TWI609010B - Charge control agent and toner - Google Patents

Description

Charge control agent and toner

The present invention relates to a charge control agent used in an image forming apparatus for developing an electrostatic latent image in the fields of electrophotography, electrographic recording, and the like, and a negative chargeability property containing a charge control agent Toner.

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

The photoreceptor has positive charging property and negative charging property according to its constitution, and is developed by the opposite-symbol charged toner when the printing portion is left in the form of an electrostatic latent image by exposure, on the other hand, The printing portion is developed by the same symbol charged toner in the case where the printing portion is subjected to reverse development.

The toner contains a binder resin, a colorant, and other additives, but in order to impart desirable charging characteristics (charge speed, charge level, charge stability, etc.), stability over time, environmental stability, etc., a charge control agent is usually used. . By adding the charge control agent, the characteristics of the toner can be greatly improved.

Further, in the case of a color toner, it is necessary to have a light color which does not affect the hue, and is preferably a colorless charge control agent. Among these light-colored or colorless charge control agents, there are a metal-stack salt compound as a hydroxybenzoic acid derivative for a negatively chargeable toner (for example, refer to Patent Documents 1 to 3) and an aromatic dicarboxylic acid metal salt compound (for example). For example, refer to Patent Document 4), an adjacent amine A metal tyrosine compound of a benzoic acid derivative (for example, refer to Patent Documents 5 to 6), an organic boron compound (for example, refer to Patent Documents 7 to 8), a biphenol compound (for example, refer to Patent Document 9), and a cup (n) arene compound. (For example, refer to Patent Documents 10 to 15) and cyclic phenol sulfide (for example, refer to Patent Documents 16 to 19). Further, there are a quaternary ammonium salt compound for use as a positively chargeable toner (see, for example, Patent Documents 20 to 22).

[Previous Technical Literature] [Patent Literature]

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

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

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

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

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

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

Patent Document 7: US Patent No. 4767688

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

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

Patent Document 10: Japanese Patent No. 2568675

Patent Document 11: Japanese Patent No. 2899038

Patent Document 12: Japanese Patent No. 3359657

Patent Document 13: Japanese Patent No. 33138871

Patent Document 14: Japanese Patent No. 3325730

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

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

Patent Document 17: International Publication No. 2007/111346

Patent Document 18: International Publication No. 2007/119797

Patent Document 19: International Publication No. 2011/016519

Patent Document 20: Japanese Patent Laid-Open Publication No. SHO 57-119364

Patent Document 21: Japanese Patent Laid-Open No. SHO 58-009154

Patent Document 22: Japanese Patent Laid-Open No. SHO 58-098742

Patent Document 23: Japanese Patent Laid-Open No. Hei 10-081680

Patent Document 24: International Publication No. 98/09959

[Non-patent literature]

Non-Patent Document 1: J. Org. Chem., 68, 2324 (2003)

However, many of these charge control agents contain a complex or a salt of a heavy metal such as chromium or zinc, which is problematic in terms of waste disposal limitations and may not be safe. Moreover, there is a problem that the color is not completely colorless, the rising speed of electrification is slow, the environmental stability of the charged amount under high temperature and high humidity is problematic, the charge amount itself is low, the oppositely charged toner is large, or the dispersion is lacking or Disadvantages such as stability of the compound, and further inability to achieve application to a polymerized toner, etc., are not satisfactory as a charge control agent.

SUMMARY OF THE INVENTION An object of the present invention is to provide a charge control agent containing a specific configurational isomer of a cyclic phenol sulfide as an active ingredient, and in view of the above circumstances, provides a use as a color toner, particularly as a polymerized toner. A charge control agent that is useful for use, has a high charge capacity, and has excellent charging characteristics with excellent environmental stability, and is safe in terms of waste disposal restrictions. Further, it is an object of the invention to provide a negatively chargeable toner for electrostatic image development which is particularly excellent in environmental stability using the charge control agent, particularly a negatively chargeable polymerized toner.

The present invention has been made in an effort to achieve the above object, and the gist thereof is as follows.

That is, the present invention provides a charge control agent containing at least one of the compounds represented by the following formula (1) as an active ingredient, and 50 mol% or more of the above compound is a cone-shaped stereo configuration or a part a configurational isomer of a partial cone type stereo configuration,

In the 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 or different, and represent a substituted or unsubstituted carbon atom. a linear or branched alkyl group of 1 to 20, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group, R ₅ , R ₆ , R ₇ and R ₈ ( The following is also collectively described as "R ₅ ~ R ₈ ") which may be the same or different, and represent a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, substituted or not. The substituted aromatic hydrocarbon group or the substituted or unsubstituted aromatic heterocyclic group, X ₁ , X ₂ , X ₃ and X ₄ (hereinafter collectively referred to as "X ₁ to X ₄ ") may be the same as each other. It may be different and represents a sulfur atom, a sulfinyl group or a sulfonyl group.

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

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

The charge control agent of the present invention has a high charge amount, has a charging property excellent in environmental stability, and has excellent characteristics in terms of waste disposal limitations and is safe, and can be suitably used for a toner. Charge control. Therefore, the present invention also mentions Supply: a charge containing at least one of the compounds represented by the above formula (1) as an active ingredient, and 50 mol% or more of the above compound is a conformational isomer of a conical stereo configuration or a partial conical stereo configuration The use of the control agent for charge control of the toner; or at least one of the compounds represented by the above formula (1) as an active ingredient, and 50 mol% or more of the above compound is a cone-shaped stereo configuration or part The use of a charge control agent for a conformational isomer of a conical stereo configuration for charge control of a toner. The above toner may also be a polymerized toner.

Furthermore, the present invention also provides a charge control method for a toner, comprising at least one of the compounds represented by the above formula (1) as an active ingredient, and 50 mol% or more of the above compound is a cone-shaped stereostructure A charge control agent for the conformational isomer of the shaped or partially tapered stereo configuration is added to the toner. In this case, the above toner may also be a polymerized toner.

The charge control agent of the present invention has a charge amount higher than that of the previous charge control agent, and has charging characteristics particularly excellent in environmental stability. The above charge control agent is completely colorless and is therefore most suitable for color toner applications, especially for polymerized toner applications. The charge control agent does not contain metals such as chromium and zinc which are concerned with environmental problems, and is excellent in dispersibility and stability of the compound.

Fig. 1 is a schematic view showing a configuration of a conformational isomer of a compound represented by the formula (1) in a conical shape.

Fig. 2 is a schematic view showing a configuration in which the stereoscopic configuration of the compound represented by the general formula (1) is a partial pyramidal configuration.

Fig. 3 is a schematic view showing a conformational isomer of a 1,2-alternating type in which the compound represented by the formula (1) is a stereo configuration.

Figure 4 is a view showing the configuration of the compound represented by the general formula (1) in the form of a 1,3-alternate structure. Schematic diagram of the isomers.

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

The charge control agent of the present embodiment contains at least one of the compounds represented by the above formula (1) as an active ingredient. The compound contains a conformational isomer having a tangular configuration as a cone or a partial cone at a specific ratio. First, the compound represented by the formula (1) will be described.

The "linear or branched alkyl group having 1 to 20 carbon atoms" represented by R ₁ to R ₄ in the formula (1) may, for example, be a methyl group, an ethyl group or a n-propyl group. 2-propyl, n-butyl, t-butyl, 2-methylpropyl, tert-butyl, n-pentyl, 1-methylbutyl, 1-ethylpropyl, 1,1-dimethyl Propyl, 1,2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl Base, 2-ethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,4-dimethylbutyl, 2 , 2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethyl-2-methylpropyl, 1,1,2-trimethyl Propyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, trioctyl, 2-ethylhexyl, 3-methylheptyl, n-decyl, isodecyl, 1-methyl Benzyl, 2-ethylheptyl, n-decyl, 1-methylindenyl, n-undecyl, 1,1-dimethylindenyl, n-dodecyl, n-tetradecyl, N-heptadecyl, n-octadecyl.

The "linear or branched alkyl group having 1 to 20 carbon atoms" represented by R ₁ to R ₄ in the formula (1) may have a substituent. Examples of the "substituent group" include a halogen atom such as a fluorine atom or a chlorine atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, a dialkylamino group, a decyl group or an alkoxy group. A carbonyl group, an epoxyalkyl group, an aromatic hydrocarbon group, or 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 20 carbon atoms, a cyclopentyl group, and a ring. a hexyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, a dialkylamino group substituted with a linear or branched alkyl group having 1 to 6 carbon atoms, and a carbon number a linear or branched fluorenyl group of 1 to 20, a linear or branched alkoxycarbonyl group having 1 to 20 carbon atoms, an epoxy group having 1 to 6 carbon atoms, or a phenyl group; , naphthyl, anthracenyl, fluorenyl, styryl, pyridyl, pyridohydrazino, quinolyl, benzothiazolyl. 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 formula (1) include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, and a fluorenyl group. , phenanthrene, sulfhydryl, sulfhydryl, sulfhydryl, three , pyrimidinyl, furyl, pyrrolyl, thienyl, quinolyl, isoquinolinyl, benzofuranyl, benzothienyl, fluorenyl, carbazolyl, benzo Azolyl, benzothiazolyl, quin A phenyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a naphthyridinyl group, a morpholinyl group, an acridinyl group.

