carbon atoms", "cycloalkyl having 5 to 10 carbon atoms" Groups "or" linear or branched alkenyl groups having 2 to 10 carbon atoms ".

As a “linear or branched alkyloxy group having 1 to 10 carbon atoms” or a “cycloalkyloxy group having 5 to 10 carbon atoms” represented by R ^{1 to} R ¹⁸ in the general formula (2) Is a “linear or branched alkyloxy group having 1 to 10 carbon atoms” represented by R ^{1 to} R ¹⁸ in the general formula (1) or a “cycloalkyloxy group having 5 to 10 carbon atoms” ] Can be given.

The “acyl group having 1 to 10 carbon atoms” in the “optionally substituted acyl group having 1 to 10 carbon atoms” represented by R ^{1 to} R ¹⁸ in the general formula (2) includes Specifically, the “acyl group having 1 to 10 carbon atoms which may have a substituent” represented by “R ^{1 to} R ¹⁸ ” in the general formula (1) The same ones as the "acyl group" can be mentioned.

“Optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms” represented by R ^{1 to} R ¹⁸ in general formula (2), “optionally substituted substituent” "Aromatic hydrocarbon group having 6 to 20 carbon atoms" in "heterocyclic group having 2 to 20 carbon atoms" or "condensed polycyclic aromatic group having 10 to 30 carbon atoms which may have a substituent"", as the" heterocyclic group having 2 to 20 carbon atoms "or" condensed polycyclic aromatic group having a carbon number of 10 to 30 "is represented by ^R 1 ^{to R 18} in the general formula (1) "Optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms", "optionally substituted heterocyclic group having 2 to 20 carbon atoms" or "substituent "Aromatic hydrocarbon group having 6 to 20 carbon atoms" in "Condensed polycyclic aromatic group having 10 to 30 carbon atoms which may be possessed", "Charcoal May be mentioned the same ones as the atoms 2-20 heterocyclic group "or" condensed polycyclic aromatic group having a carbon number of 10 to 30 ".

The “aryloxy group” in the “optionally substituted aryloxy group having 6 to 20 carbon atoms” represented by R ^{1 to} R ¹⁸ in the general formula (2) includes the above-mentioned general formula ( The same as the “aryloxy group having 6 to 20 carbon atoms” in the “optionally substituted aryloxy group having 6 to 20 carbon atoms” represented by R ^{1 to} R ¹⁸ in 1) Can be given.

“A linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent” represented by R ^{1 to} R ¹⁸ in the general formula (2), “having a substituent An optionally substituted cycloalkyl group having 5 to 10 carbon atoms ", an" optionally substituted linear or branched alkenyl group having 2 to 10 carbon atoms "," having a substituent A linear or branched alkyloxy group having 1 to 10 carbon atoms which may be substituted, a cycloalkyloxy group having 5 to 10 carbon atoms which may have a substituent, An acyl group having 1 to 10 carbon atoms which may have ", an" aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent ", and Good heterocyclic group having 2 to 20 carbon atoms "," condensation having 10 to 30 carbon atoms which may have a substituent " As the "substituent" for ring aromatic group "or" optionally substituted aryloxy group having 6 to 20 carbon atoms ", Table in R ¹ to R ¹² in the general formula (1) "A linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent", "a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent""," A linear or branched alkenyl group having 2 to 10 carbon atoms which may have a substituent "," A linear chain having 1 to 10 carbon atoms which may have a substituent " Or a branched alkyloxy group "," a cycloalkyloxy group having 5 to 10 carbon atoms which may have a substituent "," an acyl having 1 to 10 carbon atoms which may have a substituent " Group "," an aromatic hydrocarbon having 6 to 20 carbon atoms which may have a substituent "",A" heterocyclic group having 2 to 20 carbon atoms which may have a substituent ", a" condensed polycyclic aromatic group having 10 to 30 carbon atoms which may have a substituent "or" The same as the "substituent" in the "aryloxy group having 6 to 20 carbon atoms which may have a substituent", and these substituents may be further substituted with another substituent. And may be bonded to each other via a single bond, an oxygen atom or a sulfur atom to form a ring.

In the general formula (2), R ^{1 to} R ⁵ , R ^{6 to} R ¹⁰ , R ^{11 to} R ^14, and R ^{15 to} R ¹⁸ represent the same substituents as described above. May be bonded to each other via an oxygen atom or a sulfur atom to form a ring.

R ¹⁹ in the general formula ^(2), represented by R ²⁰ "linear or branched alkyl group optionally having 1 to 10 carbon atoms which may have a substituent" has "substituent A cycloalkyl group having 5 to 10 carbon atoms which may be substituted or a linear or branched alkenyl group having 2 to 10 carbon atoms which may have a substituent " Examples of the “10 linear or branched alkyl group”, “a cycloalkyl group having 5 to 10 carbon atoms” or “a linear or branched alkenyl group having 2 to 10 carbon atoms” are those represented by the general formula "A linear or branched alkyl group having 1 to 10 carbon atoms, which may have a substituent", represented by R ^{1 to} R ¹⁸ in (1), A cycloalkyl group having 5 to 10 carbon atoms "or" having a substituent "A linear or branched alkyl group having 1 to 10 carbon atoms" in "a linear or branched alkenyl group having 2 to 10 carbon atoms", "cycloalkyl having 5 to 10 carbon atoms" Groups "or" linear or branched alkenyl groups having 2 to 10 carbon atoms ".

The “acyl group having 1 to 10 carbon atoms” in the “optionally substituted acyl group having 1 to 10 carbon atoms” represented by R ¹⁹ and R ²⁰ in the general formula (2) includes An “acyl group having 1 to 10 carbon atoms” in the “acyl group having 1 to 10 carbon atoms that may have a substituent” represented by R ^{1 to} R ¹⁸ in the general formula (1). The same can be given.

Formula (1) "aromatic hydrocarbon group having carbon atoms which may have a substituent having 6 to 20" to R ^19, R ²⁰ in expressed in, or may have a "substituent "Aromatic hydrocarbon group having 6 to 20 carbon atoms" in "heterocyclic group having 2 to 20 carbon atoms" or "condensed polycyclic aromatic group having 10 to 30 carbon atoms which may have a substituent""," Optionally substituted heterocyclic group having 2 to 20 carbon atoms "or" optionally substituted condensed polycyclic aromatic group having 10 to 30 carbon atoms " An "optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms" represented by R ^{1 to} R ¹⁸ in the general formula (1), A heterocyclic group having 2 to 20 carbon atoms or a condensed polycyclic aromatic group having 10 to 30 carbon atoms which may have a substituent. "An aromatic hydrocarbon group having 6 to 20 carbon atoms", a "heterocyclic group having 2 to 20 carbon atoms which may have a substituent", or a "carbon atom optionally having a substituent" The same ones as the "condensed polycyclic aromatic group of several 10 to 30" can be mentioned.

R ¹⁹ in the general formula ^(2), represented by R ²⁰ "linear or branched alkyl group optionally having 1 to 10 carbon atoms which may have a substituent" has "substituent An optionally substituted cycloalkyl group having 5 to 10 carbon atoms, an "optionally substituted linear or branched alkenyl group having 2 to 6 carbon atoms", "having a substituent An optionally substituted acyl group having 1 to 10 carbon atoms, an "optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms", and an "optionally substituted carbon group" As the “substituent” in the “heterocyclic group having 2 to 20 atoms” or the “optionally substituted condensed polycyclic aromatic group having 10 to 30 carbon atoms”, the above-mentioned general formula (1) a where the R ¹ is represented by to R ¹⁸ 'having 1 to 10 carbon atoms which may have a substituent group linear or branched A "alkyl group", a "cycloalkyl group having 5 to 10 carbon atoms which may have a substituent", a "linear or branched group having 2 to 10 carbon atoms which may have a substituent". Alkenyl group "," a linear or branched alkyloxy group having 1 to 10 carbon atoms which may have a substituent "," 5 to 10 carbon atoms optionally having a substituent " Cycloalkyloxy group "," optionally substituted acyl group having 1 to 10 carbon atoms "," optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms " A "heterocyclic group having 2 to 20 carbon atoms which may have a substituent", a "condensed polycyclic aromatic group having 10 to 30 carbon atoms which may have a substituent" or "substitution The same as the “substituent” in the “aryloxy group having 6 to 20 carbon atoms that may have a group” It can be mentioned, these substituents may further be substituted by other substituents, a single bond or via an oxygen atom or a sulfur atom bonded to each other to form a ring.

