JP5552581B1 - Charge control agent and toner - Google Patents

Abstract

式中、Ｒ_１〜Ｒ_４は、相互に同一でも異なってもよく、置換若しくは無置換の炭素原子数１〜２０の直鎖状若しくは分岐状のアルキル基等を示し、Ｒ_５〜Ｒ_８は、相互に同一でも異なってもよく、置換若しくは無置換の炭素原子数１〜２０の直鎖状若しくは分岐状のアルキル基等を示し、Ｘ_１〜Ｘ_４は、相互に同一でも異なってもよく、硫黄原子等を示す。
The present invention contains at least one compound represented by the following general formula (1) as an active ingredient, and 50 mol% or more of the above compounds are conformational isomers in a corn conformation or a partial cone conformation. A charge control agent that is a body is provided.
[Chemical 1]

In the formula, R _{1 to} R ₄ may be the same as or different from each other, and represent a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, and R _{5 to} R ₈ are , May be the same or different from each other, and represents a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, and X _{1 to} X ₄ may be the same or different from each other Represents a sulfur atom.

Description

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

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

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

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

  In the case of a color toner, a light, preferably colorless, charge control agent that does not affect the hue is required. These light-colored or colorless charge control agents include metal complex salts of hydroxybenzoic acid derivatives (for example, see Patent Documents 1 to 3) and aromatic dicarboxylic acid metal salt compounds (for example, Patent Document 4) for negatively chargeable toners. Reference), metal complex salts of anthranilic acid derivatives (for example, see Patent Documents 5 to 6), organoboron compounds (for example, see Patent Documents 7 to 8), biphenol compounds (for example, see Patent Document 9), calix (n) There are arene compounds (for example, see Patent Documents 10 to 15) and cyclic phenol sulfides (for example, see Patent Documents 16 to 19). Further, there are quaternary ammonium salt compounds (for example, see Patent Documents 20 to 22) for positively chargeable toners.

Japanese Patent Publication No. 55-042752 JP 61-069073 A JP 61-221756 A JP-A-57-111541 JP 61-141453 A JP 62-094856 A US Pat. No. 4,767,688 JP-A-1-3066861 JP 61-003149 A Japanese Patent No. 2568675 Japanese Patent No. 2899038 Japanese Patent No. 3359657 Japanese Patent No. 3313871 Japanese Patent No. 3325730 JP 2003-162100 A JP 2003-295522 A International Publication No. 2007/111346 International Publication No. 2007/119797 International Publication No. 2011-016519 Japanese Unexamined Patent Publication No. 57-119364 JP 58-009154 A JP 58-098742 A Japanese Patent Laid-Open No. 10-081680 International Publication No. 98/09959

J. et al. Org. Chem. 68, 2324 (2003)

  However, many of these charge control agents are complexes or salts made of heavy metals such as chromium and zinc, which are problematic in terms of waste regulations and are not necessarily safe. Also, it cannot be completely colorless, has a slow charge rising speed, has a problem in the environmental stability of the charge amount at high temperature and high humidity, has a low charge amount itself, has a lot of reversely charged toner, or has dispersibility or a compound However, there was no material having satisfactory performance as a charge control agent, such as inability to be applied to polymerized toner.

  An object of the present invention is to provide a charge control agent containing a specific conformer of a cyclic phenol sulfide as an active ingredient, and in view of the above circumstances, it is particularly useful for a color toner and further for a polymerized toner. Another object of the present invention is to provide a safe charge control agent which has a high charge amount and has particularly excellent charging characteristics with respect to environmental stability, and which has no problem in waste regulation. Another object of the present invention is to provide a negatively chargeable toner for developing an electrostatic image, particularly a negatively charged polymerized toner, which is particularly excellent in environmental stability using the charge control agent.

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

  That is, the present invention contains at least one compound represented by the following general formula (1) as an active ingredient, and 50 mol% or more of the above compound has a corn conformation or a partial cone conformation. Charge control agents that are conformers are provided.

In the general formula (1), R ₁ , R ₂ , R ₃ and R ₄ (hereinafter collectively referred to as “R _{1 to} R ₄ ”) may be the same as or different from each other, and may be substituted or unsubstituted. A linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group, and R ₅ , R ₆ , R ₇ and R ₈ (hereinafter collectively referred to as “R _{5 to} R ₈ ”) may be the same as or different from each other, and is a substituted or unsubstituted linear or branched alkyl having 1 to 20 carbon atoms. Group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group, X ₁ , X ₂ , X ₃ and X ₄ (hereinafter collectively “X _{1 to} X ₄ ”) May be the same as or different from each other. Shows a sulfinyl group or a sulfonyl group.

  The present invention also provides a toner containing one or more of the above charge control agents, a colorant, and a binder resin.

  The present invention further provides a polymerized toner containing one or more of the above charge control agents, a colorant, and a binder resin.

  The charge control agent according to the present invention has a high charge amount, a charging characteristic excellent in environmental stability, and an excellent characteristic that it is safe and has no problem with waste regulations. And can be suitably used for toner charge control. Therefore, the present invention contains at least one compound represented by the general formula (1) as an active ingredient, and 50 mol% or more of the compound has a corn conformation or a partial cone conformation. Use of a charge control agent, which is a isomer, for controlling charge of a toner, or containing at least one compound represented by the general formula (1) as an active ingredient, wherein 50 mol% or more of the compound is contained. It can also be said that the charge control agent which is a conformer of a cone type conformation or a partial cone type conformation is applied to toner charge control. The toner may be a polymerized toner.

  Furthermore, the present invention contains at least one compound represented by the above general formula (1) as an active ingredient, and 50 mol% or more of the above compound has a corn conformation or a partial cone conformation. It can also be said to be a toner charge control method including adding a charge control agent, which is a isomer, to the toner. Also in this case, the toner may be a polymerized toner.

  The charge control agent according to the present invention has a charge amount higher than that of a conventional charge control agent, and has a charging property that is particularly excellent in environmental stability. Since the charge control agent is completely colorless, it is optimal for color toners, particularly for polymerized toners. The charge control agent does not contain metals such as chromium and zinc, which are concerned about environmental problems, and is excellent in dispersibility and compound stability.

It is a schematic diagram in which the conformation of the compound represented by the general formula (1) is a corn type conformer. It is a schematic diagram in which the conformation of the compound represented by the general formula (1) is a partial cone type conformer. It is a schematic diagram which shows the conformer of the 1,2-alternate type | mold conformation of the compound represented by General formula (1). It is a schematic diagram which shows the conformer of the 1,3-alternate type | mold conformation of the compound represented by General formula (1).

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

  The charge control agent according to the present embodiment contains at least one compound represented by the general formula (1) as an active ingredient. The compound contains a conformer having a corn conformation or a partial cone conformation in a specific ratio. First, the compound represented by the general formula (1) will be described.

Examples of the “linear or branched alkyl group having 1 to 20 carbon atoms” represented by R _{1 to} R ₄ in the general formula (1) include a methyl group, an ethyl group, an n-propyl group, 2-propyl group, n-butyl group, sec-butyl group, 2-methylpropyl group, tert-butyl group, n-pentyl group, 1-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1 -Dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 1,4-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethyl Til, 1-ethyl-2-methyl-propyl, 1,1,2-trimethylpropyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, tert-octyl, 2- Ethylhexyl group, 3-methylheptyl group, n-nonyl group, isononyl group, 1-methyloctyl group, 2-ethylheptyl group, n-decyl group, 1-methylnonyl group, n-undecyl group, 1,1-dimethylnonyl Group, n-dodecyl group, n-tetradecyl group, n-heptadecyl group and n-octadecyl group.