The "aromatic hydrocarbon group" or "aromatic heterocyclic group" represented by R ₁ to R ₄ in the formula (1) may have a substituent. Examples of the "substituent group" include a halogen atom such as a fluorine atom or a chlorine atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, a dialkylamino group, a decyl group or an alkoxy group. A carbonyl group, an epoxyalkyl group, an aromatic hydrocarbon group, or 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, and a ring. a hexyl group, a linear or branched alkoxy 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, Naphthyl, anthracenyl, fluorenyl, styryl, pyridyl, pyridohydrazino, quinolyl, benzothiazolyl. These substituents may be further substituted with the substituents exemplified above.

R ₁ to R ₄ in the formula (1) are preferably an unsubstituted linear or branched alkyl group having 4 to 20 carbon atoms, having 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. Further, R ₁ to R ₄ in the formula (1) are more preferably an unsubstituted linear or branched alkyl group having 10 to 20 carbon atoms, having an aromatic hydrocarbon group or an aromatic heterocyclic group as The linear or branched alkyl group having 1 to 4 carbon atoms of the substituent, the substituted or unsubstituted aromatic hydrocarbon group, or the substituted or unsubstituted aromatic heterocyclic group. Further, R ₁ to R ₄ in the formula (1) are preferably a linear or branched alkyl group having 1 to 4 carbon atoms and having an aromatic hydrocarbon group or an aromatic heterocyclic group as a substituent.

The "linear or branched alkyl group having 1 to 20 carbon atoms" represented by R ₅ to R ₈ in the formula (1) may, for example, be a methyl group, an ethyl group or a n-propyl group. 2-propyl, n-butyl, t-butyl, 2-methylpropyl, tert-butyl, n-pentyl, 1-methylbutyl, 1-ethylpropyl, 1,1-dimethyl Propyl, 1,2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl Base, 2-ethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,4-dimethylbutyl, 2 , 2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethyl-2-methyl-propyl, 1,1,2-trimethyl Propyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, trioctyl, 2-ethylhexyl, 3-methylheptyl, n-decyl, isodecyl, 1- Methyloctyl, 2-ethylheptyl, n-decyl, 1-methylindenyl, n-undecyl, 1,1-dimethylindenyl, n-dodecyl, n-tetradecyl , n-heptadecyl, n-octadecyl.

The "linear or branched alkyl group having 1 to 20 carbon atoms" represented by R ₅ to R ₈ in the formula (1) may have a substituent. Examples of the "substituent group" include a halogen atom such as a fluorine atom or a chlorine atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, a dialkylamino group, a decyl group or an alkoxy group. A carbonyl group, an epoxyalkyl group, an aromatic hydrocarbon group, or 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, and a linear or branched alkane having 1 to 6 carbon atoms. a oxy group, a dialkylamino group substituted with a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched fluorenyl group having 1 to 20 carbon atoms, and a carbon number a linear or branched alkoxycarbonyl group of 1 to 20, an epoxy group having 1 to 6 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group, an anthracenyl group, a styryl group, a pyridyl group, and a pyridine group. And fluorenyl, quinolyl, benzothiazolyl. 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 formula (1) include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, and a fluorenyl group. , phenanthryl, fluorenyl, fluorenyl, fluorenyl, pyridyl, three , pyrimidinyl, furyl, pyrrolyl, thienyl, quinolyl, isoquinolinyl, benzofuranyl, benzothienyl, fluorenyl, carbazolyl, benzo Azolyl, benzothiazolyl, quin A phenyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a naphthyridinyl group, a morpholinyl group, an acridinyl group.

The "aromatic hydrocarbon group" or "aromatic heterocyclic group" represented by R ₅ to R ₈ in the formula (1) may have a substituent. Examples of the "substituent group" include a halogen atom such as a fluorine atom or a chlorine atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, a dialkylamino group, a decyl group or an alkoxy group. A carbonyl group, an epoxyalkyl group, an aromatic hydrocarbon group, or 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, and a ring. a hexyl group, a linear or branched alkoxy 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, Naphthyl, anthracenyl, fluorenyl, styryl, pyridyl, pyridohydrazino, quinolyl, benzothiazolyl. These substituents may be further substituted with the substituents exemplified above.

R ₅ to R ₈ in the formula (1) are preferably a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group. Or substituted or unsubstituted aromatic heterocyclic group. Further, R ₅ to R ₈ in the formula (1) are more preferably a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic group. a hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group. Further, R ₅ to R ₈ in the formula (1) are more preferably an unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, and particularly preferably an unsubstituted carbon atom. a linear or branched alkyl group of 1 to 6.

X ₁ to X ₄ in the formula (1) may be a sulfur atom, a sulfinyl group or a sulfonyl group, and among them, a sulfur atom is preferred, and it is particularly preferred that all of X ₁ to X ₄ are sulfur atoms.

The compound represented by the formula (1) has a 16-membered ring structure containing four benzene rings, and becomes a large barrier when the stereo configuration changes. Therefore, the compound represented by the general formula (1) has a stereo configuration of a tapered type, a partial tapered type, a 1,2-alternating type, and a 1,3-alternating type represented by the following formulas (1A) to (1D). Four configurational isomers (also referred to as rotamers) (for example, refer to Non-Patent Document 1).

The tapered conformational isomer has a stereo configuration in which R ₁ to R _{4 are} all present in the same direction (for example, the upper side) with respect to a plane formed by a cyclic structure containing X ₁ to X ₄ . The tapered conformational isomer can be represented by the formula (1A) or the structural formula shown in FIG.

The partial cone-shaped configuration isomer has a stereo configuration in which only one of R ₁ to R ₄ is different from the other three with respect to a plane formed by a ring structure containing X ₁ to X ₄ . Direction (for example, R ₂ is the lower side, and the rest of R ₁ , R ₃ and R ₄ are the upper side). The partial cone-shaped configuration isomer can be represented by the formula (1B) or the structural formula shown in FIG.

[Chemical 3]

The 1,2-alternate configuration isomer has a stereo configuration in which two adjacent R ₁ to R ₄ are present in relation to a plane formed by a ring structure containing X ₁ to X ₄ The other two different directions (for example, R ₂ and R ₃ are the lower side, and R ₁ and R ₄ are the upper sides). The 1,2-alternate conformational isomer can be represented by the formula (1C) or the structural formula shown in FIG.

The 1,3-alternate configuration isomer has a stereo configuration in which two opposite R ₁ to R ₄ are present in relation to a plane formed by a ring structure containing X ₁ to X ₄ . The other two different directions (for example, R ₂ and R ₄ are the lower side, and R ₁ and R ₃ are the upper sides). The configurational isomer of the 1,3-alternating type can be represented by the formula (1D) or the structural formula shown in Fig. 4.

[Chemical 5]

The present inventors have found that, in the compound represented by the general formula (1), the total amount of the configuration of the conformational isomer of the conical stereo configuration and the configuration of the partial conical stereo configuration is relative to the above four When the total amount of the constituent isomers is 50 mol% or more, the charge control agent, the toner, and the polymerized toner containing the above compound are excellent in charging characteristics and environmental stability.

Further, when X ₁ to X ₄ is a sulfinyl group, a stereoisomer derived from a sulfinyl group is further produced. However, it is important for the compound of the present embodiment to have a stereo configuration of a 16-membered ring structure containing four benzene rings, so that it is not necessary to distinguish the stereochemical isomers derived from the sulfinyl group.

The compound represented by the formula (1) has four stereoconfigurations of a cone-shaped stereo configuration, a partial conical stereo configuration, a 1,2-alternating stereo configuration, and a 1,3-alternative stereo configuration. Things. In the present embodiment, it is preferred that 50 mol% or more of the compound represented by the general formula (1) is a conical stereo configuration or a partial conical stereo configuration. Further, the ratio of the compound represented by the formula (1) which is present as a tapered stereo configuration or a partial conical stereo configuration may be 55 mol% or more, 60 mol% or more, 65 mol% or more, 70 Mole% or more, 75 mol% or more, 80 mol% or more, 85 mol% or more, or 90 mol% or more. Further, the upper limit of the above ratio is not particularly limited and may be, for example, 100%. The method for calculating the content (mol%) of the compound represented by the formula (1) which is a conical stereo configuration or a partial conical stereo configuration may, for example, be a high-speed liquid chromatography (hereinafter referred to as HPLC). The method of calculating the peak area.

The compound represented by the above formula (1) may also be a compound represented by the following formula (2).

In the formula (2), R ₁ to R ₄ may be the same or different from each other, and represent an unsubstituted linear or branched alkyl group having 10 to 20 carbon atoms, having an aromatic hydrocarbon group or an aromatic hetero group. a linear or branched alkyl group having 1 to 4 carbon atoms as a substituent, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group, R ₅ to R ₈ may be the same or different from each other, and represent a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, or a The substituted or unsubstituted aromatic heterocyclic group, all of X ₁ to X ₄ represent a sulfur atom.