In the general formula (2), R ¹ and R ¹⁹ or R ⁵ and R ¹⁹ , R ⁶ and R ²⁰ or R ¹⁰ and R ²⁰ , R ¹² and R ¹⁹ or R ¹³ and R ¹⁹ , R ¹⁶ and R ²⁰ or R ¹⁷ and R ²⁰ may be bonded to each other via a single bond, an oxygen atom or a sulfur atom, directly or via a substituent, to form a ring.

In the general formula (2), R ^{1 to} R ⁵ and R ^{6 to} R ¹⁰ are preferably a halogen atom, and R ^{11 to} R ²⁰ are preferably a hydrogen atom.

  Specific examples of the hexafluoropropanebisbenzoic acid derivative represented by the general formula (1) used in the present invention are shown below, but the present invention is not limited to these compounds. In the following structural formulas, some of the hydrogen atoms and alkyl groups are omitted. Also, a mixture of two or more stereoisomers may be used.

  In the present invention, the charge control agent is preferably used after adjusting the volume average particle diameter in the range of 0.1 to 20 μm, and particularly preferably in the range of 0.1 to 10 μm. When the volume average particle diameter is smaller than 0.1 μm, the amount of the charge control agent appearing on the toner surface becomes extremely small, so that the intended charge control effect cannot be obtained. When the volume average particle diameter is larger than 20 μm, the charge control agent missing from the toner is reduced. It is not preferable because it increases and adverse effects such as in-flight contamination occur.

  When used in the polymerized toner of the present invention, the volume average particle diameter is preferably adjusted to 1.0 μm or less, and particularly preferably adjusted to a range of 0.01 to 1.0 μm. When the volume average particle size exceeds 1.0 μm, the particle size distribution of the finally obtained electrophotographic toner is widened, so that free particles are generated, which may cause a decrease in performance and reliability. is there. On the other hand, when the average particle size is in the above range, the above-mentioned disadvantages are not only eliminated, but uneven distribution between toners is reduced, dispersion in the toner is improved, and variations in performance and reliability are advantageously reduced.

  As a method for including a hexafluoropropanebisbenzoic acid derivative represented by the general formula (1), which is a charge control agent used in the present invention, in a toner, a binder resin is added together with a colorant and the like, kneaded, and pulverized. (Pulverized toner) or a method of adding a hexafluoropropanebisbenzoic acid derivative represented by the general formula (1) to a polymerizable monomer monomer and polymerizing to obtain a toner (polymerized toner). There is a method in which the toner particles are previously added to the inside of the toner particles (internal addition) and a method in which the toner particles are manufactured in advance and added to the surface of the toner particles (external addition). The preferable addition amount of the hexafluoropropanebisbenzoic acid derivative when internally added to the toner particles is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, based on 100 parts by mass of the binder resin. Used in parts by weight. When externally added to the toner particles, the amount is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 2 parts by mass, based on 100 parts by mass of the binder resin. It is also preferable that the toner particles be mechanochemically fixed to the surface of the toner particles.

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

  In the present invention, when the charge control agent and another charge control agent are used in combination, the amount of the charge is the hexafluoropropanebisbenzoic acid derivative represented by the general formula (1) per 100 parts by mass of the binder resin. The charge control agent other than the control agent is preferably 0.1 to 10 parts by mass.

  As the type of the binder resin used in the toner of the present invention, any known binder resin can be used. Styrene-based monomers, acrylate-based monomers, vinyl polymers such as methacrylate-based monomers, or copolymers of two or more of these monomers, such as polyester-based polymers, polyol resins, phenolic resins, Examples include silicone resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, terpene resin, coumarone indene resin, polycarbonate resin, and petroleum resin.

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

  Examples of the styrene monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-amylstyrene, and p-methylstyrene. -Tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chloro Styrene such as styrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, and derivatives thereof, and the like.

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

  Examples of the methacrylate monomer include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, and 2-ethyl methacrylate. Examples include methacrylic acid such as hexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate, and esters thereof.

  Examples of other monomers forming the vinyl polymer or copolymer include the following (1) to (18). (1) Monoolefins such as ethylene, propylene, butylene, and isobutylene; (2) Polyenes such as butadiene and isoprene; (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, methacrylic Lonitrile, Acri 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 and mesaconic acid; (11) maleic anhydride, citraconic acid Unsaturated dibasic anhydrides such as anhydride, itaconic anhydride and alkenyl succinic anhydride; (12) monomethyl maleate, monoethyl maleate, monobutyl maleate, monomethyl citraconic acid, 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 and mesaconic acid monomethyl ester; (13) dimethylmaleic acid, dimethyl maleic acid (14) α, β-unsaturated acids such as crotonic acid and cinnamic acid; (15) α, β-unsaturated acids such as crotonic anhydride and cinnamic anhydride Anhydrides (16) having a carboxyl group such as an anhydride of the α, β-unsaturated acid and a lower fatty acid, alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, an acid anhydride thereof, and a monoester thereof; Monomers; (17) acrylic acid or methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate; (18) 4- (1-hydroxy-1-methylbutyl) styrene; A model having a hydroxy group such as 4- (1-hydroxy-1-methylhexyl) styrene Nommer.

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

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

  Examples of the multifunctional crosslinking agent include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and those obtained by replacing the acrylate of the above compound with methacrylate, Lucyanurate and triallyl trimellitate are exemplified.

  These crosslinking agents can be used in an amount of preferably 0.01 to 10 parts by mass, and particularly preferably 0.03 to 5 parts by mass, based on 100 parts by mass of the other monomer components. Among these crosslinking monomers, aromatic divinyl compounds (particularly divinylbenzene is preferred), an aromatic group and one ether bond are preferably used from the viewpoint of fixability and offset resistance to the resin for toner. And diacrylate compounds linked by a bonding chain. Among these, a combination of monomers that results in a styrene-based copolymer or a styrene-acrylate-based copolymer is preferred.

  In the present invention, examples of the polymerization initiator used for producing a vinyl polymer or a copolymer include 2,2′-azobisisobutyronitrile and 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, cyclo Ketone peroxides such as xanone peroxide, 2,2-bis (tert-butylperoxy) butane, tert-butylhydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutylhydroper Oxide, 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-ethylhexylperoxydi -Carbonate, di-n-propylperoxydicarbonate, di-2-ethoxyethylperoxycarbonate, diethoxyisopropylperoxydicarbonate, 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-te Kisa Hydro terephthalate to t- butyl peroxy, etc. tert- butylperoxy azelate and the like.

  When the binder resin is a styrene-acrylate resin, the molecular weight distribution is determined by gel permeation chromatography (hereinafter, abbreviated as GPC) of a soluble component in tetrahydrofuran (hereinafter, abbreviated as THF) as a resin component. A resin having at least one peak in a region of ５50,000 (in terms of number average molecular weight) and at least one peak in a region of a molecular weight of 100,000 or more is preferable in terms of fixability, offset property, and storage stability. In addition, a binder resin in which a THF-soluble component has 50 to 90% of a component having a molecular weight distribution of 100,000 or less is also preferable. More preferably, it should have a main peak in the region of molecular weight of 5,000 to 30,000, most preferably in the region of 5,000 to 20,000.

  The acid value of a vinyl polymer whose binder resin is a styrene-acrylate resin is preferably 0.1 mgKOH / g to 100 mgKOH / g, more preferably 0.1 mgKOH / g to 70 mgKOH / g, and still more preferably 0.1 mgKOH / g to 50 mgKOH / g is preferred.

The monomers constituting the polyester-based polymer include the following.
Examples of the dihydric alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, Examples thereof include 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and diols obtained by polymerizing bisphenol A with a cyclic ether such as ethylene oxide or propylene oxide.