The “linear or branched alkyl group having 1 to 20 carbon atoms” represented by R _{1 to} R ₄ in the general formula (1) may have a substituent. Examples of the “substituent” include halogen atoms such as fluorine atom and chlorine atom, cyano group, hydroxy group, nitro group, alkyl group, cycloalkyl group, alkyloxy group, dialkylamino group, acyl group, alkyloxycarbonyl group , An epoxyalkyl group, an aromatic hydrocarbon group, and a heterocyclic group. Specific examples of the “substituent” include fluorine atom, chlorine atom, cyano group, hydroxy group, nitro group, linear or branched alkyl group having 1 to 20 carbon atoms, cyclopentyl group, cyclohexyl group, carbon A linear or branched alkyloxy group having 1 to 6 atoms, a dialkylamino group substituted with a linear or branched alkyl group having 1 to 6 carbon atoms, and a linear chain having 1 to 20 carbon atoms Or branched acyl group, linear or branched alkyloxycarbonyl group having 1 to 20 carbon atoms, epoxyalkyl group having 1 to 6 carbon atoms, phenyl group, naphthyl group, anthryl group, fluorenyl group, Examples thereof include a styryl group, a pyridyl group, a pyridoindolyl group, a quinolyl group, and a benzothiazolyl group. These substituents may be further substituted with the substituents exemplified above.

Examples of the “aromatic hydrocarbon group” or “aromatic heterocyclic group” represented by R _{1 to} R ₄ in the general formula (1) include a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, and an anthryl group. , Phenanthryl, fluorenyl, indenyl, pyrenyl, triazyl, pyrimidyl, furyl, pyrrolyl, thienyl, quinolyl, isoquinolyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, benzoxazolyl And benzothiazolyl group, quinoxalyl group, benzoimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, naphthyridinyl group, phenanthrolinyl group and acridinyl group.

The “aromatic hydrocarbon group” or “aromatic heterocyclic group” represented by R _{1 to} R ₄ in the general formula (1) may have a substituent. Examples of the “substituent” include halogen atoms such as fluorine atom and chlorine atom, cyano group, hydroxy group, nitro group, alkyl group, cycloalkyl group, alkyloxy group, dialkylamino group, acyl group, alkyloxycarbonyl group , An epoxyalkyl group, an aromatic hydrocarbon group, and a heterocyclic group. Specific examples of the “substituent” include a fluorine atom, a chlorine atom, a cyano group, a hydroxyl group, a nitro group, a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclopentyl group, a cyclohexyl group, and a carbon atom. A linear or branched alkyloxy group having 1 to 6 carbon atoms, a dialkylamino group substituted with a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group, a naphthyl group, an anthryl group, fluorenyl Groups, styryl groups, pyridyl groups, pyridoindolyl groups, quinolyl groups, and benzothiazolyl groups. These substituents may be further substituted with the substituents exemplified above.

R _{1 to} R ₄ in the general formula (1) have an unsubstituted linear or branched alkyl group having 4 to 20 carbon atoms, an aromatic hydrocarbon group, or an aromatic heterocyclic group as a substituent. A linear or branched alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group is preferable. R _{1 to} R ₄ in the general formula (1) are each an unsubstituted linear or branched alkyl group having 10 to 20 carbon atoms, an aromatic hydrocarbon group, or an aromatic heterocyclic group. It is more preferably a linear or branched alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group. Further, R _{1 to} R ₄ in the general formula (1) are linear or branched alkyl groups having 1 to 4 carbon atoms having an aromatic hydrocarbon group or an aromatic heterocyclic group as a substituent. It is particularly preferred.

Examples of the “linear or branched alkyl group having 1 to 20 carbon atoms” represented by R _{5 to} R ₈ in the general formula (1) include, for example, a methyl group, an ethyl group, an n-propyl group, 2-propyl group, n-butyl group, sec-butyl group, 2-methylpropyl group, tert-butyl group, n-pentyl group, 1-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1 -Dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 1,4-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethyl Til, 1-ethyl-2-methyl-propyl, 1,1,2-trimethylpropyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, tert-octyl, 2- Ethylhexyl group, 3-methylheptyl group, n-nonyl group, isononyl group, 1-methyloctyl group, 2-ethylheptyl group, n-decyl group, 1-methylnonyl group, n-undecyl group, 1,1-dimethylnonyl Group, n-dodecyl group, n-tetradecyl group, n-heptadecyl group and n-octadecyl group.

The “linear or branched alkyl group having 1 to 20 carbon atoms” represented by R _{5 to} R ₈ in the general formula (1) may have a substituent. Examples of the “substituent” include halogen atoms such as fluorine atom and chlorine atom, cyano group, hydroxy group, nitro group, alkyl group, cycloalkyl group, alkyloxy group, dialkylamino group, acyl group, alkyloxycarbonyl group , An epoxyalkyl group, an aromatic hydrocarbon group, and a heterocyclic group. Specific examples of the “substituent” include a fluorine atom, a chlorine atom, a cyano group, a hydroxyl group, a nitro group, a cyclopentyl group, a cyclohexyl group, a linear or branched alkyloxy group having 1 to 6 carbon atoms, carbon A dialkylamino group substituted with a linear or branched alkyl group having 1 to 6 atoms, a linear or branched acyl group having 1 to 20 carbon atoms, or a straight chain having 1 to 20 carbon atoms Or branched alkyloxycarbonyl group, epoxyalkyl group having 1 to 6 carbon atoms, phenyl group, naphthyl group, anthryl group, fluorenyl group, styryl group, pyridyl group, pyridoindolyl group, quinolyl group, benzothiazolyl group be able to. These substituents may be further substituted with the substituents exemplified above.

Examples of the “aromatic hydrocarbon group” or “aromatic heterocyclic group” represented by R _{5 to} R ₈ in the general formula (1) include a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, and an anthryl group. , Phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, pyridyl group, triazyl group, pyrimidyl group, furyl group, pyrrolyl group, thienyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, Examples thereof include a benzoxazolyl group, a benzothiazolyl group, a quinoxalyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothienyl group, a naphthyridinyl group, a phenanthrolinyl group, and an acridinyl group.

The “aromatic hydrocarbon group” or “aromatic heterocyclic group” represented by R _{5 to} R ₈ in the general formula (1) may have a substituent. Examples of the “substituent” include halogen atoms such as fluorine atom and chlorine atom, cyano group, hydroxy group, nitro group, alkyl group, cycloalkyl group, alkyloxy group, dialkylamino group, acyl group, alkyloxycarbonyl group , An epoxyalkyl group, an aromatic hydrocarbon group, and a heterocyclic group. Specific examples of the “substituent” include fluorine atom, chlorine atom, cyano group, hydroxy group, nitro group, linear or branched alkyl group having 1 to 6 carbon atoms, cyclopentyl group, cyclohexyl group, carbon A linear or branched alkyloxy group having 1 to 6 atoms, a dialkylamino group substituted with a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group, a naphthyl group, an anthryl group, A fluorenyl group, a styryl group, a pyridyl group, a pyridoindolyl group, a quinolyl group, and a benzothiazolyl group can be exemplified. These substituents may be further substituted with the substituents exemplified above.

R _{5 to} R ₈ in the general formula (1) are substituted or unsubstituted linear or branched alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted It is preferably an unsubstituted aromatic heterocyclic group. R _{5 to} R ₈ in the general formula (1) are substituted or unsubstituted linear or branched alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon groups, or It is more preferably a substituted or unsubstituted aromatic heterocyclic group. In addition, R _{5 to} R ₈ in the general formula (1) are more preferably an unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, and an unsubstituted carbon atom having 1 to 10 carbon atoms. Particularly preferred are 6 straight-chain or branched alkyl groups.

X _{1 to} X ₄ in the general formula (1) can be a sulfur atom, a sulfinyl group or a sulfonyl group, preferably a sulfur atom, and all of X _{1 to} X ₄ are sulfur atoms. Is particularly preferred.