The compound represented by the above formula (1) may also be a compound represented by the following formula (3).

[Chemistry 7]

In the formula (3), R ₁ to R ₄ may be the same or different from each other, and represent a linear or branched alkane having 1 to 4 carbon atoms and having an aromatic hydrocarbon group or an aromatic heterocyclic group as a substituent. Further, R ₅ to R ₈ may be the same or different from each other, and represent an unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, and all of X ₁ to X ₄ represent a sulfur atom.

The tapered or partially tapered configuration isomer of the compound represented by the formula (1) of the present embodiment can be produced by subjecting the corresponding phenol derivative to a known cyclization reaction or subsequent In the oxidation reaction after the cyclization reaction (for example, refer to Patent Documents 23 to 24), a corresponding cyclic phenol sulfide precursor is produced, and then a known O-alkylation reaction or the like is produced (for example, see Non-Patent Document 1). Further, the group represented by R ₅ to R ₈ may be subjected to a cross-coupling reaction such as Suzuki coupling by a corresponding cyclic phenol sulfide precursor substituted with a halogen atom such as an iodine atom or a bromine atom. And import the desired base.

The compound represented by the formula (1) of the present embodiment can be produced, for example, by the method disclosed in Non-Patent Document 1. A compound in which all of R ₁ to R ₄ corresponding to the compound represented by the formula (1) are a hydrogen atom is used, and the reaction conditions are appropriately selected, whereby the desired compound can be selectively produced. For example, in a 9:1 (v/v) mixed solution of tetrahydrofuran (hereinafter also referred to as THF) and N,N-dimethylformamide (hereinafter also referred to as DMF), sodium hydride and benzyl bromide are used for reflux. The reaction was carried out for 2 hours, whereby a configurational isomer having a conical stereo configuration as a main product was obtained. Further, through the following three steps (A) to (C), a configurational isomer having a partial cone-shaped solid configuration as a main product can be obtained.

(A) a step of reacting sodium carbonate with benzyl bromide in reflux in acetone, (B) a step of reacting sodium hydride with benzyl bromide at 0 ° C in DMF, and (C) using in acetone The step of reacting cesium carbonate with benzyl bromide under reflux.

The four configurational isomers of the compound represented by the formula (1) can be used, for example, to separate various configurational isomers by HPLC. Therefore, it is also possible to mix the separated various configurational isomers in a desired ratio, and adjust to 50 mol% or more of the compound represented by the general formula (1) to be a conical stereo configuration or a partial conical stereo configuration. The isomer is configured to be applied to a charge control agent.

The charge control agent of the present embodiment is excellent in charge control characteristics, environmental resistance, and durability, and when used for polymerizing a toner, fog-free image density, dot reproducibility, and fine line reproduction can be obtained. Good image.

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

Further, when the charge control agent of the present embodiment is used for polymerizing a toner, it is preferred to use the volume average particle diameter to 1.0 μm or less, and more preferably to adjust the range to 0.01 μm to 1.0 μm. Use it. When the volume average particle diameter exceeds 1.0 μm, the particle size distribution of the finally obtained toner for electrophotography may become wide or free particles may be generated, resulting in deterioration in performance or reliability. On the other hand, when the average particle diameter is within the above range, not only the above disadvantages are eliminated, but also the uneven distribution between the toners is reduced, the dispersion in the toner is improved, and the performance and reliability are uneven. It is more advantageous to be smaller.

As a method of including the charge control agent of the present embodiment in the toner, there is a method of previously adding to the inside of the toner particles, and pre-manufacturing the toner. A method in which particles are added to the surface of the toner particles. Examples of the method of adding the toner to the inside of the toner particles include a method in which the charge control agent is added to a binder resin together with a coloring agent, and the mixture is kneaded and then pulverized (pulverized toner); or polymerizable. A method (polymerized toner) in which a charge control agent is added to a monomer to polymerize it to obtain a toner. In the case of being added to the inside of the toner particles, the amount of the charge control agent added is preferably 0.1 to 10 parts by mass, more preferably 100 parts by mass, based on 100 parts by mass of the binder resin. It is 0.2 to 5 parts by mass. On the other hand, when it is added to the surface of the toner particles, the amount of the charge control agent added is preferably 0.01 to 5 based on 100 parts by mass of the binder resin. It is added in such a manner that it is added in an amount of 0.01 to 2 parts by mass. Further, it is preferable to mechanically fix it to the surface of the toner particles.

Further, the charge control agent of the present embodiment may be used in combination with other known negatively chargeable charge control agents. Preferred charge control agents for use include azo-based iron complex or staggered salt, azo-chromium complex or staggered salt, azo-based manganese complex or staggered salt, and azo-based cobalt. a compound or a wrong salt, an azo zirconium complex or a wrong salt, a chromium complex or a wrong salt of a carboxylic acid derivative, a zinc complex or a wrong salt of a carboxylic acid derivative, or an aluminum wrong of a carboxylic acid derivative a zirconium complex or a wrong salt of a salt or a salt of a carboxylic acid. The above carboxylic acid derivative is preferably an aromatic hydroxycarboxylic acid, more preferably 3,5-di-t-butylsalicylic acid. Further, a boron complex or a wrong salt, a negatively chargeable resin type charge control agent, and the like can be given.

In the case where the charge control agent of the present embodiment and the other charge control agent are used in combination, the charge control agent other than the charge control agent of the present embodiment is preferably 0.1 to 10 mass based on 100 parts by mass of the binder resin. Share.

Any of the binder resins used in the toner of the present embodiment may be used as long as it is known. Examples of the binder resin include a vinyl polymer such as a styrene monomer, an acrylate monomer, or a methacrylate monomer, or a copolymer containing two or more of these monomers; and a polyester system; Polymer; polyol resin; phenol resin; polyoxygen tree Fat; polyurethane resin; polyamide resin; furan resin; epoxy resin; xylene resin; terpene resin; benzofuran-indene resin; polycarbonate resin; petroleum resin. The above copolymer can be produced by using a crosslinking agent.

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

Examples of the styrene-based monomer include styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, and 2,4-dimethyl Styrene, p-n-pentyl styrene, p-tert-butyl styrene, p-n-hexyl styrene, p-n-octyl styrene, p-n-decyl styrene, p-n-decyl styrene, p-dodecane Styrene derivatives such as styrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene.

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

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

As the other monomer forming the ethylene-based polymer and the copolymer, the following (1) to (18) can be used. (1) monoolefins such as ethylene, propylene, butylene, and isobutylene; (2) polyenes such as butadiene and isoprene; and (3) halogenated vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride. Ethylene; (4) vinyl acetate such as vinyl acetate, vinyl propionate or vinyl benzoate; (5) vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and isobutyl vinyl ether (6) vinyl ketones such as methyl vinyl ketone, hexyl vinyl ketone, and methyl isopropenyl ketone; (7) N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinyl anthracene, N-vinylpyrrolidone; (8) vinyl naphthalenes; (9) acrylonitrile , acrylic acid or methacrylic acid derivatives such as methacrylonitrile and acrylamide; (10) maleic acid, methyl maleic acid, itaconic acid, alkenyl succinic acid, fumaric acid , unsaturated dibasic acid such as meconic acid; (11) unsaturated dibasic acid anhydride such as maleic anhydride, methyl maleic anhydride, itaconic anhydride, alkenyl succinic anhydride; (12) maleic acid Acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, methyl maleic acid monomethyl ester, methyl maleic acid monoethyl ester, methyl maleene Unsaturated dibasic acid monoesters such as monobutyl phthalate, monomethyl itaconate, monomethyl stearyl succinate, monomethyl fumarate, monomethyl mebaconate; (13) cis-butane (1) an unsaturated dibasic acid diester such as dimethyl enedomethane or dimethyl fumarate; (14) an α,β-unsaturated acid such as crotonic acid or cinnamic acid; (15) butyric anhydride, cinnamon α,β-unsaturated acid anhydride such as acid anhydride; (16) the α,β-unsaturated acid and lower fat a mixed monomer having an acid, an alkenyl malonic acid, an alkenyl glutaric acid, an alkenyl adipic acid, an acid anhydride, and a monovalent ester such as a monovalent ester; (17) 2-hydroxyethyl acrylate; Acrylic acid or hydroxyalkyl methacrylate such as 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate; (18) 4-(1-hydroxy-1-methylbutyl)styrene, 4 a monomer having a hydroxyl group such as -(1-hydroxy-1-methylhexyl)styrene.

In the toner of the present embodiment, the vinyl polymer of the binder resin or the copolymer thereof may have a crosslinked structure which is crosslinked by 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 and 1,3-butylene glycol diacrylate; a diacrylate compound of an alkanediol such as 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate or neopentyl glycol diacrylate or Corresponding dimethacrylate compound; diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 二A diacrylate compound of an oxyalkylene glycol such as acrylate or dipropylene glycol diacrylate or a corresponding methacrylate compound.