  It is preferable to use a trihydric or higher alcohol in order to crosslink the polyester resin. Examples of trihydric or higher polyhydric alcohols 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 and the like. Can be

  As the acid component forming the polyester polymer, phthalic acid, isophthalic acid, benzenedicarboxylic acids such as terephthalic acid or anhydrides thereof, succinic acid, adipic acid, sebacic acid, alkyldicarboxylic acids such as azelaic acid or the like. Unsaturated dibasic acids such as maleic acid, 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. The trivalent or higher polyvalent carboxylic acid component includes 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, empole trimer Examples include body acids, their anhydrides, and partially lower alkyl esters.

  When the binder resin is a polyester resin, at least one peak is present in the molecular weight distribution of the THF-soluble component of the resin component in a region having a molecular weight of 3,000 to 50,000 when the fixing property and the offset resistance of the toner are reduced. In addition, a binder resin in which the THF-soluble component contains 60 to 100% of a component having a molecular weight of 100,000 or less is also preferable. More preferably, at least one peak exists in a region having a molecular weight of 5,000 to 20,000. In the present invention, the molecular weight distribution of the binder resin is measured by GPC using THF as a solvent.

When the binder resin is a polyester resin, the acid value thereof is preferably 0.1 mgKOH / g to 100 mgKOH / g, more preferably 0.1 mgKOH / g to 70 mgKOH / g, and still more preferably 0.1 mgKOH / g. ~ 50 mgKOH / g is good.
Further, the hydroxyl value is preferably 30 mgKOH / g or less, more preferably 10 mgKOH / g to 25 mgKOH / g.

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

  As the amorphous polyester resin, those synthesized from a polycarboxylic acid component, preferably an aromatic polycarboxylic acid and a polyhydric alcohol component are suitably used. As the crystalline polyester resin, those synthesized from a divalent carboxylic acid component, preferably an aliphatic dicarboxylic acid and a dihydric alcohol component are suitably used.

As the binder resin that can be used in the toner of the present invention, a resin containing a monomer component capable of reacting with both of the vinyl polymer component and / or the polyester-based resin component can also be used. Among the monomers constituting the polyester resin component, those which can react with the vinyl polymer include, for example, unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid and itaconic acid, and 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.
When a polyester-based polymer, a vinyl polymer and another binder resin are used in combination, it is preferable that the total binder resin has a resin having an acid value of 0.1 to 50 mgKOH / g by 60% by mass or more.

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

  The binder resin of the toner and the composition containing the binder resin have a glass transition temperature (Tg) of preferably from 35 to 80 ° C, particularly preferably from 40 to 75 ° C, from the viewpoint of toner storability. If the Tg is lower than 35 ° C., the toner tends to deteriorate in a high-temperature atmosphere, and offset tends to occur during fixing. If the Tg exceeds 80 ° C., the fixability tends to decrease.

  In the polymerized toner of the present invention, 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 lower than 80 ° C., the toner and the image stability of the toner after fixing and during storage may be deteriorated. On the other hand, if the softening point exceeds 140 ° C., the low-temperature fixability may deteriorate.

  Examples of the magnetic substance usable in the present invention include (1) magnetic iron oxides such as magnetite, maghemite, and ferrite, and iron oxides containing other metal oxides. Or (2) metals such as iron, cobalt, nickel, or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, Alloys with metals such as tungsten and vanadium. (3) and mixtures thereof are used.

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 and the like. Or a combination of two or more. Particularly preferred magnetic materials are fine powders of iron tetroxide or γ-iron sesquioxide.

  In addition, 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, and gallium. Is raised. Preferred different elements are selected from magnesium, aluminum, silicon, phosphorus, or zirconium. The foreign element may be incorporated in the iron oxide crystal lattice, may be incorporated in 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 the salts of the different elements when the magnetic material is formed. In addition, by adjusting the pH after the formation of the magnetic particles, or by adjusting the pH by adding a salt of each element, the particles can be precipitated on the surface of the particles.

  The amount of the magnetic material to be used is 10 to 200 parts by mass, preferably 20 to 150 parts by mass, based on 100 parts by mass of the binder resin. These magnetic materials preferably have a number average particle size of 0.1 to 2 μm, more preferably 0.1 to 0.5 μm. The number average diameter can be determined by measuring a photograph enlarged by a transmission electron microscope with a digitizer or the like.

  As the magnetic properties of the magnetic material, those having a coercive force of 20 to 150 Oersted, a saturation magnetization of 50 to 200 emu / g, and a residual magnetization of 2 to 20 emu / g are preferable, respectively, when 10 K Oe is applied.

  The magnetic material can also be used as a coloring agent. In the case of a black toner, the colorant that can be used in the present invention 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, the following colorants may be used. Examples of the magenta colorant include a condensed azo compound, a diketopyrrolopyrrole compound, an anthraquinone compound, a quinacridone compound, a basic dye, a lake dye, a naphthol dye, a benzimidazolone compound, a thioindigo compound, and a perylene compound. Specifically, examples of the pigment-based magenta colorant 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. Butt Red 1, 2, 10, 13, 15, 23, 29, 35 and the like.
The pigment may be used alone, but it is more preferable to use the pigment and the pigment together to improve the sharpness from the viewpoint of the image quality of a full-color image.

  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 Red 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as Disperse Piolet 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. And basic dyes such as basic violett 1,3,7,10,14,15,21,25,26,27,28.

  As the cyan coloring agent, a copper phthalocyanine compound and its derivative, anthraquinone, and a basic dye lake compound 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. Acid Blue 45 or a copper phthalocyanine pigment obtained by substituting 1 to 5 phthalimidomethyl groups in a phthalocyanine skeleton.

  As the yellow colorant, a condensed azo compound, an isoindolinone compound, an anthraquinone compound, an azo metal complex, a methine compound, or an allylamide compound is used. Specifically, as the pigment for yellow, 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 orange pigments include red lead, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, benzidine orange G, induslen brilliant orange RK, and indanthrene brilliant orange GK. Examples of the violet pigment include manganese violet, fast violet B, and methyl violet lake. Examples of green pigments include chromium oxide, chrome green, pigment green, malachite green lake, and final yellow green G. Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.
The amount of the colorant to be used is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

  The toner of the present invention may be used as a two-component developer by mixing with a carrier. The carrier used in the present invention may be a normal carrier such as ferrite or magnetite or a resin-coated carrier.

  The resin-coated carrier is composed of carrier core particles and a coating material which is a resin for coating (coating) the surface of the carrier core particles, and the resin used for the coating material includes styrene-acrylate copolymer, styrene-methacrylic acid. Styrene-acrylate resins such as ester copolymers, acrylate resins such as acrylate copolymers and methacrylate copolymers, and fluorine-containing materials such as polytetrafluoroethylene, monochlorotrifluoroethylene polymer, and polyvinylidene fluoride Resins, silicone resins, polyester resins, polyamide resins, polyvinyl butyral, and amino acrylate resins are preferable, and other resins that can be used as a carrier (coating) material such as an ionomer resin and a polyphenylene sulfide resin may be used. These resin alone or may be used more.

  Further, 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 of coating at least the surface of the carrier core with a resin coating agent, a method of dissolving or suspending a resin in a solvent and attaching it to the applied carrier core, or a method of simply mixing in a powder state Can be applied. 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, based on the resin-coated carrier.

  Examples of the use of coating a magnetic material with a coating agent of a mixture of two or more kinds include (1) dimethyldichlorosilane and dimethylsilicon oil (mass ratio 1: 5) per 100 parts by mass of titanium oxide fine powder. A mixture treated with 12 parts by mass of the mixture and (2) a mixture treated with 20 parts by mass of a mixture of dimethyldichlorosilane and dimethylsilicone oil (mass ratio 1: 5) with respect to 100 parts by mass of the silica fine powder.

  Among the above resins, a styrene-methyl methacrylate copolymer, a mixture of a fluorinated resin and a styrene copolymer, or a silicone resin is preferably used, and a silicone resin is particularly preferred.

  Examples of the mixture of the fluorinated resin and the styrene-based copolymer include, for example, a mixture of polyvinylidene fluoride and styrene-methyl methacrylate copolymer, a mixture of polytetrafluoroethylene and styrene-methyl methacrylate copolymer, Vinylidene fluoride-tetrafluoroethylene copolymer (copolymer mass ratio 10: 90-90: 10), styrene-2-ethylhexyl acrylate copolymer (copolymer mass ratio 10: 90-90: 10), and styrene- A mixture with a 2-ethylhexyl acrylate-methyl methacrylate copolymer (copolymer mass ratio of 20 to 60: 5 to 30:10:50) can be used.