  The compound represented by the general formula (1) has a 16-membered ring structure including four benzene rings, which is a great barrier when the conformation changes. Therefore, the compound represented by the general formula (1) includes a corn type, a partial corn type, a 1,2-alternate type, and a 1,3-conformation whose conformation is represented by the following formulas (1A) to (1D). There are four types of conformational isomers (also referred to as rotamers) that are the alternate type (see, for example, Non-Patent Document 1).

A cone-type conformer is a three-dimensional structure in which all of R _{1 to} R ₄ are present in the same direction (for example, the upper side) with respect to a plane formed by a cyclic structure including X _{1 to} X _4. Has a conformation. The cone-type conformer can be represented by the general formula (1A) or the structural formula shown in FIG.

The partial cone type conformer has a direction different from the other three in only one of R _{1 to} R _{4 with} respect to the plane formed by the cyclic structure including X _{1 to} X ₄ (for example, R ₂ is on the lower side and the remaining R ₁ , R ₃ and R ₄ are on the upper side). The partial corn type conformer can be represented by the general formula (1B) or the structural formula shown in FIG.

The 1,2-alternate type conformer has a direction in which two adjacent R _{1 to} R ₄ are different from the other two relative to the plane formed by the cyclic structure including X _{1 to} X ₄ ( For example, it has a conformation in which R ₂ and R ₃ are on the lower side and R ₁ and R ₄ are on the upper side. The 1,2-alternate type conformer can be represented by the general formula (1C) or the structural formula shown in FIG.

The 1,3-alternate type conformer has a direction in which two of R _{1 to} R ₄ are different from the other two with respect to a plane formed by a cyclic structure including X _{1 to} X _4. (For example, R ₂ and R ₄ are on the lower side, and R ₁ and R ₃ are on the upper side). The 1,3-alternate type conformer can be represented by the general formula (1D) or the structural formula shown in FIG.

  In the compound represented by the general formula (1), the inventors of the present invention have a conformation of a cone type conformation and a partial cone type conformation with respect to the total amount of the above-mentioned four kinds of conformers. It has been found that when the total amount of the isomers is 50 mol% or more, the charge control agent, toner and polymerized toner containing the above compound are excellent in terms of charging characteristics and environmental stability.

In the case X ₁ to X ₄ is a sulfinyl group, causing additional stereoisomers resulting from the sulfinyl group. However, since the conformation with respect to the 16-membered ring structure containing four benzene rings is important for the compound according to this embodiment, it is not necessary to distinguish and judge the stereoisomers derived from the stereochemistry of the sulfinyl group.

  The compound represented by the general formula (1) has four types of conformations: a corn conformation, a partial cone conformation, a 1,2-alternate conformation, and a 1,3-alternate conformation. Conformational isomers exist. In this embodiment, it is preferable that 50 mol% or more of the compound represented by the general formula (1) has a corn conformation or a partial cone conformation. The ratio of the compound represented by the general formula (1) existing as a corn type conformation or a partial cone type conformation is 55 mol% or more, 60 mol% or more, 65 mol% or more, 70 mol% or more. 75 mol% or more, 80 mol% or more, 85 mol% or more, or 90 mol% or more. The upper limit of the ratio is not particularly limited, but may be 100%, for example. As a method for calculating the content (mol%) of the compound represented by the general formula (1) which is a corn type conformation or a partial cone type conformation, for example, a high performance liquid chromatograph (hereinafter abbreviated as HPLC) is used. ) To calculate from the peak area.

一般式（２）中、Ｒ_１〜Ｒ_４は、相互に同一でも異なってもよく、無置換の炭素原子数１０〜２０の直鎖状若しくは分岐状のアルキル基、芳香族炭化水素基若しくは芳香族複素環基を置換基として有する炭素原子数１〜４の直鎖状若しくは分岐状のアルキル基、置換若しくは無置換の芳香族炭化水素基、又は置換若しくは無置換の芳香族複素環基を示し、Ｒ_５〜Ｒ_８は、相互に同一でも異なってもよく、置換若しくは無置換の炭素原子数１〜１０の直鎖状若しくは分岐状のアルキル基、置換若しくは無置換の芳香族炭化水素基、又は置換若しくは無置換の芳香族複素環基を示し、Ｘ_１〜Ｘ_４のすべては、硫黄原子を示す。The compound represented by the general formula (1) may be a compound represented by the following general formula (2).

In the general formula (2), R _{1 to} R ₄ may be the same or different from each other, and are an unsubstituted linear or branched alkyl group having 10 to 20 carbon atoms, an aromatic hydrocarbon group or an aromatic group. A linear or branched alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group having an aromatic heterocyclic group as a substituent , R _{5 to} R ₈ may be the same as or different from each other, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or indicate the unsubstituted aromatic heterocyclic groups, all of X ₁ to X _4, represents a sulfur atom.

一般式（３）中、Ｒ_１〜Ｒ_４は、相互に同一でも異なってもよく、芳香族炭化水素基又は芳香族複素環基を置換基として有する炭素原子数１〜４の直鎖状又は分岐状のアルキル基を示し、Ｒ_５〜Ｒ_８は、相互に同一でも異なってもよく、無置換の炭素原子数１〜１０の直鎖状又は分岐状のアルキル基を示し、Ｘ_１〜Ｘ_４のすべては、硫黄原子を示す。The compound represented by the general formula (1) may be a compound represented by the following general formula (3).

In General Formula (3), R _{1 to} R ₄ may be the same as or different from each other, and are each a straight chain having 1 to 4 carbon atoms having an aromatic hydrocarbon group or an aromatic heterocyclic group as a substituent, or A branched alkyl group, R _{5 to} R ₈ may be the same as or different from each other, and represent an unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, and X _{1 to} X All _four indicate sulfur atoms.

The corn type or partial corn type conformer of the compound represented by the general formula (1) according to this embodiment is obtained by converting a corresponding phenol derivative into a known cyclization reaction, or an oxidation reaction following the cyclization reaction ( For example, the corresponding cyclic phenol sulfide precursor can be produced by carrying out a known O-alkylation reaction or the like (see, for example, non-patent documents). Reference 1). In addition, the group represented by R _{5 to} R ₈ is subjected to a cross-coupling reaction such as Suzuki coupling with a corresponding cyclic phenol sulfide precursor substituted with a halogen atom such as an iodine atom or a bromine atom. Desired groups can be introduced.

The compound represented by the general formula (1) according to the present embodiment can be produced, for example, by the method described in Non-Patent Document 1. By using a compound in which R _{1 to} R ₄ corresponding to the compound represented by the general formula (1) are all hydrogen atoms, a desired compound can be selectively produced by appropriately selecting reaction conditions. . For example, refluxing using sodium hydride and benzyl bromide in a 9: 1 (v / v) mixed solution of tetrahydrofuran (hereinafter also abbreviated as THF) and N, N-dimethylformamide (hereinafter also referred to as DMF). Under the reaction for 2 hours below, a conformer having a corn type conformation can be obtained as a main product. Further, through the following three steps (A) to (C), a conformer having a partial cone type conformation can be obtained as a main product.
(A) reacting in acetone with sodium carbonate and benzyl bromide under reflux;
(B) reacting at 0 ° C. with sodium hydride and benzyl bromide in DMF,
(C) The process made to react under reflux using cesium carbonate and benzyl bromide in acetone.

  The four conformers of the compound represented by the general formula (1) can be separated from various conformers by, for example, HPLC. Therefore, the separated various conformers are mixed at a desired ratio, and 50 mol% or more of the compound represented by the general formula (1) is conformation isomer of corn type conformation or partial cone type conformation. It is also possible to adjust to form a body and apply it to the charge control agent.

  The charge control agent according to the present embodiment is excellent in charge control characteristics, environmental resistance, and durability, and has no fog, good image density, dot reproducibility, and fine line reproducibility when used in a polymerized toner. Can be obtained.