Further, a diacrylate compound having a diol having an aromatic group or an ether bond or a corresponding dimethacrylate compound may also be used. For example, a polyester type diacrylate (trade name: MANDA (manufactured by Nippon Kayaku Co., Ltd.)) can be cited.

Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, and oligoester acrylate. An acrylate of an alcohol or a corresponding methacrylate; an allyl ester such as triallyl cyanurate or triallyl trimellitate or a guanamine.

The crosslinking agent is preferably used in an amount of 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, per 100 parts by mass of the other monomer component. Among these crosslinking agents, those which are preferably used in the resin for toner from the viewpoints of fixability and offset resistance include aromatic divinyl compounds (especially divinylbenzene). a diacrylate compound linked by an aromatic group and a bond chain containing one ether bond. Among these, a combination of a monomer which becomes a styrene-type copolymer and a styrene-acrylate type copolymer is preferable.

In the present embodiment, examples of the polymerization initiator used in the production of the ethylene-based polymer or copolymer include 2,2'-azobisisobutyronitrile and 2,2'-azobis ( 4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methyl Butyronitrile), 2,2'-azobisisobutyric acid dimethyl ester, 1,1'-azobis(1-cyclohexanecarbonitrile), 2-(aminomethylmercaptoazo)-isobutyl Nitrile, 2,2'-azobis(2,4,4-trimethylpentane), 2-phenylazo-2',4'-dimethyl-4'-methoxyvaleronitrile, 2,2'-azobis(2-methylpropane), methyl ethyl ketone peroxide, acetoxyacetone peroxide, cyclohexanone peroxide, etc., ketone peroxide, 2,2-double (peroxidation Tributyl)butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, peroxidation Tributyl cumene, dicumyl peroxide, α-(t-butylperoxy) cumene, isobutyl peroxide, octyl peroxide, cerium peroxide, lauric acid peroxide, 3,5,5-trimethylhexyl peroxide, benzammonium peroxide, m-tolyl peroxide, Diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, peroxycarbonate Di-2-ethoxyethyl ester, diethoxyisopropyl peroxydicarbonate, bis(3-methyl-3-methoxybutyl)peroxycarbonate, acetamidine cyclohexylsulfonyl peroxidation , tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy laurate, tert-butyl benzoate , tert-butyl isopropyl peroxycarbonate, di-tert-butyl peroxy isophthalate, tert-butyl peroxyallyl carbonate, isoamyl peroxy-2-ethylhexanoate, peroxidation Di-tert-butyl hexahydroterephthalate, tert-butyl peroxydicarboxylate, and the like.

In the case where the binder resin is a styrene-acrylate resin, the molecular weight distribution of the THF soluble component of the resin component by gel permeation chromatography (hereinafter abbreviated as GPC) has a molecular weight of 3,000 to 50,000 (quantity The resin having at least one peak in the region of the average molecular weight conversion and having at least one peak in the region having a molecular weight of 100,000 or more is preferable in terms of fixability, offset property, and preservability. Further, a binder resin having a molecular weight distribution of 100,000 or less of a THF soluble component of 50 to 90% is also preferable. Further, it is more preferably in the region of a molecular weight of 5,000 to 30,000, and preferably has a main peak in a region of 5,000 to 20,000.

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

The following may be mentioned as a monomer which comprises a polyester-type polymer.

Examples of the glycol component include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, and triethylene glycol. , 5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A or polymerized ethylene oxide, ring on bisphenol A A diol or the like obtained by a cyclic ether such as oxypropane.

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

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

When the binder resin is a polyester resin, it is preferably a molecular weight of 3,000 to 50,000 in the molecular weight distribution of the THF soluble component of the resin component in terms of fixability and offset resistance of the toner. There is at least one peak in the region, and a binder resin having a molecular weight of 100,000 or less of THF soluble component of 60 to 100% is also preferable. Further, it is more preferable that at least one peak exists in a region having a molecular weight of 5,000 to 20,000.

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

When the binder resin is a polyester resin, the acid value is preferably from 0.1 mgKOH/g to 100 mgKOH/g, more preferably from 0.1 mgKOH/g to 70 mgKOH/g, and still more preferably from 0.1 mgKOH/g to 50 mgKOH/g. . In addition, the acid value refers to the mass of potassium hydroxide necessary for neutralizing the free fatty acid in 1 g of the binder resin, and is measured in accordance with JIS K-0070.

Further, the hydroxyl value is preferably 30 mgKOH/g or less, more preferably 10 mgKOH/g to 25 mgKOH/g. Furthermore, the so-called hydroxyl value means that the binder resin is used for the neutralization using acetic anhydride. The mass of potassium hydroxide necessary for the acetic acid produced by the hydroxy group in g to be acetonitrile is measured in accordance with JIS K-0070.

In the present embodiment, two or more kinds of a non-crystalline polyester resin and a crystalline polyester resin may be used in combination. In this case, it is preferred to select a material in consideration of the compatibility of each resin.

The amorphous polyester resin is preferably one selected from the group consisting of polybasic carboxylic acid components, preferably aromatic carboxylic acid and polyol components.

The crystalline polyester resin is preferably a self-dicarboxylic acid component, preferably a combination of an aliphatic dicarboxylic acid and a glycol component.

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

In the case where a polyester polymer, a vinyl polymer, and another binder resin are used in combination, the resin having an acid value of 60% by mass or more of the entire binder resin is preferably 0.1 mgKOH/g to 50 mgKOH/g.

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

(1) The sample may be used by removing an additive other than the binder resin (polymer component), or calculating the acid value and content of the component other than the binder resin and the crosslinked binder resin. The pulverized product of the sample was accurately weighed from 0.5 g to 2.0 g, and the weight of the polymer component was defined as W (g). For example, when the acid value of the binder resin is measured from the toner, the acid value and content of the colorant or the magnetic substance are separately measured, and the acid value of the binder resin is calculated by calculation.

(2) Place the sample in a 300 (mL) beaker and add toluene/ethanol (volume ratio 4/1). The mixed solution was dissolved in 150 (mL).

(3) Using a 0.1 mol/L potassium hydroxide (KOH) ethanol solution, titration was carried out using a potentiometric titration apparatus.

(4) Using the amount of the potassium hydroxide solution at this time as S (mL), and measuring the blank sample, and using the potassium hydroxide solution at this time as B (mL), using the following formula (1) )Calculation. Where f is a coefficient of potassium hydroxide concentration.

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

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

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

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

Specific examples of the magnetic material include Fe ₃ O ₄ , γ-Fe ₂ O ₃ , ZnFe ₂ O ₄ , Y ₃ Fe ₅ O ₁₂ , CdFe ₂ O ₄ , Gd ₃ Fe ₅ O ₁₂ , CuFe ₂ O ₄ , PbFe ₁₂ O, NiFe ₂ O ₄ , NdFe ₂ O, BaFe ₁₂ O ₁₉ , MgFe ₂ O ₄ , MnFe ₂ O ₄ , LaFeO ₃ , iron powder, cobalt powder, nickel powder, etc., the above magnetic bodies may be used alone or in combination Use more than two types. A preferred magnetic material is a fine powder of triiron tetroxide or γ-ferric oxide.

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

The above-mentioned different element can be mixed with a salt of each of the different elements when the magnetic substance is formed, and inserted into the particles by pH adjustment. Further, it is possible to precipitate on the surface of the particles by adjusting the pH after the formation of the magnetic particles or by adjusting the pH of the salt of each element.

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

Further, as the magnetic body, it is preferable that the magnetic characteristics under application of 10 K Oersted are: coercive force of 20 Oersted to 150 Oersted, and saturation magnetization of 50 emu/g to 200 emu/g. The residual magnetization is 2emu/g~20emu/g.

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

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

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

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

As the cyan colorant, a copper phthalocyanine compound and a derivative thereof, a hydrazine, a basic dye lake compound can be used. Specifically, as the cyan coloring agent of the pigment system, CI Pigment Blue 2, 3, 15, 16, 17, CI Reducing Blue 6, CI Acid Blue 45 or a phthalocyanine skeleton is substituted for 1 to 5 phthalic acid. Copper phthalocyanine pigment of formamidine imine.

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

Examples of the orange pigment include red chrome yellow, molybdenum orange, permanent orange GTR, pyrazole orange, sulfur-resistant orange, benzidine orange G, indanthrene brilliant orange RK, and indanthrene bright orange GK. Examples of the violet pigment include manganese violet, fast violet B, and methyl violet lake. As Examples of the green pigment include chromium oxide, chrome green, pigment green, peacock green lake, and ultimate yellow green G. Examples of the white pigment include zinc white, titanium oxide, antimony white, and zinc sulfide. The amount of the coloring agent to be used is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the binder resin.