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

  As the magnetic material of the carrier core, an oxide such as ferrite, iron-rich ferrite, magnetite, and γ-iron oxide, a metal such as iron, cobalt, and nickel, or an alloy thereof can be used. The 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 are a copper-zinc-iron ferrite containing copper, zinc, and iron as main components, and a manganese-magnesium-iron ferrite containing manganese, magnesium, and iron as main components.

The resistance value of the carrier is preferably adjusted to 10 ⁶ 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 carrier may have a particle size of 4 to 200 μm, preferably 10 to 150 μm, more preferably 20 to 100 μm. In particular, the resin-coated carrier preferably has a 50% particle size of 20 to 70 μm.

  In the case of a two-component developer, the toner of the present invention is preferably used in an amount of 1 to 200 parts by mass, more preferably 2 to 50 parts by mass, based on 100 parts by mass of the carrier. Good to do.

  The toner of the present invention may further contain a wax. The wax used in the present invention includes the following. For example, aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax and sasol wax. Oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax. Or their block copolymers. Plant waxes such as candelilla wax, carnauba wax, wood wax, and jojoba wax. Animal wax like beeswax, lanolin, whale wax. Mineral waxes such as ozokerite, ceresin and petrolatum, and waxes mainly containing fatty acid esters such as montanic acid ester wax and caster wax. Fatty acid esters such as deoxidized carnauba wax are partially or entirely deoxidized.

  Examples of waxes further include saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or linear alkyl carboxylic acids having a further linear alkyl group. Unsaturated fatty acids such as pludonic acid, eleostearic acid, and vinalic acid. Saturated alcohols such as stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnaupyl alcohol, seryl alcohol, mesylyl alcohol, or long-chain alkyl alcohol. Polyhydric alcohols such as sorbitol. Fatty acid amides such as linoleic acid amide, olefinic acid amide and lauric acid amide. Saturated fatty acid bisamides such as methylenebiscapric amide, ethylenebislauric amide and hexamethylenebisstearic amide. Unsaturated fatty acid amides such as ethylenebisoleic acid amide, hexamethylenebisoleic acid amide, N, N'-dioleyladipamide and N, N'-dioleylsepacinamide; Aromatic bisamides such as m-xylene bisstearic acid amide and N, N'-distearylisophthalic acid amide. Fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate. A wax obtained by grafting an aliphatic hydrocarbon wax with a vinyl monomer such as styrene or acrylate. Partial ester compounds of fatty acids such as behenic acid monoglyceride and polyhydric alcohols. Examples thereof include methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

  The wax preferably used is a polyolefin obtained by radical polymerization of an olefin under high pressure. A polyolefin obtained by purifying a low-molecular-weight by-product obtained during polymerization of a high-molecular-weight polyolefin. Polyolefin polymerized under low pressure using a catalyst such as a Ziegler catalyst or a metallocene catalyst. Polyolefin polymerized using radiation, electromagnetic waves or light. A low molecular weight polyolefin obtained by thermally decomposing a high molecular weight polyolefin. Paraffin wax, microcrystalline wax, Fischer-Tropsch wax. Synthetic hydrocarbon wax synthesized by the Zintall method, the Hydrochol method, the Aage method, and the like. A synthetic wax having a compound having one carbon atom as a monomer; and a hydrocarbon wax having a functional group such as a hydroxyl group or a carboxyl group. A mixture of a hydrocarbon wax and a hydrocarbon wax having a functional group. Waxes obtained by graft-modifying these waxes with a vinyl monomer such as styrene, maleic ester, acrylate, methacrylate, and maleic anhydride are used as a base.

  In addition, these waxes may be those obtained by sharpening the molecular weight distribution using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a liquid crystal deposition method, a low molecular weight solid fatty acid, Those from which high molecular weight solid alcohols, low molecular weight solid compounds and other impurities have been removed are preferably used.

  The wax used in the present invention preferably has a melting point of 50 to 140 ° C, more preferably 70 to 120 ° C, in order to balance the fixing property and the offset resistance. If the temperature is lower than 50 ° C., the blocking resistance tends to decrease. If the temperature is higher than 140 ° C., the anti-offset effect is hardly exhibited.

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 simultaneously exhibited.
Examples of the type of the wax having a plasticizing action include a wax having a low melting point, a wax having a branched structure or a structure having a polar group in the molecular structure, and a wax having a releasing action having a high melting point. Examples of the structure of the wax and the molecule include those having a straight-chain structure and those having no functional group. Examples of use include a combination of two or more different waxes having a difference in melting point of 10 ° C to 100 ° C, and a combination of a polyolefin and a graft-modified polyolefin.

  When two kinds of waxes are selected, in the case of waxes having the same structure, a wax having a relatively low melting point exhibits a plasticizing effect, and a wax having a high melting point exhibits a releasing effect. At this time, when the difference in the melting points is 10 to 100 ° C., the functional separation is effectively exhibited. When the temperature is lower than 10 ° C., the function separation effect is hardly exhibited, and when the temperature is higher than 100 ° C., the function is hardly emphasized by the interaction. In this case, the melting point of at least one of the waxes is preferably from 70 to 120 ° C., more preferably from 70 to 100 ° C., and the function separation effect tends to be easily exhibited.

  In addition, waxes having a relatively branched structure, those having a polar group such as a functional group, and those modified with a component different from the main component exert a plasticizing action, and those having a more linear structure or a functional group. Non-polar and unmodified straight groups having no group exhibit a releasing effect. Preferred combinations include a combination of a polyethylene homopolymer or copolymer having ethylene as a main component and a polyolefin homopolymer or copolymer having an olefin other than ethylene as a main component; a combination of a polyolefin and a graft-modified polyolefin; an alcohol wax, a fatty acid wax or an ester wax. Combination of Fischer-Tropsch wax or polyolefin wax with paraffin wax or microcrystal wax; combination of Fischer-Tropsch wax and Porri olefin wax; combination of paraffin wax and microcrystal wax; carnauba wax, candelilla Wax, rice wax or montan wax and carbonized The combination of Motokei wax and the like.

  In any case, it is preferable that the endothermic peak observed in the DSC measurement of the toner has a peak top temperature of a maximum peak in a region of 70 to 110 ° C, more preferably a peak top temperature in a region of 70 to 110 ° C. Good to be. This makes it easier to balance toner storability and fixability.

  In the toner of the present invention, the total content of these waxes is preferably from 0.2 to 20 parts by mass, more preferably from 0.5 to 10 parts by mass, based on 100 parts by mass of the binder resin. Is effective.

  In the present invention, the melting point of the wax is defined as the temperature at the peak top of the maximum endothermic peak of the wax measured by DSC.

  In the present invention, in the DSC measurement of the wax or the toner, it is preferable to measure with a high-precision internal heating type input compensation type differential scanning calorimeter. The measuring method is performed according to ASTM D3418-82. As a DSC curve used in the present invention, a DSC curve measured when the temperature is raised at a temperature rate of 10 ° C./min after the temperature is raised and lowered once to obtain a previous history is used.

  A fluidity improver may be added to the toner of the present invention. The fluidity improver improves the fluidity (makes it more fluid) of the toner by adding it to the toner surface. For example, fluorinated resin powders 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 non-alumina, and 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 them, finely divided silica, finely divided titanium oxide and finely divided alumina are preferred, and silica treated with a silane coupling agent or a silicone oil is preferred. The particle diameter of the fluidity improver is preferably from 0.001 to 2 μm as an average primary particle diameter, particularly preferably from 0.002 to 0.2 μm.

  Preferred fine powder silica is fine powder produced by gas phase oxidation of a silicon halide-containing material, and is what is called dry silica or fumed silica.

  Commercially available silica fine powder produced by vapor phase oxidation of a silicon halide compound includes, for example, those commercially available under the following trade names. AEROSIL (manufactured by Nippon Aerosil Co., Ltd., the same applies hereinafter) -130, -300, -380, -TT600, -MOX170, -MOX80, -COK84: Ca-O-SiL (manufactured by CABOT Inc., hereinafter the same) -M-5 , -MS-7, -MS-75, -HS-5, -EH-5, Wacker HDK (manufactured by PACKER-CHEEMIEGMBH, hereinafter the same) -N20 V15, -N20E, -T30, -T40: D-CFineSilicica (Manufactured by Dow Corning KK): Franco1 (manufactured by Franci1 KK).