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

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

  As a method of adding the charge control agent according to the present embodiment to the toner, there are a method of previously adding the toner inside the toner particles and a method of previously manufacturing the toner particles and adding them to the surface of the toner particles. As a method of adding the toner particles to the inside, for example, the charge control agent is added to a binder resin together with a colorant and the like, kneaded and then pulverized (pulverized toner), or a polymerizable monomer monomer. Examples thereof include a method (polymerized toner) in which the charge control agent is added and polymerized to obtain a toner. When added inside the toner particles, the amount of the charge control agent added may be 0.1 to 10 parts by mass of the compound represented by the general formula (1) with respect to 100 parts by mass of the binder resin. Preferably, it is 0.2-5 mass parts. On the other hand, when added to the surface of the toner particles, the charge control agent is added in an amount of 0.01 to 5 parts by mass of the compound represented by the general formula (1) with respect to 100 parts by mass of the binder resin. It is preferable to add so that it may become 0.01-2 mass parts, and it is more preferable. Further, it is preferable that the toner particles are fixed mechanochemically.

  Further, the charge control agent according to the present embodiment can be used in combination with other known negatively chargeable charge control agents. Preferred charge control agents to be used in combination include azo iron complexes or complex salts, azo chromium complexes or complex salts, azo manganese complexes or complex salts, azo cobalt complexes or complex salts, azo zirconium complexes or complex salts, and chromium complexes of carboxylic acid derivatives. Or a complex salt, a zinc complex or complex salt of a carboxylic acid derivative, an aluminum complex or complex salt of a carboxylic acid derivative, and a zirconium complex or complex salt of a carboxylic acid derivative. The carboxylic acid derivative is preferably an aromatic hydroxycarboxylic acid, more preferably 3,5-di-tert-butylsalicylic acid. Furthermore, a boron complex or complex salt, a negatively chargeable resin type charge control agent and the like can be mentioned.

  When the charge control agent according to this embodiment is used in combination with another charge control agent, the addition amount of the charge control agent other than the charge control agent according to this embodiment is 0. 1-10 mass parts is preferable.

  Any known binder resin may be used as the binder resin used in the toner of the exemplary embodiment. Examples of the binder resin include vinyl polymers such as styrene monomers, acrylate monomers and methacrylate monomers, or copolymers composed of two or more of these monomers; Polyol resin; silicone resin; polyurethane resin; polyamide resin; furan resin; epoxy resin; xylene resin; terpene resin; The copolymer produced by adding a crosslinking agent may be used.

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

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

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

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

  The following (1) to (18) may be used as other monomers that form a copolymer with a vinyl polymer. (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 methyl vinyl ether, ethyl vinyl ether and isobutyl vinyl ether; (6) Methyl vinyl ketone, hexyl vinyl ketone and methyl isopropenyl ketone. (7) N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone; (8) vinylnaphthalenes; (9) acrylonitrile, methacrylonitrile, Acrylamide, etc. (10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; (11) maleic anhydride, citraconic anhydride, Unsaturated dibasic acid anhydrides such as itaconic acid anhydride and alkenyl succinic acid anhydride; (12) maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester Unsaturated dibasic acid monoesters such as citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester; (13) dimethylmaleic acid, dimethylfumaric acid, etc. Saturated (14) α, β-unsaturated acids such as crotonic acid and cinnamic acid; (15) α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride; (16) Monomers having a carboxy group such as mixed acid anhydrides of 留, 硫 -unsaturated acids and lower fatty acids, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, these acid anhydrides and monoesters thereof; (17) Acrylic acid or methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; (18) 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1- Monomers having a hydroxy group such as hydroxy-1-methylhexyl) styrene.

  In the toner according to the exemplary embodiment, the vinyl polymer of the binder resin or the copolymer thereof may have a crosslinked structure that is crosslinked with a crosslinking agent having two or more vinyl groups.

  Examples of the crosslinking agent having two vinyl groups include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1, Diacrylate compounds of alkylene diols such as 5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate or the corresponding dimethacrylate compounds; diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol Oxides such as diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate Diacrylate compounds or the corresponding methacrylate compounds alkylene diol and the like.

  Moreover, you may use the diacrylate compound of the diol which has an aromatic group or an ether bond, or a corresponding dimethacrylate compound. For example, polyester type diacrylates (trade name: MANDA (manufactured by Nippon Kayaku Co., Ltd.)) can be mentioned.

  Polyfunctional crosslinking agents include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, polyol ester acrylate or the corresponding methacrylate; triallyl cyanurate, tri Examples include allyl esters or amides such as allyl trimellitate.

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

  In this embodiment, as a polymerization initiator used for manufacture of a vinyl polymer or a copolymer, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate 1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo- 2 ', 4'-dimethyl-4'-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide Sides, ketone peroxides such as cyclohexanone peroxide, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetra Methylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide, decanoyl Peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl Syl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, diethoxyisopropyl peroxydicarbonate, bis (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclo Hexylsulfonyl peroxide, tert-butylperoxyacetate, tert-butylperoxyisobutyrate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxylaurate, tert-butylperoxybenzoate To tert-butyl peroxyisopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, isoamyl peroxy-2-ethyl Sanoeto, di -tert- butyl peroxy the hexa hydro terephthalate, etc. tert- butylperoxy azelate and the like.

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

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

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

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

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

  In the case where the binder resin is a polyester-based resin, at least one peak is present in the molecular weight region of 3,000 to 50,000 in the molecular weight distribution of the THF soluble component of the resin component, and the toner fixing property and offset resistance property are reduced. In terms of the THF soluble content, a binder resin in which a component having a molecular weight of 100,000 or less is 60% to 100% is also preferable. More preferably, at least one peak exists in a region having a molecular weight of 5,000 to 20,000.

  In this embodiment, the molecular weight distribution of the binder resin is measured by GPC using THF as a solvent. The said molecular weight is the number average molecular weight of standard polystyrene conversion measured with the HLC-8220GPC apparatus (made by Tosoh Corporation), for example.

  When the binder resin is a polyester resin, the acid value is preferably 0.1 mgKOH / g to 100 mgKOH / g, more preferably 0.1 mgKOH / g to 70 mgKOH / g, and 0.1 mgKOH / g. More preferably, it is -50 mgKOH / g. In addition, an acid value means the mass of potassium hydroxide required in order to neutralize the free fatty acid in 1 g of binder resin, and is measured based on JIS K-0070.

  The hydroxyl value is preferably 30 mgKOH / g or less, and more preferably 10 mgKOH / g to 25 mgKOH / g. The hydroxyl value means the mass of potassium hydroxide required to neutralize acetic acid produced when acetylating the hydroxyl group in 1 g of the binder resin with acetic anhydride, and conforms to JIS K-0070. Measured.

  In the present embodiment, two or more of an amorphous polyester resin and a crystalline polyester resin may be mixed and used. In this case, it is preferable to select materials taking into consideration the compatibility of the respective resins.

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

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

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

  Moreover, when using together a polyester polymer, a vinyl polymer, and another binder resin, what has 60 mass% or more of resin whose acid value of the whole binder resin is 0.1 mgKOH / g-50 mgKOH / g. preferable.

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

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

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

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

Specific examples of the magnetic material include Fe ₃ O ₄ , γ-Fe ₂ O ₃ , ZnFe ₂ O ₄ , Y ₃ Fe ₅ O ₁₂ , CdFe ₂ O ₄ , Gd ₃ Fe ₅ O ₁₂ , CuFe ₂ O ₄ , PbFe ₁₂ O, NiFe ₂ O ₄ , NdFe ₂ O, BaFe ₁₂ O ₁₉ , MgFe ₂ O ₄ , MnFe ₂ O ₄ , LaFeO ₃ , iron powder, cobalt powder, nickel powder, etc. Or two or more types can be used in combination. A particularly suitable magnetic substance is a fine powder of triiron tetroxide or γ-iron sesquioxide.