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

The resin-coated carrier contains a carrier core particle and a coating material as a resin covering the surface of the carrier core particle. The resin used in the coating material is preferably a styrene-acrylate resin such as a styrene-acrylate copolymer or a styrene-methacrylate copolymer, an acrylate copolymer or a methacrylate copolymer. Acrylate resin, fluororesin such as polytetrafluoroethylene, trifluoromonochloroethylene polymer, polyvinylidene fluoride, polyfluorene oxide resin, polyester resin, polyamide resin, polyvinyl butyral, acrylamide Base resin. Further, a resin which can be used as a coating (coating material) of a carrier, such as an ionic polymer resin or a polyphenylene sulfide resin, can be used. These resins may be used singly or in combination of plural kinds.

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

The use example of the magnetic material coated with the coating (coating agent) of the mixture of two or more types is (1) 12 parts by mass of dimethyldichloromethane and dimethyl with respect to 100 parts by mass of the titanium oxide fine powder. For the treatment of a mixture of base oil (mass ratio 1:5), (2) 20 parts by mass of dimethyl dichloromethane and dimethyl hydrazine oil (mass ratio 1:5) with respect to 100 parts by mass of the cerium oxide micropowder The mixture is treated as a mixture.

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

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

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

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

The resistance value of the carrier can adjust the degree of unevenness on the surface of the carrier and the amount of the resin to be coated to be 10 ⁶ Ω ‧ cm to 10 ¹⁰ Ω ‧ cm. The particle diameter of the carrier may be from 4 μm to 200 μm, preferably from 10 μm to 150 μm, more preferably from 20 μm to 100 μm. More preferably, the resin coated carrier has a 50% particle size of 20 μm to 70 μm.

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

The toner of the present embodiment may further contain a wax. In the present embodiment, the wax used is as follows. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax, sand wax, and the like, aliphatic hydrocarbon wax, oxidized polyethylene wax and the like An aliphatic hydrocarbon wax or such intercalated copolymer, a plant wax such as candelabra wax, carnauba wax, wood wax, jojoba wax, animal wax such as beeswax, lanolin, and cetyl wax. Mineral waxes such as ceresin, pure ceresin, petrolatum, waxes such as montanic acid ester wax and ricin wax, which are mainly composed of fatty acid esters, deoxidized carnauba wax and the like, some or all of fatty acid esters are deoxidized. By.

Examples of the wax include saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid or a linear alkyl carboxylic acid further having a linear alkyl group; brassic acid, citric acid, and strontium An unsaturated fatty acid such as oxalic acid; a saturated alcohol such as stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnaubaol, wax alcohol, methyl sterol or long-chain alkyl alcohol; a polyhydric alcohol such as sorbitol; Fatty amide such as ceramide, olefin amide, laurylamine; saturated fatty acid bis-amine such as methylene biguanide, ethyl bis-laurate, hexamethylene bis-lipidamine; An unsaturated fatty amide such as bis-indolylamine, hexamethylene bis-indoleamine, N,N'-dioleyl decylamine or N,N'-dioleyl hydrazine; Aromatic bis-amines such as meta-xylene distearylamine, N,N'-distearyl metabenzamide; calcium stearate, calcium laurate, zinc stearate, magnesium stearate a fatty acid metal salt; a wax obtained by grafting an aliphatic hydrocarbon wax with a vinyl monomer such as styrene or acrylate; a partial ester of a fatty acid such as tetradecanoic acid monoglyceride and a polyhydric alcohol; a compound; a methyl ester compound having a hydroxyl group obtained by hydrogenating a vegetable oil.

Examples of the wax which can be preferably used include a polyolefin obtained by radically polymerizing an olefin under high pressure, and a polyolefin obtained by purifying a low molecular weight by-product obtained by polymerizing a high molecular weight polyolefin; A polyolefin obtained by polymerizing a catalyst such as a 戚格勒 catalyst or a metallocene catalyst; a polyolefin obtained by polymerization using radiation, electromagnetic waves or light; and a low molecular weight polycondensation obtained by thermally decomposing a high molecular weight polyolefin Olefins; paraffin waxes, microcrystalline waxes, Fischer-Tropsch waxes; synthetic hydrocarbons synthesized by the Synthol method, the Hydrochol method, the Arge method, etc. Wax; a synthetic wax having a carbon number of one compound as a monomer, having a hydroxyl group a hydrocarbon wax having a functional group such as a carboxyl group; a mixture of a hydrocarbon wax and a hydrocarbon wax having a functional group; and the wax as a precursor by styrene, maleic acid ester, acrylate, methacrylic acid ester, A wax which is graft-modified with a vinyl monomer such as maleic anhydride.

Further, it is preferred to use such a wax to suppress a molecular weight distribution by a compression sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a solution crystallization method, or to remove a low molecular weight solid fatty acid, and to low. A molecular weight solid alcohol, a low molecular weight solid compound or other impurities.

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

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

Examples of the type of the wax having a plasticizing effect include a wax having a relatively low melting point or a wax having a molecular structure and a wax having a structure, or a wax having a structure having a polar group. A wax, a wax having a linear structure on a molecular structure, or a non-polar wax having no functional group. As a use example, a combination of a difference in melting point of two or more different waxes of 10 ° C to 100 ° C, a combination of a polyolefin and a graft-modified polyolefin, and the like can be given.

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

Further, in the case of a wax, a branched structure or a polar group having a functional group is relatively The plasticizer may be used for the modification by a component different from the main component, and the mold release effect may be exhibited by a linear structure, a non-polarity group having no functional group, or an unmodified straight line. As a preferable combination of the wax, a combination of a polyethylene homopolymer or copolymer containing ethylene as a main component and a polyolefin homopolymer or copolymer mainly composed of an olefin other than ethylene; polyolefin and grafting; a combination of a polyolefin; a combination of an alcohol wax, a fatty acid wax or an ester wax and a hydrocarbon wax; a Fischer-Tropsch wax or a combination of a polyolefin wax and a paraffin wax or a microcrystalline wax; a combination of a Fischer-Tropsch wax and a polyolefin wax; A combination of microcrystalline wax; a combination of carnauba wax, canary wax, rice bran wax or montan wax and a hydrocarbon wax.

In either case, it is preferred that the peak end temperature of the peak of the endothermic peak observed in the DSC measurement of the toner has a maximum peak in the region of 70 ° C to 110 ° C, more preferably 70 ° C to 110 ° C. The area has the peak top temperature of the largest peak. Thereby, the balance of toner preservability and fixability is easily obtained.

In the toner of the present embodiment, the total content of the waxes is preferably 0.2 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the binder resin.

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

In the present embodiment, the DSC measurement of the wax or the toner is preferably carried out by a high-precision internal thermal power compensation type differential scanning calorimeter. The method of measurement is carried out in accordance with ASTM D3418-82. In the present embodiment, the DSC curve measured when the temperature is raised at a temperature of 10 ° C/min after the temperature rise and the temperature reduction are obtained one time is used.

A fluidity improver can be added to the toner of the present embodiment. The fluidity improving agent improves (becomes easy to flow) the fluidity of the toner by being added to the surface of the toner. For example, fluorine black resin powder such as carbon black, fine vinylidene fluoride fine powder or polytetrafluoroethylene fine powder, fine powdered cerium oxide such as wet preparation cerium oxide or dry preparation cerium oxide, fine powder without titanium oxide, and the like, may be mentioned. The fine powder is not alumina and the surface treatment is carried out by using a decane coupling agent, a titanium coupling agent or a polyoxygenated oil to treat cerium oxide, treat titanium oxide, and treat oxidation. aluminum. Among them, preferred are fine powder of cerium oxide, fine powder of non-titanium oxide, fine powder of non-alumina, and more preferably, the surface treatment of cerium oxide is carried out by a decane coupling agent or a polyoxygenated oil. The particle size of the fluidity improver is preferably from 0.001 μm to 2 μm, more preferably from 0.002 μm to 0.2 μm as the average primary particle diameter.

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

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

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

Examples of the organic ruthenium compound include hydroxypropyltrimethoxydecane, phenyltrimethoxydecane, n-hexadecyltrimethoxydecane, n-octadecyltrimethoxydecane, and vinylmethoxydecane. Vinyl triethoxy decane, vinyl triethoxy decane, dimethyl vinyl chlorodecane, divinyl chloro decane, γ-methyl propylene methoxy propyl trimethoxy decane, hexamethyl bis Decane, trimethyl decane, trimethylchlorodecane, dimethyl dichloride Decane, methyltrichlorodecane, allyldimethylchlorodecane, allylphenyldichlorodecane, benzyldimethylchlorodecane, bromomethyldimethylchlorodecane, α-chloroethyltrichloride Decane, β-chloroethyltrichlorodecane, chloromethyldimethylchlorodecane, triorganosilyl mercaptan, trimethyldecyl mercaptan, triorganosilyl acrylate, vinyl dimethyl oxime Base decane, dimethyl ethoxy decane, trimethyl ethoxy decane, trimethyl methoxy decane, methyl triethoxy decane, isobutyl trimethoxy decane, dimethyl dimethoxy Decane, diphenyldiethoxydecane, hexamethyldioxane, 1,3-divinyltetramethyldioxane, 1,3-diphenyltetramethyldioxane, and each One molecule has 2 to 12 oxoxane units and the unterminated unit contains 0 to 1 dimethyl polyoxyalkylene bonded to the hydroxyl group on Si, respectively. Further, a polyoxygenated oil such as dimethylpolyphthalic acid oil can be mentioned. These may be used alone or in combination of two or more.