  Further, a treated silica fine powder obtained by subjecting a silica fine powder generated by vapor-phase oxidation of a silicon halide to a hydrophobic treatment is more preferable. In the treated silica fine powder, those obtained by treating the silica fine powder such that the degree of hydrophobicity measured by a methanol titration test preferably indicates a value of 30 to 80% are particularly preferable. Hydrophobicity is imparted by chemically or physically treating with an organosilicon compound or the like which reacts or physically adsorbs with silica fine powder. As a preferable method, a method in which silica fine powder generated by vapor-phase oxidation of a silicon halide compound is treated with an organic silicon compound is preferable.

  Examples of the organic silicon 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. And dimethylpolysiloxane containing 0 to 1 hydroxyl group bonded thereto. Further, a silicone oil such as dimethyl silicone oil is used. These are used alone or as a mixture of two or more.

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

  The toner of the present invention has, as other additives, protection of photoreceptors and carriers, improvement of cleaning properties, adjustment of thermal, electrical, and physical properties, resistance adjustment, softening point adjustment, and improvement of fixing rate. Various metal soaps, fluorine surfactants, dioctyl phthalate, tin oxide, zinc oxide, carbon black, antimony oxide, etc., and inorganic fine powders such as titanium oxide, aluminum oxide, alumina, etc. It can be added according to. Further, these inorganic fine powders may be hydrophobized if necessary. Also, lubricants such as polytetrafluoroethylene, zinc stearate, and polyvinylidene fluoride, abrasives such as cesium oxide, silicon carbide, and strontium titanate, an anti-caking agent, and white and black fine particles having a polarity opposite to that of toner particles are used. Can be used in small amounts 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 controlling the charge amount. It is also preferable to treat with a treating agent or various treating agents.

  In the present invention, the charge control agent together with the additives and the toner as described above is thoroughly mixed and stirred with a mixer such as a Henschel mixer, a ball mill, a Nauter mixer, a V-type mixer, a W-type mixer, a super mixer, and the like. By subjecting the particle surface to external addition uniformly, the intended toner for electrostatic charge development can also be obtained.

  The toner of the present invention is thermally stable, does not undergo a thermal change during the electrophotographic process, and can maintain stable charging characteristics. Further, since the toner is uniformly dispersed in any binder resin, the charge distribution of the fresh toner is very uniform. Therefore, in the toner of the present invention, even in the untransferred and collected toner (waste toner), almost no change is observed in the saturated triboelectric charge amount and the charge distribution as compared with the fresh toner. However, when reusing waste toner from the toner for developing an electrostatic image of the present invention, a polyester resin containing an aliphatic diol may be selected as a binder resin, or a metal-crosslinked styrene-acrylate copolymer may be used. By manufacturing the toner by using a binder resin and adding a large amount of polyolefin to the binder resin, the difference between the fresh toner and the waste toner can be further reduced.

  The toner of the present invention can be produced by a known production 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. A method (pulverization method) of kneading the mixture with a heating kneader such as a hot roll kneader, solidifying by cooling, pulverizing, and then classifying is preferable.

  Further, it can also be produced by a method in which the mixture is dissolved in a solvent, atomized by spraying, dried and classified. Further, a toner production method by a polymerization method in which a predetermined material is mixed with a monomer to form a binder resin to form an emulsion or a suspension and then polymerized to obtain a toner, a so-called core material and a shell material comprising a shell material The microcapsule toner can also be manufactured by a method in which a predetermined material is contained in a core material, a shell material, or both. Further, the toner of the present invention can be produced by sufficiently mixing a desired additive and toner particles with a mixer such as a Henschel mixer, if necessary.

  The method for producing the toner of the present invention by 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. The mixing can be performed using a known stirrer, for example, a Henschel mixer, a super mixer, a ball mill, or the like. The obtained mixture is hot-melt kneaded using a closed kneader or a single or twin screw extruder. After cooling the kneaded material, it is roughly pulverized using a crusher or a hammer mill, and finely pulverized using a pulverizer such as a jet mill or a high-speed rotor rotary mill. Furthermore, classification is performed to a predetermined particle size using an air classifier, for example, an inertia classification type elbow jet utilizing the Coanda effect, a cyclone (centrifugal) classification type microplex, a DS separator, or the like. Further, when an external additive is applied to the surface of the toner, the toner and the external additive are mixed by stirring with a high-speed stirrer such as a Henschel mixer or a super mixer.

  Further, the toner of the present invention can also be produced by a suspension polymerization method or an emulsion polymerization method. In the suspension polymerization method, 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 to form a simple substance. After preparing the monomer composition, a suitable stirrer or disperser such as a homomixer, a homogenizer, an atomizer, a microfluidizer, and the like are added to a continuous phase containing the monomer composition and the dispersion stabilizer, for example, an aqueous phase. Disperse using a liquid fluid nozzle, a gas-liquid fluid nozzle, an electric emulsifier or the like. Preferably, the agitation speed, temperature, and time are adjusted so that the droplets of the polymerizable monomer composition have a desired size of the toner particles, and granulation is performed. At the same time, a 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, such as 0.1 to 1.0 μm, although excellent in uniformity as compared with the particles obtained by the above suspension polymerization method. It is also possible to produce the particles by so-called seed polymerization in which a polymerizable monomer is added later to grow particles, or a method in which emulsified particles are united and fused to an appropriate average particle size.

  Since the production by these polymerization methods does not go through a pulverizing step, there is no need to impart brittleness to the toner particles, and furthermore, a large amount of a low softening point substance, which was difficult to use in the conventional pulverization method, can be used. The range of choices can be expanded. The release agent and the colorant, which are hydrophobic materials, are less likely 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 of the present invention by a polymerization method, characteristics such as image reproducibility, transferability, and color reproducibility can be further improved, and the particle diameter of the toner is reduced to correspond to minute dots. A toner having a sharp particle size distribution can be easily obtained.

  As the polymerizable monomer used when producing the toner of the present invention by a polymerization method, a vinyl polymerizable monomer capable of radical polymerization is used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

  Monofunctional polymerizable monomers include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butyl Styrene-based polymerizable monomers such as styrene, p-tert-butylstyrene, pn-hexylstyrene, p-phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl Acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, benzyl acrylate, dimethyl phosphate methyl acrylate, dibutyl phosphate ethyl acrylate Acrylate-based 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, vinyl hexyl ketone, such as vinyl ketones vinyl isopropyl ketone.

  The polymerization initiation used when the toner of the present invention is produced by the polymerization method may be a known initiator such as an organic peroxide. 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'-azobisisobutyi Sodium lonitrile sulfonate, ferrous sulfate or hydrogen peroxide.

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

  As these dispersants, commercially available ones may be used as they are, but in order to obtain finely dispersed particles having a uniform particle size, the inorganic compound can also be formed in a dispersion medium under high-speed stirring.

  The toner obtained by the polymerization method tends to have a smaller degree of unevenness of toner particles as compared with a toner obtained by a pulverization method without special treatment, and has an irregular shape. When the area is increased, the toner adhesion is increased, and as a result, contamination in the apparatus is reduced, and a higher image density and a higher quality image can be easily obtained.

  Also, in the case of a toner obtained by a 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 are passed through a hot air flow, or a mechanical impact method in which mechanical energy is applied to treat the toner particles. A method of reducing the degree of unevenness of the surface. Examples of effective devices for reducing the degree of unevenness include a mechano-fusion system (manufactured by Hosokawa Micron Co., Ltd.) to which a dry mechanochemical method is applied, an I-type jet mill, and a hybridizer (Nara Kikai) which is a mixing device having a rotor and a liner. Henschel mixer, which is a mixer having high-speed stirring blades, and the like.