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

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

  The usage-amount of the said magnetic body can be 10-200 mass parts of magnetic bodies with respect to 100 mass parts of binder resin, and it is preferable to set it as 20-150 mass parts. The number average particle diameter of these magnetic materials is preferably 0.1 μm to 2 μm, and more preferably 0.1 μm to 0.5 μm. The number average particle diameter can be obtained by measuring a photograph taken with a transmission electron microscope with a digitizer or the like.

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

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

When used as a color toner, examples of the colorant include the following. As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dyes, lake dyes, naphthol dyes, benzimidazolone compounds, thioindigo compounds, and perylene compounds can be used. Specifically, examples of pigment-based magenta colorants include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207, 209, C.I. I. Pigment violet 19, C.I. I. Vat red 1, 2, 10, 13, 15, 23, 29, 35 and the like.
Although the above pigment may be used alone, it is more preferable from the viewpoint of the image quality of a full color image to improve the sharpness by using a dye and a pigment together.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Examples of waxes include saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or linear alkyl carboxylic acids having a linear alkyl group; brassic acid, eleostearic acid, parinaric acid, etc. Unsaturated fatty acids; Stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnauvir alcohol, seryl alcohol, melyl alcohol, saturated alcohols such as long chain alkyl alcohols; polyhydric alcohols such as sorbitol; nolic acid amide, oleic acid amide, Fatty acid amides such as lauric acid amide; saturated fatty acid bisamides such as methylene biscapric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis olein Unsaturated fatty acid amides such as amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide; m-xylene bisstearic acid amide, N, N′-distearyl isophthalic acid amide, etc. Aromatic bisamides; Fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate; Wax grafted onto aliphatic hydrocarbon waxes using vinyl monomers such as styrene or acrylate; Examples include partial ester compounds of fatty acids such as acid monoglycerides and polyhydric alcohols; methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The fluidity improver has a number average particle size of 5 nm to 100 nm, more preferably 5 nm to 50 nm. Specific surface area by nitrogen adsorption of preferably not less than ^{30 m} 2 / g as measured by BET ^method, that of 60m ² / g~400m 2 / g is more preferable. The surface-treated fine powder is preferably not less than ^{20 m} 2 / g, and more preferably, especially ^{40m 2} / ^g~300m 2 / g. The application amount of these fine powders is preferably 0.03 to 8 parts by mass with respect to 100 parts by mass of the toner particles.

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

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

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

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

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

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

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

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

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

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

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

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

  Monofunctional polymerizable monomers include styrene, α-methyl styrene, β-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene, pn-butyl. Styrenic polymerizable monomers such as styrene, p-tert-butylstyrene, pn-hexylstyrene, p-phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl Acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, benzyl acrylate, dimethyl phosphate methyl acrylate, dibutyl phosphate ethyl acetate Acrylate polymerizable monomers such as relate 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 ethers such as vinyl methyl ether and vinyl isobutyl ether Vinyl methyl ketone, vinyl hexyl ketone, vinyl ketones such as vinyl isopropyl ketone.

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

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

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

  The toner obtained by the above polymerization method tends to have less irregularities on the toner particles than the toner obtained by the pulverization method without any special treatment, and is indefinite, so that the electrostatic latent image carrier and the toner are in contact with each other. The area is increased and the toner adhesion is increased. As a result, there is less in-machine contamination, and a higher image density and a higher quality image can be easily obtained.

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

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

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

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

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

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

  In addition, the polymerized toner according to the present embodiment draws a cumulative distribution from the smaller diameter side for each of the volume and number with respect to the particle size range (channel) obtained by dividing the particle size distribution measured by the following method. Calculated from (D84% / D16%) × 1/2, where the particle size is defined as volume D16%, the particle size at cumulative 50% is defined as volume D50%, and the particle size at cumulative 84% is defined as volume D84%. The volume average particle size distribution index (GSDv) is preferably 1.15 to 1.30, more preferably 1.15 to 1.25.

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

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

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

When the toner according to the present embodiment, the true specific gravity is preferably 0.9g ^/ cm ³ ~1.2g / cm 3 in the case of non-magnetic toner, although the case of the magnetic toner depends on the type and content of the magnetic powder 0.9g ^/ cm ³ ~4.0g ^/ cm 3 is preferable. The true specific gravity of the toner is calculated as follows. 1.000 g of toner is precisely weighed, put into a 10 mmφ tablet molding machine, and compression molded while applying a pressure of 200 kgf / cm ² (1961 N / cm ² ) under vacuum. The height of this cylindrical molded product is measured with a micrometer, and the true specific gravity is calculated from this.

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

In the present embodiment, SF-1 and SF-2 indicating the shape factor of the toner are, for example, toner particles enlarged 1000 times using an optical microscope (for example, BH-2 manufactured by Olympus Corporation) equipped with a CCD camera. The group is sampled to be about 30 in one field of view, and the obtained image is transferred to an image analyzer (for example, Luzex FS manufactured by Nireco Co., Ltd.), and the same operation is repeated until there are about 1000 toner particles. The shape factor was calculated. The shape factor (SF-1) and the shape factor 2 (SF-2) are calculated by the following equations (4) and (5), respectively.
SF-1 = ((ML ² × π) / 4A) × 100 (4)
(In the formula, ML represents the maximum particle length, and A represents the projected area of one particle.)
SF-2 = (PM ² / 4Aπ) × 100 (5)
(In the formula, PM represents the perimeter of the particle and A represents the projected area of one particle).

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

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

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

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

  The toner according to the exemplary embodiment preferably has a toner melt index (MI value) of 10 g / 10 min 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 kgf (98 N).

In the toner according to the exemplary embodiment, the melting start temperature of the toner is preferably 80 ° C. to 180 ° C., and the 4 mm drop temperature is preferably 90 ° C. to 220 ° C. In this case, the toner melting start temperature is obtained by compressing and molding toner particles to produce a cylindrical test piece having a diameter of 10 mm and a thickness of 20 mm. -500C) and is defined as a value at which melting starts and the piston starts to descend when measured at a load of 20 kgf / cm ² (196 N / cm ² ). In the same measurement, the temperature when the piston drops by 4 mm is defined as the 4 mm drop temperature.

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

In the toner according to the exemplary embodiment, the melt viscosity of the toner is preferably 1000 poise to 50000 poise, and more preferably 1500 poise to 38000 poise. In this case, the toner melt viscosity is obtained by compressing and molding toner particles to prepare a cylindrical test piece having a diameter of 10 mm and a thickness of 20 mm, and using this, a thermal melt property measuring apparatus, for example, a flow tester (CFT-500C manufactured by Shimadzu Corporation). It is defined as a value when measured at a load of 20 kgf / cm ² (196 N / cm ² ).

  The solvent dissolution residue of the toner according to the exemplary embodiment is 0% by mass to 30% by mass as a THF insoluble content, 0% by mass to 40% by mass as an ethyl acetate insoluble content, and 0% by mass to 30% by mass as a chloroform insoluble content. Those are preferred. The solvent dissolution residue here is obtained by uniformly dissolving or dispersing 1 g of toner in 100 mL of each solvent of THF, ethyl acetate, and chloroform, filtering this solution or dispersion under reduced pressure, drying the filtrate, and quantifying this value. From this, the ratio of the insoluble matter in the organic solvent in the toner is calculated.

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

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

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

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

[Example 1]
Analysis of the purity, composition ratio, and the like of the conformational isomer of the compound represented by the general formula (1) such as corn type or partial corn type was performed by HPLC. The HPLC measurement conditions are as follows.
Apparatus: LC-10A manufactured by Shimadzu Corporation, column: Develosil ODS-HG-5 manufactured by Nomura Chemical Co., Ltd., inner diameter 4.6, column length 250 mm, column temperature: 40 ° C., mobile phase: THF / methanol / water / tri Fluoroacetic acid = 450/400/150/2 (v / v / v / v), flow rate: 1.0 mL / min, measurement wavelength: 296 nm, injection volume: 1 μL, sample concentration: 1000 mg / L.
These compounds were purified by column chromatography, adsorption purification using silica gel, activated carbon, activated clay, etc., recrystallization using a solvent or crystallization. The compound was identified by NMR analysis.