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

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

For the purpose of controlling the charge amount, etc., by means of polyoxynitride Treatment of paints, various modified polyoxyxylene varnishes, polyoxygenated oils, various modified polyoxygenated oils, decane coupling agents, decane coupling agents with functional groups, other organic hydrazine compounds, or various treatment agents good.

In the present embodiment, the charge control agent is combined with the additive and the toner as described above, by a Henschel mixer, a ball mill, a Nauta mixer, a V-type mixer, a W-type mixer, a high-speed mixer, etc. The mixture is thoroughly mixed and stirred, and the surface of the toner particles is uniformly subjected to external addition treatment, whereby the intended electrostatic charge developing toner can also be obtained.

The toner of the present embodiment is also stable to heat, and does not change due to heat during the electrophotographic process, and can maintain stable charging characteristics. Further, it can be uniformly dispersed in any of the binder resins, so that the charge distribution of the fresh toner is very uniform. Therefore, even if the toner of the present embodiment is untransferred or recovered toner (waste toner), there is almost no change in the saturated triboelectric charge amount and the charge distribution as compared with the fresh toner. On the other hand, in the case of recycling the waste toner generated from the electrostatic charge image developing toner of the present embodiment, a polyester resin containing an aliphatic diol is selected from the binder resin. The method of producing a toner by using a metal crosslinked styrene-acrylate copolymer as a binder resin and adding a large amount of a polyolefin thereto can further reduce the difference between the fresh toner and the waste toner.

The toner of the present embodiment can be produced by a known production method. When the production method is exemplified, it is preferred that the toner constituent material such as a binder resin, a charge control agent, and a colorant is sufficiently mixed by a mixer such as a ball mill, and the resulting mixture is heated by a hot roll kneader or the like. The kneading device is a method in which the kneading device is sufficiently kneaded, cooled and solidified, and classified by pulverization (pulverization method).

Further, it can also be produced by dissolving the above mixture in a solvent, atomizing it by spraying, drying and classifying it. Further, it can also be produced by mixing a specific material in a monomer constituting the binder resin, emulsification or preparing a suspension, and then polymerizing it to obtain a toner by a polymerization method. a toner manufacturing method in which a core material or a shell material is used in a so-called microcapsule toner containing a core material and a shell material These two methods contain specific materials. Further, if necessary, the desired additive and the toner particles are sufficiently mixed by a mixer such as a Henschel mixer, whereby the toner of the present embodiment can be produced.

The method for producing the toner of the present embodiment by the above pulverization method will be described in detail. First, the binder resin, the color former, the charge control agent, and other necessary additives are uniformly mixed. A known agitator such as a Henschel mixer, a high speed mixer, a ball mill or the like can be used for the mixing. The resulting mixture was subjected to hot melt kneading using a closed kneader or a single screw or twin screw extruder. After the kneaded material is cooled, it is coarsely pulverized by a crusher or a hammer mill, and further pulverized by a pulverizer such as a jet mill or a high-speed rotor rotary mill. Further, an air classifier is used, for example, an Elbow-Jet using an inertial grading method of the Coanda effect, a Microplex, a DS separator in a cyclone (centrifugal) classification method. Etc., grade to a specific granularity. Further, when the surface of the toner is treated with an external additive or the like, the toner and the external additive are stirred and mixed by a high speed mixer such as a Henschel mixer, a high speed mixer or the like.

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

If it is produced by an emulsion polymerization method, it is obtained by the above suspension polymerization method. Compared with the particles, the uniformity is excellent, but the average particle diameter is extremely small 0.1 μm to 1.0 μm. Therefore, depending on the case, so-called seed polymerization in which the particles are grown by adding the polymerizable monomer to the core is used. The method is either a method in which the emulsified particles are combined and melted to a suitable average particle diameter.

Since the production by the polymerization method does not undergo the pulverization step, it is not necessary to impart brittleness to the toner particles, and the low-softening point substance which is difficult to use in the previous pulverization method can be used in a large amount, so that the selection range of the material can be expanded. Since the release agent or the coloring agent which is a hydrophobic material is hard to be exposed on the surface of the toner particles, contamination of the toner carrying member, the photoreceptor, the transfer roller, and the fixing device can be reduced.

By producing the toner of the present embodiment by a polymerization method, characteristics such as image reproducibility, transferability, and color reproducibility can be further improved. Further, in order to cope with minute spots and to reduce the particle diameter of the toner, it is possible to easily obtain a toner having a steep particle size distribution.

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

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

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

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

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

The toner obtained by the above polymerization method tends to have less unevenness of the toner particles than the toner obtained by the pulverization method which is not subjected to special treatment, and is indefinite, so that it is increased. The contact area between the electrostatic latent image carrier and the toner increases the toner adhesion, and as a result, the internal contamination is small, and it is easy to obtain a higher image density and higher product. Quality image.

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

One of the values indicating the degree of unevenness of the toner particles is an average circularity. The average circularity (C) is obtained by dividing the circularity (Ci) of the following formula (2) and dividing the sum of the circularities of all the particles measured by the following formula (3). The value obtained by measuring the total number of particles (m).

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

The value of the above average circularity is preferably from 0.955 to 0.995, more preferably from 0.960 to 0.985. When the toner particles are adjusted such that the average circularity is within this range, there is a tendency that the transfer residual toner is less likely to be generated, and the retransfer tends to be less likely to occur.

In the case of the toner of the present embodiment, in terms of imageability and productivity of the toner, for example, a micron sizer (for example, manufactured by Shinko Co., Ltd.) is used. In the measurement of the particle size distribution measuring machine, in the case of pulverizing the toner, it is preferred that the particle diameter of the toner is in the range of 2 μm to 15 μm in terms of volume-based average particle diameter, more preferably 3 μm to 12 μm. Within the scope. When the average particle diameter is more than 15 μm, the resolution and the sharpness tend to be weakened. When the average particle diameter is less than 2 μm, the resolution is good, but the yield is deteriorated during the production of the toner. The problem of high cost or the tendency of the toner to scatter in the machine and soak in the skin affects health.

On the other hand, in the case of polymerizing the toner, it is preferably in the range of from 3 μm to 9 μm, more preferably in the range of from 4 μm to 8.5 μm, still more preferably in the range of from 5 μm to 8 μm. When the volume average particle diameter is less than 4 μm, the fluidity of the toner is lowered, the chargeability of each particle is liable to lower, and the charge distribution is broadened, so that it is liable to cause coverage of the background or overflow of the toner from the developer. Moreover, if it is less than 4 μm, it may become very difficult to clean. When the volume average particle diameter is more than 9 μm, the resolution is lowered, so that sufficient image quality may not be obtained, and it is difficult to satisfy the high image quality requirements in recent years.

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

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

Further, it is preferable that the particle diameter uniformity is high (volume average particle diameter/number average particle diameter is 1.00 to 1.30).

In the case of the toner for electrostatic charge development of the present embodiment, the specific surface area of the toner is preferably 1.2 m ² /g to 5.0 m ^{2 in the} measurement of the BET specific surface area of nitrogen as the desorbed gas. g. More preferably 1.5m ² /g~3.0m ² / g. For the measurement of the specific surface area, for example, a BET specific surface area measuring device (for example, manufactured by Shimadzu Corporation, FlowSorb II 2300) is used to remove the adsorbed gas on the surface of the toner at 50 ° C for 30 minutes. The nitrogen was quenched and nitrogen gas was again adsorbed, and the temperature was again raised to 50 ° C, and the value obtained from the degassing amount at this time was defined as the specific surface area.

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

In the case of the toner of the present embodiment, the true specific gravity in the case of the non-magnetic toner is preferably from 0.9 g/cm ³ to 1.2 g/cm ³ , and in the case of the magnetic toner, due to the magnetic powder The type and content vary, but it is preferably from 0.9 g/cm ³ to 4.0 g/cm ³ . The true specific gravity of the toner was calculated as follows. 1.00 g of the toner was accurately weighed, placed in a 10 mm Φ tablet former, and compression-molded while applying a pressure of 200 kgf/cm ² (1961 N/cm ² ) under vacuum. The height of the cylindrical molded product was measured by a micrometer to calculate the true specific gravity.