  As one of the values indicating the degree of unevenness of the toner particles, it can be expressed by an average circularity. The average circularity (C) is the number of all particles obtained by calculating the circularity (Ci) by the following equation (2) and further summing the circularity of all the 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 measuring method, a dispersion in which about 5 mg of toner is dispersed in 10 ml of water in which about 0.1 mg of nonionic surfactant is dissolved is prepared, and the dispersion is irradiated with ultrasonic waves (20 kHz, 50 W) for 5 minutes. With the concentration of the dispersion at 5,000 to 20,000 particles / μL, the circularity distribution of particles having a circle equivalent diameter of 0.60 μm or more and less than 159.21 μm is measured using the flow type particle image measurement device.

  The value of the average circularity is preferably from 0.955 to 0.995, and more preferably, when the toner particles are adjusted to 0.960 to 0.985, a phenomenon that causes an increase in untransferred toner is small. Tend to be less likely to occur.

  In the case of the toner of the present invention, from the viewpoint of image quality and toner productivity, in the measurement using a laser type particle size distribution analyzer such as Micron Sizer (for example, manufactured by Seishin Enterprise Co., Ltd.), in the case of the pulverized toner, Is preferably in the range of 2 to 15 μm, more preferably in the range of 3 to 12 μm in terms of volume-based average particle size. When the average particle diameter is more than 15 μm, the resolution and sharpness tend to be dull. When the average particle diameter is less than 2 μm, the resolution is good, but the cost is high due to the deterioration of the yield during toner production. There is a tendency for health problems such as toner scattering and skin penetration inside the machine.

  On the other hand, in the case of a polymerized toner, it is preferably in the range of 3 to 9 μm, more preferably in the range of 4 to 8.5 μm, and particularly preferably in the range of 5 to 8 μm. When the volume average particle size is smaller than 4 μm, the toner fluidity is reduced, the chargeability of each particle is easily reduced, and the charge distribution is widened, so that fogging on the background and toner spilling from the developing device are likely to occur. . On the other hand, if it is smaller than 4 μm, the cleaning property may be extremely difficult. When the volume average particle size is larger than 9 μm, the resolution is reduced, and thus sufficient image quality cannot be obtained, and it may be difficult to satisfy the recent demand for high image quality.

  In the polymerized toner of the present invention, the particle size distribution measured by the following method is divided into a particle size range (channel). The volume average calculated from (D84% / D16%) 1/2 when the diameter is defined as volume D16%, and the particle diameter at which cumulative 50% is defined as volume D50% and the particle size at which cumulative 84% is defined as volume D84%. The particle size distribution index (GSDv) is preferably from 1.15 to 1.30, and more preferably from 1.15 to 1.25.

  Regarding the particle size distribution of the toner, in the case of the toner of the present invention, the particle content of 2 μm or less is desirably 10 to 90% on a number basis, for example, by particle size measurement using a Coulter counter (TA-II manufactured by Coulter Co., Ltd.). It is desirable that the content of particles having a size of 0.7 μm or more is 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 desirable.

In the case of the toner for electrostatic charge development of the present invention, the specific surface area of the toner is preferably from 1.2 to 5.0 m ² / g in a BET specific surface area measurement using nitrogen as a desorption gas. More preferably, it is 1.5 to 3.0 m ² / g. The specific surface area is measured, for example, by using a BET specific surface area measuring device (eg, FlowSorb II2300, manufactured by Shimadzu Corporation) at 50 ° C. for 30 minutes after desorbing the adsorbed gas on the toner surface, and quenching with liquid nitrogen. The gas is re-adsorbed, the temperature is raised again to 50 ° C., and the value is defined as the value obtained from the degassing amount at this time.

In the case of the toner of the present invention, 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 a magnetic toner although it depends on the type and content of the magnetic powder preferably 0.2 to 2.0 g / cm ^3.

In the case of the toner of the present invention, the true specific gravity of the non-magnetic toner is preferably 0.9 to 1.2 g / cm ³ , and in the case of the magnetic toner, it depends on the type and the content of the magnetic powder. 0.0 g / cm ³ is desirable. The true specific gravity of the toner is calculated as follows. 1.000 g of the toner is precisely weighed, placed in a tablet molding machine having a diameter of 10 mm, and compression-molded while applying a pressure of 200 kgf / cm ² under vacuum. The height of the columnar molded product is measured with a micrometer, and the true specific gravity is calculated from this.

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

In the present invention, SF-1 and SF-2 indicating the shape factor of the toner are, for example, a group of toner particles magnified 1000 times using an optical microscope equipped with a CCD camera (for example, BH-2 manufactured by Olympus Corporation). Is sampled so as to have about 30 pieces in one visual field, 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 about 1000 pieces of toner particles are obtained. The shape factor was calculated. The shape factor (SF-1) and the shape factor 2 (SF-2) are calculated by the following equations.
SF-1 = ((ML ² × π) / 4A) × 100
(In the formula, ML indicates the maximum length of a particle, and A indicates the projected area of one particle.)
SF-2 = (PM ² / 4Aπ) × 100
(Where PM is the perimeter of the particle and A is the projected area of one particle).

  SF-1 represents the distortion of the particles. The closer the particle is to a sphere, the closer to 100, and the longer the particle is, the larger the numerical value becomes. SF-2 represents the irregularities of the particles. The closer the particle is to a sphere, the closer to 100, and the more complex the shape of the particle, the larger the numerical value.

In the toner of the present invention, the volume resistivity of the toner is preferably 1 × 10 ¹² to 1 × 10 ¹⁶ Ω · cm in the case of a non-magnetic toner, and depends on the type and content of the magnetic powder in the case of a magnetic toner. However, it is desirable that the resistance is 1 × 10 ⁸ to 1 × 10 ¹⁶ Ω · cm. In this case, the toner volume resistivity is determined by compressing the toner particles to prepare a disk-shaped test piece having a diameter of 50 mm and a thickness of 2 mm, and setting it on a solid electrode (for example, SE-70 manufactured by Ando Electric Co., Ltd.). Using a high insulation resistance meter (for example, 4339A manufactured by Hewlett-Packard Co., Ltd.), it is defined as a value one hour after continuous application of a DC voltage of 100 V.

In the toner of the present invention, the dielectric loss tangent of the toner is desirably 1.0 × 10 ^{−3 to} 15.0 × 10 ^{−3 in} the case of a non-magnetic toner. ^{Depending on} the case, those having a density of 2 × 10 ⁻³ to 30 × 10 ⁻³ are desirable. In this case, the dielectric loss tangent of the toner is determined by compressing and molding the toner particles, producing a disk-shaped test piece having a diameter of 50 mm and a thickness of 2 mm, setting this on a solid electrode, and using an LCR meter (for example, Hewlett-Packard). The dielectric loss tangent value (Tan δ) obtained when measuring at a measurement frequency of 1 KHz and a peak-to-peak voltage of 0.1 KV using 4284A manufactured by Co., Ltd.) is defined.

  The toner of the present invention preferably has an Izod impact value of 0.1 to 30 kg · cm / cm. The Izod impact value of the toner in this case is measured by melting a toner particle to prepare a plate-shaped test piece, and measuring the plate in accordance with JIS K-7110 (hard plastic impact test method).

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

In the toner of the present invention, the melting start temperature of the toner is preferably from 80 to 180 ° C., and the 4 mm drop temperature is preferably from 90 to 220 ° C. In this case, the toner melting start temperature is determined by compressing the toner particles to prepare a cylindrical test piece having a diameter of 10 mm and a thickness of 20 mm, and using a heat melting property measuring apparatus such as a flow tester (for example, CFT manufactured by Shimadzu Corporation). -500C), and defined as a value at which melting starts when the load is measured at a load of 20 kgf / cm ² and the piston starts to descend. In a similar measurement, the temperature at which the piston has dropped 4 mm is defined as a 4 mm drop temperature.

  The glass of the present invention preferably has a glass transition temperature (Tg) of 35 to 80C, more preferably 40 to 75C. In this case, the glass transition temperature of the toner is measured using a differential thermal analysis (hereinafter abbreviated as DSC) apparatus, and after the temperature is raised at a certain temperature, rapidly cooled, and then re-heated, the peak value of the phase change appears. It is defined as what is required. When the Tg of the toner is lower than 35 ° C., the offset resistance and storage stability tend to decrease, and when it exceeds 80 ° C., the fixing strength of the image tends to decrease. It is preferable that the endothermic peak observed in the DSC measurement of the toner of the present invention has a peak top temperature of a maximum peak in a region of 70 to 120 ° C.