[Synthesis Example 1 (Synthesis of Composition A)]
In a 1 L four-necked flask equipped with a stirrer, a condenser tube and a thermometer, in general formula (1), all of R _{1 to} R ₄ are hydrogen atoms, all of R _{5 to} R ₆ are tert-butyl groups, X ₁ 45.5 g of a compound in which all of X ₄ are sulfur atoms, DMF 70 mL, THF 620 mL are added, and 40.4 g of sodium hydride (containing 60% (w / w) in oil) is added at room temperature with stirring. Stir for 0.5 hour. 172 g of benzyl bromide was added dropwise and heated, and stirred for 2 hours under reflux. After cooling to room temperature, 100 mL of water was added and stirred for 30 minutes. After THF was distilled off under reduced pressure, 300 mL of water and 400 mL of chloroform were added, and the organic layer was collected by a liquid separation operation. The organic layer is washed successively with dilute hydrochloric acid, water, and saturated brine, dried over anhydrous magnesium sulfate, and concentrated to dryness, whereby all of R _{1 to} R ₄ are benzyl groups, R _{5 to} R in the general formula (1). 68 g of a yellow solid which is a composition A of a compound in which all of ₈ is a tert-butyl group and all of X _{1 to} X ₄ are sulfur atoms was obtained. As a result of the HPLC analysis, the composition ratio of composition A was 70% for the conformer in the corn conformation, 9% for the conformer in the partial cone conformation, and the 1,3-alternate conformation. The conformational isomer of the locus was 6%.

[Example 2]
[Synthesis Example 2 (Synthesis of Composition B)]
In a 5 L four-necked flask equipped with a stirrer, a condenser tube and a thermometer, in general formula (1), all of R _{1 to} R ₄ are hydrogen atoms, all of R _{5 to} R ₈ are tert-butyl groups, X ₁ 100 g of a compound in which ˜X ₄ is a sulfur atom, 3 L of acetone, 190 g of benzyl bromide, and 118 g of sodium carbonate were added and heated, followed by stirring at 50 ° C. for 48 hours. After cooling to room temperature and concentrating, the precipitated crystals were collected by filtration, washed with water, and then dissolved in 1 L of chloroform. After sequentially washing with dilute hydrochloric acid, water and saturated brine, drying over anhydrous magnesium sulfate and concentrating, in general formula (1), R ₁ and R ₃ are benzyl groups, R ₂ and R ₄ are hydrogen atoms, R ₅ 90 g (yield 73%) of white crystals I of a compound in which all of ˜R ₈ are tert-butyl groups and all of X _{1 to} X ₄ are sulfur atoms were obtained. As a result of HPLC analysis, the syn-1,3-type stereoisomer (for example, see Non-Patent Document 1) was 97.8%.

NMR spectrum was measured for the obtained white crystal I to identify the structure.
^The following 60 hydrogen signals were detected by ¹ H-NMR (CDCl ₃ ). δ (ppm) = 0.79 (18H), 1.34 (18H), 5.49 (4H), 6.96 (4H), 7.24 (2H), 7.30-7.33 (4H) 7.62 (4H), 7.68 (4H), 7.97 (2H)

89.7 g of the obtained white crystals I and 1.8 L of DMF were added to a 5 L four-necked flask equipped with a stirrer, a condenser tube and a thermometer, and sodium hydride (containing 60% (w / w) in oil) at room temperature. 5.46 g was added with stirring and further stirred for 0.5 hour. After cooling to 5 ° C., 17.2 g of benzyl bromide was added, and the mixture was further stirred for 4.5 hours. 2 L of water was added dropwise, and the mixture was further stirred for 0.5 hour. The precipitated crystals were collected by filtration, dissolved in 3.9 L of chloroform, and washed successively with dilute hydrochloric acid, water, and saturated brine. After drying over anhydrous magnesium sulfate, concentration was performed to obtain 98 g of a yellow oil. Subsequently, after purification by column chromatography (carrier: silica gel, eluent: hexane / chloroform), crystallization using methanol was performed, and further washing with methanol was followed by drying under reduced pressure to give a general formula ( 1) in which one of R _{1 to} R ₄ is a hydrogen atom, the remaining three are benzyl groups, all of R ₂ are tert-butyl groups, and all of X _{1 to} X ₄ are sulfur atoms 54.6 g (56% yield) of white crystals II was obtained. As a result of HPLC analysis, the purity was 99.4%.

NMR spectrum was measured for the obtained white crystal II to identify the structure.
^The following 66 hydrogen signals were detected by ¹ H-NMR (CDCl ₃ ). δ (ppm) = 0.85 (18H), 1.25 (9H), 1.27 (9H), 5.12-5.17 (4H), 5.37 (2H), 6.96-6. 97 (4H), 7.14-7.15 (3H), 7.25-7.36 (8H), 7.48-7.50 (4H), 7.55 (2H), 7.60 (2H) ), 7.71 (1H)

The obtained white crystals II (50 g), acetone (4 L), cesium carbonate (81.8 g) and benzyl bromide (40.7 g) were added to a 5 L four-necked flask equipped with a stirrer, a condenser and a thermometer, heated, and stirred under reflux for 2 hours. did. After cooling to room temperature, the precipitated crystals were collected by filtration and washed with water. After dissolving in chloroform and sequentially washing with dilute hydrochloric acid, water, and saturated saline, drying over anhydrous magnesium sulfate and concentrating all of R _{1 to} R ₄ in formula (1) are benzyl groups, R _{5 to} R 54 g (yield 99%) of a compound B in which all of ₈ is a tert-butyl group and all of X _{1 to} X ₄ are sulfur atoms was obtained as a yellow oil. As a result of HPLC analysis, the composition ratio of the composition B was 13% for the conformer of the cone type conformation and 85% of the conformer for the partial cone type conformation.

[Example 3]
Synthesis Example 3 (Synthesis of corn type conformer)
68 g of composition A synthesized in Example 1 was dissolved in 500 mL of chloroform and purified by column chromatography (carrier: silica gel, eluent: hexane / chloroform), followed by crystallization using methanol, and further using methanol. In the general formula (1), all of R _{1 to} R ₄ are benzyl groups, all of R _{5 to} R ₈ are tert-butyl groups, and all of X _{1 to} X ₄ are sulfur atoms. As a result, 36 g (yield 52.8%) of white crystals III, which is a conformer of a cone type conformation (purity 98.8%), was obtained.

The obtained white crystals III were subjected to NMR spectrum measurement to identify the structure.
^The following 72 hydrogen signals were detected by ¹ H-NMR (CDCl ₃ ). δ (ppm) = 1.06 (36H), 5.24 (8H), 7.16-7.18 (12H), 7.22 (8H), 7.47-7.48 (8H)

[Example 4]
[Synthesis Example 4 (Synthesis of Partial Cone Conformer)]
54 g of composition B synthesized in Example 2 was purified by column chromatography (carrier: silica gel, eluent: hexane / chloroform), crystallized with methanol, further washed with methanol, In the general formula (1), by drying, all of R _{1 to} R ₄ are benzyl groups, all of R _{5 to} R ₈ are tert-butyl groups, and all of X _{1 to} X ₄ are sulfur atoms, Thus, 45.2 g (yield 84.4%) of white crystals IV which is a conformer of a partial cone type conformation (purity 99.1%) was obtained.