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

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

In the present embodiment, the SF-1 and SF-2 indicating the shape factor of the toner are, for example, an optical microscope (for example, BH-2 manufactured by Olympus Co., Ltd.) equipped with a CCD camera, in a field of view 30. The toner particle group magnified to 1000 times is sampled in a left-right manner, and the obtained image is transmitted to an image analysis device (for example, LUZEXF FS manufactured by NIRECO Co., Ltd.), and the same operation is repeated to the relative toner particles. The shape factor is calculated for about 1000. 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)

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

SF-2=(PM ² /4Aπ)×100 (5)

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

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

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

In the toner of the embodiment, the dielectric loss tangent of the toner is preferably 1.0 × 10 ^-3 to 15.0 × 10 ^-3 in the case of the non-magnetic toner, and in the case of the magnetic toner. It varies depending on the type and content of the magnetic powder, but is preferably 2 × 10 ^-3 to 30 × 10 ^-3 . In the case of the dielectric loss tangent of the toner in this case, the toner particles were compression-molded to prepare a disk-shaped test piece having a diameter of 50 mm and a thickness of 2 mm, which was fixed to the solid electrode and used for LCR test. The device (for example, manufactured by Hewlett Packard Co., Ltd. 4284A), which is obtained by measuring at a frequency of 1 kHz and a peak-to-peak voltage of 0.1 kV, is defined as a dielectric loss tangent of the toner.

In the toner of the present embodiment, the Izod impact value of the toner is preferably from 0.1 kg‧cm/cm to 30 kg‧cm/cm. The Ehrlich impact value of the toner in this case is a test piece in which a toner particle is thermally fused to a plate shape, and is measured in accordance with JIS Standard K-7110 (impact test method for a hard plastic).

In the toner of the present embodiment, the melt index (MI value) of the toner is preferably from 10 g/10 min to 150 g/10 min. The melt index (MI value) of the toner in this case is measured based on JIS standard K-7210 (method A). In this case, the measurement temperature was 125 ° C, and the load was set to 10 kgf (98 N).

In the toner of the present embodiment, the melting start temperature of the toner is preferably from 80 ° C to 180 ° C, and the temperature at which the film is lowered by 4 mm is preferably from 90 ° C to 220 ° C. In this case, the toner particles are compression-molded to produce a cylindrical test piece having a diameter of 10 mm and a thickness of 20 mm, and is fixed to a heat-melting property measuring device such as a rheometer (flow) In the tester) (for example, CFT-500C manufactured by Shimadzu Corporation), the value at which the melting starts and the piston starts to decrease when measured at a load of 20 kgf/cm ² (196 N/cm ² ) is defined as the melting start of the toner. temperature. Further, the same measurement was carried out, and the temperature at which the piston was lowered by 4 mm was defined as a temperature of 4 mm.

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

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

In the toner of the present embodiment, the melt viscosity of the toner is preferably from 1,000 poise to 50,000 poise, more preferably from 1,500 poise to 38,000 poise. In the case of the toner melt viscosity in this case, the toner particles are compression-molded to produce a cylindrical test piece having a diameter of 10 mm and a thickness of 20 mm, and is fixed to a hot melt characteristic measuring device such as a rheometer (for example, On the CFT-500C manufactured by Shimadzu Corporation, the value measured at a load of 20 kgf/cm ² (196 N/cm ² ) was defined as the melt viscosity of the toner.

The solvent of the toner of the present embodiment dissolves the residual component, and is preferably 0% by mass to 30% by mass as the THF-insoluble component, 0% by mass to 40% by mass as the ethyl acetate-insoluble component, and 0% as the chloroform-insoluble component. Mass%~30% by mass. In the solvent-dissolved residual component herein, 1 g of the toner was uniformly dissolved/dispersed in 100 ml of each solvent of THF, ethyl acetate, and chloroform, and the solution or dispersion was subjected to pressure filtration, and the filtrate was dried for quantification. From this value, the ratio of the insoluble matter to the organic solvent in the toner is calculated, and the value thus obtained is defined as the solvent-dissolved residual component of the toner.

The toner of the embodiment can be used as a one-component display as one of image forming methods Shadow mode. The one-component development method refers to a method in which a thinned toner is supplied to a latent image carrier to develop a latent image. The toner is usually formed by using a toner conveying member, a toner layer thickness controlling member, and a toner replenishing auxiliary member, and the replenishing auxiliary member and the toner conveying member and the toner layer thickness controlling member are used. The device is in contact with the toner conveying member.

The case where the toner of the present embodiment is applied to the two-component developing method will be specifically described. The two-component developing method is a method in which a toner and a carrier (having a function as a charging imparting material and a toner conveying material) are used, and the carrier may use the above-mentioned magnetic material or glass beads. The developer (toner and carrier) is stirred by a stirring member to generate a specific amount of charge, and is transferred to the developing portion by a magnetic roller or the like. The developer is held on the surface of the roller by magnetic force on the magnetic roller to form a magnetic brush controlled to a proper height by a layer such as a developer control panel. The developer moves on the roller accompanying the rotation of the developing roller, and contacts the electrostatic charge latent image holding body or faces at a fixed interval in a non-contact state to visualize the latent image development. In the case of development in a non-contact state, generally, by generating a DC electric field between the developer and the latent image holder, a driving force for the toner to fly in a space of a fixed interval can be obtained, but for development Clearer images can also be applied in a way that overlaps the communication.

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

[Examples]

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

[Example 1]

The analysis of the purity, composition ratio, and the like of the conformational isomer of the compound represented by the formula (1), such as a cone type or a partial cone type, is carried out by HPLC. The HPLC measurement conditions are as follows.

Device: 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/trifluoroacetic acid=450/400/150/2 (v/v/v/v), flow rate: 1.0 mL/min, measurement wavelength: 296 nm, injection amount: 1 μL, sample concentration: 1000 mg/L .

Purification of these compounds is carried out by purification by column chromatography, adsorption purification by silica gel, activated carbon, activated clay, or the like, by recrystallization or crystallization of a solvent. Further, the identification of the compound was carried out by NMR (Nuclear Magnetic Resonance) analysis.

[Synthesis Example 1 (Synthesis of Composition A)]

In a four-liter four-necked flask equipped with a stirrer, a cooling tube and a thermometer, all of R ₁ to R ₄ in the formula (1) are added as a hydrogen atom, and all of R ₅ to R ₆ are a third butyl group, X ₁ to X _{4 .} 45.5 g of a compound having a sulfur atom, 70 ml of DMF, and 620 mL of THF were added, and sodium hydride (60% (w/w) in oil) was added with stirring at room temperature, and the mixture was stirred for 0.5 hour. 172 g of benzyl bromide was added dropwise and heated, and the mixture was stirred under reflux for 2 hours. After allowing to cool to room temperature, 100 mL of water was added and the mixture was stirred for 30 minutes. After distilling off THF under reduced pressure, 300 mL of water and 400 mL of chloroform were added, and an organic layer was taken by liquid separation operation. The organic layer was washed successively with dilute hydrochloric acid, water and saturated aqueous sodium chloride, and dried over anhydrous magnesium sulfate, and concentrated to dryness, whereby R ₁ to R ₄ in the formula (1) were all benzyl, R _{5 .} All of ~R ₈ are 68 g of a yellow solid of composition A of a compound of a third butyl group and all of X ₁ to X ₄ being a sulfur atom. As a result of HPLC analysis, the composition ratio of the composition A was 70%, the configuration of the cone-shaped stereo configuration was 70%, and the configuration of the partial cone-shaped configuration was 9%, 1,3-alternate. The conformational isomer of the stereo configuration is 6%.

[Embodiment 2] [Synthesis Example 2 (Synthesis of Composition B)]

In a four-liter four-necked flask equipped with a stirrer, a cooling tube and a thermometer, all of R ₁ to R ₄ in the formula (1) are added as a hydrogen atom, and R ₅ to R _{6 are} all a third butyl group, X ₁ to X _{4 .} 100 g of a compound of all sulfur atoms, 3 L of acetone, 190 g of benzyl bromide, and 118 g of sodium carbonate were heated and stirred at 50 ° C for 48 hours. After cooling to room temperature, the crystals which were concentrated by filtration were washed with water, and then dissolved in 1 L of chloroform. After washing with dilute hydrochloric acid, water and saturated brine, the mixture is dried over anhydrous magnesium sulfate and concentrated to obtain R ₁ and R ₃ in the formula (1) as a benzyl group, and R ₂ and R ₄ are a hydrogen atom. The white crystal I 90 g (yield 73%) of the compound in which all of R ₅ to R ₈ are a tributyl group and all of X ₁ to X ₄ are sulfur atoms. As a result of HPLC analysis, the stereoisomer of syn-1, type 3 (for example, refer to Non-Patent Document 1) was 97.8%.

The structure was identified by measuring the NMR spectrum of the obtained white crystal I.

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) )

The obtained white crystal I 89.7 g and DMF 1.8 L were added to a 5-liter four-necked flask equipped with a stirrer, a cooling tube, and a thermometer, and sodium hydride was added while stirring at room temperature (60% (w/w) in oil) 5.46 g, and further stirred for 0.5 hours. After cooling to 5 ° C, 17.2 g of benzyl bromide was added, followed by stirring 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 taken out by filtration, dissolved in 3.9 L of chloroform, and washed sequentially with dilute hydrochloric acid, water, and saturated brine. After drying over anhydrous magnesium sulfate, it was concentrated, whereby 98 g of a yellow oil was obtained. Then, it is purified by column chromatography (carrier: silicone, eluent: hexane/chloroform), and then subjected to crystallization using methanol, followed by washing with methanol, followed by drying under reduced pressure, thereby obtaining a general formula ( 1) 54.6 g of white crystal II in which one of R ₁ to R ₄ is a hydrogen atom and the remaining three are benzyl groups, all of R ₂ are a third butyl group, and all of X ₁ to X ₄ are sulfur atoms. The rate is 56%). As a result of HPLC analysis, the purity was 99.4%.