The toner of the present invention preferably has a melt viscosity of 1,000 to 50,000 poise, more preferably 1500 to 38,000 poise. In this case, the melt viscosity of the toner is determined by compression molding of toner particles to prepare a cylindrical test piece having a diameter of 10 mm and a thickness of 20 mm, and using a heat melting 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-dissolved residue of the toner of the present invention is preferably 0 to 30% by mass as a THF-insoluble component, 0 to 40% by mass as an ethyl acetate-insoluble component, and 0 to 30% by mass as a chloroform-insoluble component. The solvent-dissolved residue is obtained by uniformly dissolving or dispersing 1 g of the toner in 100 ml of each of THF, ethyl acetate and chloroform, filtering the solution / dispersion under pressure, drying the filtrate, and quantifying the solution. The value is calculated from the ratio of the insoluble matter in the organic solvent in the toner.

  The toner of the present invention can be used in a one-component developing system which is one of image forming methods. The one-component developing method is a method of developing a latent image by supplying a thinned toner to a latent image carrier. 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 abut respectively. This is performed using a device.

  The case where the toner of the present invention is applied to the two-component developing method will be specifically described. The two-component development system is a system that uses a toner and a carrier (having a role as a charge-imparting material and a toner conveying material), and uses the above-described magnetic material or glass beads for the carrier. The developer (toner and carrier) is agitated by the agitating member to generate a predetermined amount of electric charge, and is conveyed to a development site by a magnet roller or the like. On the magnet roller, the developer is held on the roller surface by the 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 with the rotation of the developing roller, and contacts the electrostatic latent image holding member or faces the electrostatic latent image holding member at a predetermined interval in a non-contact state, thereby developing and visualizing the latent image. In the case of development in a non-contact state, a driving force for causing the toner to fly in a space at a fixed interval can be obtained by generating a DC electric field between the developer and the latent image holding member. In order to develop an image, the present invention can be applied to a method of superimposing an alternating current.

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

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the following examples. In the present invention, all “parts” represent “parts by mass”.

The hexafluoropropanebisbenzoic acid derivative represented by the general formula (1) used in the present invention may be purified by column chromatography, adsorption and purification using silica gel, activated carbon and activated clay, recrystallization and crystallization using a solvent, and the like. Made by. The compound was identified by ¹ H-NMR analysis (nuclear magnetic resonance apparatus manufactured by JEOL Ltd., JNM-ECA-600). The melting point was measured at a heating rate of 2 ° C./min using a melting point measuring apparatus (B-545, manufactured by Buchi).

[Synthesis Example 1] Synthesis of (A-1) 2,2-bis (4-carboxyphenyl) hexafluoropropane (39.23 g) and tetrahydrofuran (900 mL) were added to Kolben, and the mixture was stirred and N-dimethylformamide was added. (1.75 g) and thionyl chloride (17.43 mL) were added, and the mixture was heated under reflux. After 2 hours, the reaction solution was cooled to room temperature, concentrated under reduced pressure, and diluted with 1,4-dioxane (250 mL). While adding 4-chloroaniline (30.62 g), 1,4-dioxane (650 mL) and triethylamine (24.29 g) and stirring, the diluent was slowly added dropwise. After stirring at room temperature for 4 hours, the mixture was poured into 1 L of 1.5 M hydrochloric acid to obtain a white precipitate. After being collected by filtration and the residue was repeatedly dispersed and washed with city water until pH 7, the residue was dispersed and washed with 500 mL of methanol. The solid was removed by filtration under reduced pressure, and dried under reduced pressure at 60 ° C. overnight to obtain a white solid (58.38 g, 95.5%). The result of the melting point measurement was 235.3 ° C.

The structure of the obtained white crystal was identified using NMR.
^The following 12 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).
δ (ppm) = 10.60-10.50 (2H), 8.10-7.90 (4H), 7.85-7.70 (4H), 7.55-7.30 (8H)

[Measurement method of charge amount]
Using a blow-off charge meter (TB-200, manufactured by Toshiba Chemical Co., Ltd.), the charge control agent or toner, which is the compound synthesized above, is charged, and then the initial charge and saturation charge (charge time) in each environment. 30 minutes). The conditions for measuring the blow-off charge amount are as follows.
Developer amount: 0.2000 g ± 0.005 g,
Blow time: 60 seconds,
N ₂ blow pressure: 0.2kgf / cm ² (silicon coat F96-150),
T / C = 4% (T / C: mass ratio of toner / carrier),
Ball mill rotation speed: 110 rpm.

  [Example 1]

[Measurement of Charge Amount of Compound Only as Charge Control Agent]
(A-1) obtained in Synthesis Example 1 was mixed and shaken at a ratio of 0.5 part to 100 parts of a silicon-coated ferrite carrier (F96-150, manufactured by Powder Tech). Then, (A-1) is charged. After charging, the saturation charge was measured in an atmosphere (NN) at a temperature of 25 ° C. and a humidity of 50%. Table 1 shows the results of the measurement of the charge amount of the compound as the charge control agent alone.

[Comparative Example 1]
For comparison, the saturation charge amount was measured in the same manner as in Example 1 using a commercially available charge control agent (TN-105: white salicylic acid complex, manufactured by Hodogaya Chemical Industry Co., Ltd.) as a comparative compound (B-1). Was. Table 1 shows the results of the measurement of the charge amount of the compound as the charge control agent alone.

  From the results of the triboelectric charging evaluation of the compounds alone in Table 1, the compound represented by the general formula (1) synthesized was a commercially available charge control agent (TN-105: white salicylic acid complex, manufactured by Hodogaya Chemical Industry Co., Ltd.) The negative chargeability greatly exceeded that of

  [Example 2]

[Preparation of Evaluation Toner]
91 parts of a polyester resin (manufactured by Mitsubishi Rayon Co., Ltd., trade name: FC-316, acid value: 9 mgKOH / g), 1 part of the compound (A-1) obtained in Synthesis Example 1, carbon black (manufactured by Mitsubishi Chemical Corporation) , Trade name MA-100) and 3 parts of low molecular weight polypropylene (trade name: Viscol 550P, manufactured by Sanyo Chemical Co., Ltd.) were melt-mixed by a heating and mixing device (twin-screw kneader) at 130 ° C. The cooled mixture was roughly pulverized by a hammer mill, finely pulverized by a jet mill, and classified to obtain a non-magnetic toner having a volume average particle diameter of 9 ± 0.5 μm.

[Measurement of charge amount of toner]
The obtained non-magnetic toner (toner for evaluation) is precisely weighed in a PP container at a ratio of 4 to 100 parts by mass (toner: carrier) with a non-concoat ferrite carrier (F-150 manufactured by Powdertech Co., Ltd.). After charging for 30 minutes using a ball mill under an atmosphere (NN) at a temperature of 25 ° C. and a humidity of 50%, the saturated charge amount is measured using a blow-off powder charge amount measuring device (TB-200, manufactured by Toshiba Chemical Corporation). It was measured. Table 2 shows the results of the saturation charge (μC / g) of the non-magnetic toner.

[Environmental stability measurement]
The obtained nonmagnetic toner (evaluation toner) was precisely weighed in a PP container at a ratio of 4 to 100 parts by mass (toner: carrier) with a non-coated ferrite carrier (F-150 manufactured by Powdertech Co., Ltd.), and the following measurement was performed. The sample was placed in a thermo-hygrostat (LH-30, manufactured by Nagano Kagaku Co., Ltd.) set in an environment for 12 hours or more. Next, it was charged for 30 minutes using a ball mill placed in a thermo-hygrostat. The sample taken out of the thermo-hygrostat was immediately measured for the charge amount by a blow-off powder charge amount measuring device (manufactured by Toshiba Chemical Corporation). The measurement environment of the environmental change stability was a low temperature and low humidity environment (LL) at a temperature of 10 ° C. and a humidity of 30% RH (relative humidity) and a high temperature and high humidity environment (HH) at a temperature of 35 ° C. and a humidity of 85% RH. The “saturated charge amount under the LL atmosphere” and the “saturated charge amount under the HH atmosphere” vary from the “saturated charge amount under the NN atmosphere” (L / N ratio and N / H ratio), and the “saturated charge amount under the LL atmosphere” The ratio (L / H ratio) between the "charge amount" and the "saturated charge amount in an HH atmosphere" was determined. Table 2 shows the results of the saturation charge (μC / g) and environmental stability of the non-magnetic toner.