The obtained white crystal IV was measured for NMR spectrum to identify the structure.
^The following 72 hydrogen signals were detected by ¹ H-NMR (CDCl ₃ ). δ (ppm) = 0.74 (9H), 0.85 (18H), 1.22 (9H), 4.82 (2H), 4.92 (2H), 5.08 (2H), 5.11 (2H), 6.91 (2H), 7.07 (3H), 7.32 (15H), 7.61 (2H), 7.68 (4H), 7.77 (2H)

[Comparative Example 1]
[Comparative Synthesis Example 1 (Synthesis of Comparative Composition C)]
In a 1 L four-necked flask equipped with a stirrer, a condenser tube and a thermometer, in general formula (1), all of R _{1 to} R ₄ are hydrogen atoms, all of R _{5 to} R ₆ are tert-butyl groups, X ₁ 84.0 g of a compound in which all of X ₄ are sulfur atoms, 800 mL of DMF, and 102 g of potassium carbonate were added, and 112.3 g of benzyl chloride was added dropwise thereto at room temperature while heating, followed by stirring at 100 ° C. for 8 hours. After allowing to cool to room temperature, the reaction solution was added to 3 L of diluted hydrochloric acid, and the precipitated crude crystals were collected by filtration. After repeating dispersion washing with water, followed by dispersion washing with methanol, by drying, in the general formula (1), all of R _{1 to} R ₄ are benzyl groups, all of R _{5 to} R ₈ are tert-butyl groups, As a result, 118 g (yield: 98.2%) of white-white crystals which are the composition C of the compound in which all of X _{1 to} X ₄ are sulfur atoms were obtained. As a result of the HPLC analysis, the composition ratio of composition C was 1% for the conformer in the corn conformation, 16% for the conformer in the partial cone conformation, and the 1,2-alternate conformation. The conformer of the locus was 4%, and the conformer of the 1,3-alternate conformation was 77%.

[Comparative Example 2]
[Comparative Synthesis Example 2 (Synthesis of 1,3-alternate type conformer)]
118 g of composition C synthesized in Comparative Synthesis Example 1 was dissolved in 600 mL of THF while heating, and then cooled to room temperature. The precipitated crystals are collected by filtration, washed with THF, and then dried to dry all of R _{1 to} R ₄ in the general formula (1), all of R _{5 to} R ₈ are tert-butyl groups, X _{1 to} X ₄ is a compound in which all of them are sulfur atoms, and 58.4 g (yield: 46.3%) of white plate-like crystals V, which is a 1,3-alternate type conformer (purity 99.1%). )

NMR spectrum was measured for the obtained white plate crystal V to identify the structure.
^The following 72 hydrogen signals were detected by ¹ H-NMR (CDCl ₃ ). δ (ppm) = 0.84 (36H), 5.07 (8H), 7.01 (8H), 7.06 (8H), 7.14 (12H)

Table 1 shows the content of each conformer for Synthesis Examples 1 to 4 and Comparative Synthesis Examples 1 to 2. In the table, “molar ratio” means a conformer of a corn type conformation and a partial cone type conformation among the four conformers of the compound represented by the general formula (1). Is a value obtained by dividing the total by the number of moles of the four conformers and can be calculated by the following formula (6).
(Molar ratio) = (number of moles of conformer in corn type conformation + number of moles of conformer in conformation of partial cone type) / (number of moles of conformer in conformation of cone type) + Number of moles of conformer in the partial cone conformation + number of moles of conformer in the 1,2-alternate conformation + number of moles of the conformer in the 1,3-alternate conformation) × 100 (%) (6)

[Example 5]
[Production of Non-magnetic Toner 1]
Styrene-acrylate copolymer resin (Mitsui Chemicals, trade name CPR-100, acid value 0.1 mg KOH / g) 91 parts, composition A 1 part, carbon black (Mitsubishi Chemical Corporation, trade name MA- 100) 5 parts and 3 parts of low molecular weight polypropylene (manufactured by Sanyo Chemical Co., Ltd., trade name Biscol 550P) were melt-mixed by a 130 ° C. heating mixing apparatus (biaxial extrusion kneader). The cooled mixture was roughly pulverized with a hammer mill, then finely pulverized with a jet mill, and classified to obtain a nonmagnetic toner having a volume average particle size of 9 ± 0.5 μm.

[Evaluation of Non-magnetic Toner 1]
This toner is mixed and shaken at a ratio of 4 to 100 parts by mass (toner: carrier) with a non-coated ferrite carrier (F-150 manufactured by Powdertech Co., Ltd.), and then the toner is negatively charged. The saturation charge amount was measured in an atmosphere of a temperature of 25 ° C. and a humidity of 50% with a quantity measuring device. Further, the case of mixing with a silicon-coated ferrite carrier (F96-150, manufactured by Powder Tech Co., Ltd.) was similarly evaluated. The results are summarized in Table 2.
Furthermore, environmental stability under high temperature and high humidity (30 ° C., 85% RH) was evaluated. The environmental stability was evaluated in the following four stages according to the rate of decrease of the saturation charge amount at a temperature of 25 ° C. and a humidity of 50% under high temperature and high humidity. The results are summarized in Table 2.
A: Stable (saturation charge reduction rate is less than 5%)
○: Slightly stable (saturation charge reduction rate is 5% or more and less than 10%)
Δ: Slightly unstable (saturation charge reduction rate is 10% or more and less than 15%)
X: unstable (saturation charge reduction rate is 15% or more)

[Example 6]
[Production and Evaluation of Nonmagnetic Toner 2]
In the production method of Example 5, composition A was replaced with composition B, non-magnetic toner 2 was prepared, and saturation charge amount was measured in a blow-off powder charge amount measuring device in an atmosphere at a temperature of 25 ° C. and a humidity of 50%. Went. Further, the case of mixing with a silicon-coated ferrite carrier (F96-150, manufactured by Powder Tech Co., Ltd.) was similarly evaluated. Furthermore, environmental stability was evaluated. The results are summarized in Table 2.

[Example 7]
[Production and Evaluation of Nonmagnetic Toner 3]
In the production method of Example 5, composition A was replaced with white crystals III (cone conformational isomer) to prepare nonmagnetic toner 3, which was measured at a temperature of 25 ° C. and a humidity of 50% with a blow-off powder charge measuring device. The saturation charge amount was measured under the atmosphere of Further, the case of mixing with a silicon-coated ferrite carrier (F96-150, manufactured by Powder Tech Co., Ltd.) was similarly evaluated. Furthermore, environmental stability was evaluated. The results are summarized in Table 2.

[Example 8]
[Production and Evaluation of Nonmagnetic Toner 4]
In the production method of Example 5, the composition A was replaced with white crystals IV (partial cone type conformer) to prepare a nonmagnetic toner 4, and a temperature of 25 ° C. and a humidity of 50 were measured with a blow-off powder charge measuring device. The saturation charge amount was measured in a% atmosphere. Further, the case of mixing with a silicon-coated ferrite carrier (F96-150, manufactured by Powder Tech Co., Ltd.) was similarly evaluated. Furthermore, environmental stability was evaluated. The results are summarized in Table 2.

[Comparative Example 3]
[Production and Evaluation of Comparative Nonmagnetic Toner 1]
In the production method of Example 5, the composition A was replaced with the composition C to prepare a comparative nonmagnetic toner 1, and the saturation charge amount was measured in a blow-off powder charge amount measuring device in an atmosphere at a temperature of 25 ° C. and a humidity of 50%. Measurements were made. Further, the case of mixing with a silicon-coated ferrite carrier (F96-150, manufactured by Powder Tech Co., Ltd.) was similarly evaluated. Furthermore, environmental stability was evaluated. The results are summarized in Table 2.