[Comparative Example 2]
For comparison, a commercially available charge control agent (TN-105: white salicylic acid complex, manufactured by Hodogaya Chemical Industry Co., Ltd.) was used as a comparative compound (B-1), and the charge control agent was used in the same manner as in Example 2. The saturation chargeability of the compound evaluation toner was measured. Table 2 shows the results of the saturation charge (μC / g) and environmental stability of the non-magnetic toner.

  From the results of the triboelectrification evaluation in Table 2, the compound represented by the general formula (1) thus synthesized exhibited negative chargeability. The compound represented by the general formula (1) used in the present invention is a compound containing no metal and is excellent in safety to humans and the environment. Further, since it is almost white, it can be freely colored and used. Therefore, the compound represented by the general formula (1) used in the present invention is definitely useful as a charge control agent.

From the results of the environmental stability measurement shown in Table 2, the toner produced using the charge control agent of the compound of the present invention has better environmental stability than the toner produced using a commercially available white charge control agent. It was found to have
[Example 3]
[Measurement of charge amount of evaluation toner]
The non-magnetic toner containing the compound (A-1) obtained in Synthesis Example 1 was mixed with a silicon-coated ferrite carrier (F96-150 manufactured by Powdertech Co., Ltd.) in a ratio of 4 to 100 parts by mass (toner: carrier). After precisely weighing it in a PP container and charging it for 30 minutes using a ball mill in an atmosphere (NN) at a temperature of 25 ° C. and a humidity of 50%, a blow-off powder charge amount measuring device (TB-200, manufactured by Toshiba Chemical Corporation) ) Was used to measure the saturation charge. Table 3 shows the results of the saturation charge (μC / g) and environmental stability of the non-magnetic toner.

[Environmental stability measurement]
The obtained non-magnetic toner (toner for evaluation) was precisely weighed in a PP container at a ratio of 4 to 100 parts by mass (toner: carrier) with a silicon-coated ferrite carrier (F96-150 manufactured by Powdertech Co., Ltd.). The sample was placed in a thermo-hygrostat (LH-30, manufactured by Nagano Scientific Co., Ltd.) set for the measurement environment for 12 hours or more. Next, it was charged for 30 minutes using a ball mill placed in a thermo-hygrostat. The charge of the sample taken out of the thermo-hygrostat was immediately measured by a blow-off powder charge meter (manufactured by Toshiba Chemical Corporation). The measurement environment of the environmental change stability was a low temperature and low humidity environment (LL) at a temperature of 10 ° C. and a humidity of 30% RH (relative humidity) and a high temperature and high humidity environment (HH) at a temperature of 35 ° C. and a humidity of 85% RH. The “saturated charge amount under a low-temperature and low-humidity environment (LL)” and the “saturated charge amount under a high-temperature and high-humidity environment (HH)” vary from the “saturated charge amount under an NN atmosphere” (L / N ratio and N / H ratio). ), And the ratio (L / H ratio) of “saturated charge amount under low temperature and low humidity environment (LL)” to “saturated charge amount under high temperature and high humidity environment (HH)”. Table 3 shows the results of the saturation charge (μC / g) and environmental stability of the non-magnetic toner.

[Comparative Example 3]
For comparison, a commercially available charge control agent (TN-105: white salicylic acid complex, manufactured by Hodogaya Chemical Industry Co., Ltd.) was used as a comparative compound (B-1) to saturate the non-magnetic toner in the same manner as in Example 3. The chargeability and environmental stability were measured. Table 3 shows the results of the saturation charge (μC / g) and environmental stability of the non-magnetic toner.

  From the results of the triboelectric charging evaluation in Table 3, the synthesized compound represented by the general formula (1) showed negative charging properties. The compound represented by the general formula (1) used in the present invention is a compound containing no metal and is excellent in safety to humans and the environment. Further, since it is almost white, it can be freely colored and used. Therefore, the compound represented by the general formula (1) used in the present invention is definitely useful as a charge control agent.

  From the results of the environmental stability measurement shown in Table 3, the toner produced using the charge control agent of the present invention has excellent environmental stability as compared with a toner produced using a commercially available white charge control agent. It was found to have

  The compound represented by the general formula (1) according to the present invention has excellent charging performance. In addition, it does not contain heavy metals such as chromium compounds that are concerned about environmental issues, and is excellent in safety for humans and the environment. Further, the present invention can provide a toner which is suitable as a charge control agent for a color toner and is extremely useful as a pulverized toner or a polymerized toner.

Claims (4)

A charge control agent containing at least one hexafluoropropanebisbenzoic acid derivative represented by the following general formula (1) as an active ingredient.

[Wherein, R ^{1 to} R ¹⁸ may be the same or different from each other;
Hydrogen atom, deuterium atom, halogen atom, hydroxyl group, cyano group, trifluoromethyl group, nitro group,
A linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent,
A cycloalkyl group having 5 to 10 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 10 carbon atoms which may have a substituent,
A linear or branched alkyloxy group having 1 to 10 carbon atoms which may have a substituent,
A cycloalkyloxy group having 5 to 10 carbon atoms which may have a substituent,
An acyl group having 1-10 carbon atoms that may have a substituent,
An aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,
A heterocyclic group having 2 to 20 carbon atoms which may have a substituent,
A condensed polycyclic aromatic group having 10 to 30 carbon atoms which may have a substituent,
Or represents an aryloxy group having 6 to 20 carbon atoms which may have a substituent,
R ¹⁹ and R ²⁰ may be the same or different from each other;
Hydrogen atom, deuterium atom,
A linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent,
A cycloalkyl group having 5 to 10 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 10 carbon atoms which may have a substituent,
An acyl group having 1-10 carbon atoms that may have a substituent,
An aromatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent,
A heterocyclic group having 2 to 20 carbon atoms which may have a substituent,
Represents a condensed polycyclic aromatic group having 10 to 30 carbon atoms which may have a substituent, wherein R ^{1 to} R ⁵ , R ^{6 to} R ¹⁰ , R ^{11 to} R ¹⁴ and R ^{15 to} R ¹⁸ May be bonded to each other by adjacent groups to form a ring. ] The charge control agent according to claim 1, which comprises at least one kind of a 4,4-hexafluoropropanebisbenzoic acid derivative represented by the following general formula (2) as an active ingredient.

[Wherein, R ^{1 to} R ¹⁸ may be the same or different from each other;
Hydrogen atom, deuterium atom, halogen atom, hydroxyl group, cyano group, trifluoromethyl group, nitro group,
A linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent,
A cycloalkyl group having 5 to 10 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 10 carbon atoms which may have a substituent,
A linear or branched alkyloxy group having 1 to 10 carbon atoms which may have a substituent,
A cycloalkyloxy group having 5 to 10 carbon atoms which may have a substituent,
An acyl group having 1-10 carbon atoms that may have a substituent,
An aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,
A heterocyclic group having 2 to 20 carbon atoms which may have a substituent,
A condensed polycyclic aromatic group having 10 to 30 carbon atoms which may have a substituent,
Or represents an aryloxy group having 6 to 20 carbon atoms which may have a substituent,
R ¹⁹ and R ²⁰ may be the same or different from each other;
Hydrogen atom, deuterium atom,
A linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent,
A cycloalkyl group having 5 to 10 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 10 carbon atoms which may have a substituent,
An acyl group having 1-10 carbon atoms that may have a substituent,
An aromatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent,
A heterocyclic group having 6 to 20 carbon atoms which may have a substituent,
Here, R ^{1 to} R ⁵ , R ^{6 to} R ¹⁰ , R ^{11 to} R ^14, and R ^{15 to} R ¹⁸ represent a condensed polycyclic aromatic group having 9 to 20 carbon atoms which may have a substituent. May be bonded to each other by adjacent groups to form a ring. ]   A toner comprising: a charge control agent containing at least one of the hexafluoropropanebisbenzoic acid derivatives according to claim 1 as an active ingredient; a colorant; and a binder resin.   The polymerized toner according to claim 3.