[Comparative Example 4]
[Production and Evaluation of Comparative Nonmagnetic Toner 2]
In the production method of Example 5, the composition A was replaced with white plate-like crystals V (1,3-alternate type conformer) to prepare a comparative nonmagnetic toner 2, which was measured with a blow-off powder charge measuring device. The saturation charge amount was measured in an atmosphere at a temperature of 25 ° C. and a humidity of 50%. Further, the case of mixing with a silicon-coated ferrite carrier (F96-150, manufactured by Powder Tech Co., Ltd.) was similarly evaluated. Furthermore, environmental stability was evaluated. The results are summarized in Table 2.

  As is clear from the above results, in Examples 5 to 8, it was found that the charge amount was high and excellent environmental stability was exhibited.

[Example 9]
[Preparation of resin dispersion]
80 parts of a polyester resin (Mitsubishi Rayon Co., Ltd., DIACRON ER-561), 320 parts of ethyl acetate, and 32 parts of isopropyl alcohol are mixed, and a homogenizer (Made Co., Ltd., foamless mixer NGM-0.5TB) is used. While stirring at 5000 rpm to 10,000 rpm, an appropriate amount of 0.1% by mass of ammonia water was added dropwise to effect phase inversion emulsification, and the solvent was removed while reducing the pressure with an evaporator to obtain a resin dispersion. The volume average particle diameter of the resin particles in this dispersion was 0.2 μm (the resin particle concentration was adjusted to 20% by mass with ion-exchanged water).

[Preparation of Charge Control Agent Dispersion]
0.2 parts of sodium dodecylbenzenesulfonate, 0.2 part of sorbon T-20 (manufactured by Toho Chemical Co., Ltd.) and 17.6 parts of ion-exchanged water were mixed and dissolved, and composition A2. 0 parts, zirconia beads (bead particle size 0.65 mmφ, equivalent to 15 mL) were added and dispersed with a paint conditioner (UNION NJ (USA), Red Devil No. 5400-5L) for 3 hours. . The zirconia beads were removed using a sieve and adjusted with ion-exchanged water to obtain a 10% by mass charge control agent dispersion.

[Preparation of polymerization toner]
125 parts of the resin dispersion, 1.0 part of a 20% by weight sodium dodecylbenzenesulfonate aqueous solution and 125 parts of ion-exchanged water are added to a reaction vessel equipped with a thermometer, pH meter, and stirrer, and the liquid temperature is controlled at 30 ° C. While stirring, the mixture was stirred at 150 rpm for 30 minutes. A 1% by mass aqueous nitric acid solution was added to adjust the pH to 3.0, and the mixture was further stirred for 5 minutes. While dispersing with a homogenizer (IKA Japan, Ultra Tarrax T-25), 0.125 part of polyaluminum chloride was added, the temperature was raised to 50 ° C., and the mixture was further dispersed for 30 minutes. After adding 62.5 parts of the resin dispersion and 4.0 parts of the charge control agent dispersion, a 1% by mass aqueous nitric acid solution was added to adjust the pH to 3.0, and the mixture was further dispersed for 30 minutes. While stirring at 400 rpm to 700 rpm using a stirrer, 8.0 parts of a 5% by mass aqueous sodium hydroxide solution was added, and stirring was continued until the volume average particle diameter of the toner reached 9.5 μm. After the liquid temperature was raised to 75 ° C., the mixture was further stirred for 2 hours, and after confirming that the volume average particle size was 6.0 μm and the particle shape was spheroidized, it was rapidly cooled using ice water. The sample was collected by filtration and dispersed and washed with ion exchange water. Dispersion washing was repeated until the electric conductivity of the filtrate after dispersion became 20 μS / cm or less. Thereafter, the toner particles were obtained by drying with a dryer at 40 ° C. The obtained toner was sieved with a 166 mesh (aperture 90 μm) sieve to obtain an evaluation toner.

[Evaluation]
2 parts of the obtained toner for evaluation and 100 parts of a non-coated ferrite carrier (F-150 manufactured by Powdertech Co., Ltd.) were mixed and shaken to charge the toner negatively, and then the charge amount of blow-off powder was charged. The saturation charge amount was measured in an atmosphere of a temperature of 25 ° C. and a humidity of 50% with a measuring device. Further, the case of mixing with a silicon-coated ferrite carrier (F96-150, manufactured by Powder Tech Co., Ltd.) was similarly evaluated. Furthermore, environmental stability was evaluated. The results are summarized in Table 3.

[Example 10]
In the production method of Example 9, a toner was prepared under the same conditions as in Example 9 except that the charge control agent dispersion was prepared using Composition B instead of Composition A, and the saturation charge amount was measured. went. Furthermore, environmental stability was evaluated. The results are summarized in Table 3.

[Example 11]
In the production method of Example 9, the toner was prepared under the same conditions as in Example 9 except that the charge control agent dispersion liquid was prepared using white crystals III (cone-type conformer) instead of the composition A. The saturation charge amount was measured. Furthermore, environmental stability was evaluated. The results are summarized in Table 3.

[Example 12]
In the production method of Example 9, a toner was prepared under the same conditions as in Example 9 except that a charge control agent dispersion was prepared using white crystals IV (partial cone type conformer) instead of Composition A. The saturation charge amount was measured. Furthermore, environmental stability was evaluated. The results are summarized in Table 3.

[Comparative Example 5]
In the production method of Example 9, a toner was prepared under the same conditions as in Example 9 except that the charge control agent dispersion was prepared using the composition C instead of the composition A, and the saturation charge amount was measured. went. Furthermore, environmental stability was evaluated. The results are summarized in Table 3.

[Comparative Example 6]
Example 9 is the same as Example 9 except that the charge control agent dispersion was prepared using white plate-like crystals V (1,3-alternate type conformer) instead of the composition A in the production method of Example 9. A toner was prepared under the same conditions, and the saturation charge amount was measured. Furthermore, environmental stability was evaluated. The results are summarized in Table 3.

[Comparative Example 7]
In the production method of Example 9, a toner was prepared under the same conditions as in Example 9 except that the operation of adding the charge control agent dispersion was omitted, and the saturation charge amount was measured. The results are summarized in Table 3.

  As is apparent from the above results, the charge containing as an active ingredient a compound represented by the general formula (1), in which 50 mol% or more is a corn conformation or a conformation isomer of a partial cone conformation. It has been found that the polymerized toner using the control agent has a high charge amount and exhibits excellent environmental stability.

  The charge control agent according to the present invention has clearly higher charging performance and superior environmental stability than conventional charge control agents. Further, it is completely colorless and is optimal for color toners, particularly for polymerized toners. Furthermore, it does not contain heavy metals such as chromium compounds, which are concerned about environmental problems, and can provide a very useful toner.

Claims (5)

Containing at least one compound represented by the following general formula (1) as an active ingredient,
The charge control agent whose 50 mol% or more of the said compound is a conformer of a cone type | mold conformation or a partial cone type conformation.

[In the general formula (1), R ₁ , R ₂ , R ₃ and R ₄ may be the same or different from each other, and are substituted or unsubstituted linear or branched alkyl having 1 to 20 carbon atoms. Represents a group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group, R ₅ , R ₆ , R ₇ and R ₈ may be the same or different from each other; Or an unsubstituted straight-chain or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group, X ₁ , X ₂ , X ₃ and X ₄ may be the same as or different from each other, and each represents a sulfur atom, a sulfinyl group or a sulfonyl group. ] The charge control agent according to claim ₁ , wherein in the general formula (1), all of X ₁ , X ₂ , X ₃ and X ₄ are sulfur atoms. In the general formula (1), R ₁ , R ₂ , R ₃ and R ₄ may be the same as or different from each other, and have 1 carbon atom having an aromatic hydrocarbon group or an aromatic heterocyclic group as a substituent. The charge control agent according to claim 1 or 2, which is a group selected from -4 linear or branched alkyl groups. A toner containing one or more of the charge control agents according to any one of claims 1 to 3 , a colorant, and a binder resin. A polymerized toner comprising one or more of the charge control agents according to any one of claims 1 to 3 , a colorant, and a binder resin.

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