The structure was identified by measuring the NMR spectrum of the obtained white crystal II.

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)

50 g of the obtained white crystals II, 4 L of acetone, 81.8 g of cesium carbonate, and 40.7 g of benzyl bromide were placed in a four-necked flask equipped with a stirrer, a cooling tube, and a thermometer, and heated, and the mixture was stirred under reflux for 2 hours. After cooling to room temperature, the precipitated crystals were taken by filtration and washed with water. After dissolving in chloroform, washing with dilute hydrochloric acid, water, and saturated brine, followed by drying with anhydrous magnesium sulfate, and concentrating to obtain a yellow oil, all of R ₁ to R ₄ in the formula (1) are benzyl. A composition B of 54 g (yield 99%) of a compound in which all of R ₅ to R ₈ are a tributyl group and all of X ₁ to X ₄ are sulfur atoms. As a result of HPLC analysis, the composition ratio of the composition B was 13% for the conformal isomer of the cone-shaped stereo configuration and 85% for the partial isomer of the cone-shaped stereo configuration.

[Example 3] [Synthesis Example 3 (Synthesis of Conical Isomers of Cone Type)]

68 g of the composition A synthesized in Example 1 was dissolved in 500 mL of chloroform, and purified by column chromatography (carrier: silicone, eluent: hexane/chloroform), followed by crystallization using methanol, and further used. After washing with methanol, it is dried under reduced pressure to obtain all of R ₁ to R ₄ in the formula (1) as a benzyl group, R ₅ to R _{8 are} all a third butyl group, and all of X ₁ to X ₄ are sulfur atoms. Compound, and as a conformational isomer of a cone-shaped stereo configuration (purity: 98.8%), white crystal III 36 g (yield 52.8%).

The structure was identified by measuring the NMR spectrum of the obtained white crystal III.

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 a partial cone-shaped conformational isomer)]

The composition B synthesized in Example 2 was purified by column chromatography (carrier: silicone, eluent: hexane/chloroform), and then subjected to crystallization using methanol, followed by washing with methanol, and then subtracted. Pressing and drying, thereby obtaining a compound in which all of R ₁ to R ₄ in the formula (1) are a benzyl group, R ₅ to R _{8 are} all a third butyl group, and all of X ₁ to X ₄ are sulfur atoms, and as a partial cone A configuration of the stereoisomer of the stereo configuration (purity 99.1%) of white crystal IV 45.2 g (yield 84.4%).

The structure was identified by measuring the NMR spectrum of the obtained white crystal IV.

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 (comparison of Comparative Composition C)]

In a four-liter four-necked flask equipped with a stirrer, a cooling tube and a thermometer, all of R ₁ to R ₄ in the formula (1) are added as a hydrogen atom, and all of R ₅ to R ₆ are a third butyl group, X ₁ to X _{4 .} 84.0 g of a compound having a sulfur atom, 800 ml of DMF, and 102 g of potassium carbonate were added dropwise to a solution of 112.3 g of benzyl chloride at room temperature, followed by heating and stirring at 100 ° C for 8 hours. After cooling to room temperature, the reaction liquid was added to 3 L of dilute hydrochloric acid, and the precipitated coarse crystals were taken by filtration. Further, the dispersion is washed by water, followed by washing with methanol, and then dried, whereby R ₁ to R ₄ in the formula (1) are all benzyl, and R ₅ to R _{8 are} all third. 118 g of an off-white crystal of the composition C of a compound of butyl and X ₁ to X _{4 which are} all sulfur atoms (yield 98.2%). As a result of HPLC analysis, the composition ratio of the composition C was that the configuration of the cone-shaped stereo configuration was 1%, and the configuration of the partial cone-shaped configuration was 16%, 1,2-alternating. The conformational isomer of the stereo configuration is 4%, and the conformational isomer of the 1,3-alternate stereo configuration is 77%.

[Comparative Example 2] [Comparative Synthesis Example 2 (Synthesis of Configurational Isomers of 1,3-Alternating Type)]

Comparatively, 118 g of the composition C synthesized in Synthesis Example 1 was dissolved in 600 mL of THF while heating, and then cooled to room temperature. The precipitated crystals are removed by filtration, washed with THF, and dried to obtain all of R ₁ to R ₄ in the formula (1) as a benzyl group, and R ₅ to R _{8 are} all a third butyl group, X. ₁ to X ₄ were all compounds of a sulfur atom, and 58.4 g of a white plate crystal V (yield 46.3%) as a configurational isomer of 1,3-alternate type (purity: 99.1%).

The structure was identified by measuring the NMR spectrum of the obtained white plate crystal V.

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)

For Synthesis Examples 1 to 4 and Comparative Synthesis Examples 1 and 2, the contents of the respective configuration isomers are shown in Table 1. Further, in the table, the "mole ratio" is a configuration of the four configurational isomers of the compound represented by the general formula (1), and the configuration of the conical stereo configuration and the partial conical stereo configuration The value obtained by dividing the total number of the structures by the number of moles of the four configurational isomers can be calculated by the following formula (6).

(Morby) = (Moole number of conformational isomer of cone-shaped stereo configuration + Moir number of configurational isomer of partial cone-shaped stereo configuration) / (Construction of cone-shaped stereo configuration) Moir number of isomers + Mottle number of conformational isomers of partial cone-shaped stereo configuration +1, Moir number of configuration isomers of 2-alternating stereo configuration + 1,3-alternate Moir number of conformational isomers of a stereo configuration) × 100 (%) (6)

[Example 5] [Manufacture of Non-Magnetic Toner 1]

91 parts of styrene-acrylate copolymer resin (manufactured by Mitsui Chemicals, Inc., trade name: CPR-100, acid value: 0.1 mgKOH/g), composition A 1 part, carbon black (manufactured by 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 Viscol 550P) were melt-mixed by a 130 ° C heating and mixing device (biaxial extrusion kneading machine). The cooled mixture was coarsely pulverized by a hammer mill, then finely pulverized by a jet mill, and classified to obtain a non-magnetic toner having a volume average particle diameter of 9 ± 0.5 μm.

[Evaluation of Non-Magnetic Toner 1]

The toner was mixed and shaken with a non-coated ferrite carrier (F-150 manufactured by POWDERTECH Co., Ltd.) in a ratio of 4 to 100 parts by mass (toner: carrier) to negatively charge the toner. Thereafter, the measurement of the saturated charge amount was carried out in an environment of a temperature of 25 ° C and a humidity of 50% by a blown powder type charge amount measuring device. Further, the same evaluation was carried out in the case of mixing with a ferrite carrier (manufactured by POWDERTECH Co., Ltd., F96-150). The results are summarized in Table 2.

Further, the environmental stability under high temperature and high humidity (30 ° C, 85% RH) was evaluated. The environmental stability is evaluated in the following four stages according to the rate of decrease in the saturated charge amount in the environment of high temperature and high humidity with respect to the temperature of 25 ° C and a humidity of 50%. The results are summarized in Table 2.

◎: Stable (saturated charge rate reduction rate is less than 5%)

○: Slightly stable (saturation charge rate reduction rate is 5% or more and less than 10%)

△: slightly unstable (saturation charge rate reduction rate is 10% or more and less than 15%)

×: unstable (saturation charge rate reduction rate is 15% or more)

[Embodiment 6] [Manufacture and Evaluation of Non-Magnetic Toner 2]

In the production method of the fifth embodiment, the composition A is replaced with the composition B, and the non-magnetic toner 2 is prepared, and the saturated powder is charged by the blown powder type charge amount measuring device at a temperature of 25 ° C and a humidity of 50%. Determination of the amount. The same evaluation was also carried out in the case of mixing with a ferrite carrier (manufactured by POWDERTECH Co., Ltd., F96-150). Further, the environmental stability was evaluated. The results are summarized in Table 2.

[Embodiment 7] [Manufacture and Evaluation of Non-Magnetic Toner 3]

In the production method of Example 5, the composition A was replaced with white crystal III (conical isomer of cone type) to prepare a non-magnetic toner 3, and the temperature was measured at 25 ° C by a blown powder type charge amount measuring device. The measurement of the saturated charge amount is carried out in an environment with a humidity of 50%. The same evaluation was also carried out in the case of mixing with a ferrite carrier (manufactured by POWDERTECH Co., Ltd., F96-150). Further, the environmental stability was evaluated. The results are summarized in Table 2.

[Embodiment 8] [Manufacture and Evaluation of Non-Magnetic Toner 4]

In the production method of Example 5, the composition A was replaced with a white crystal IV (a partial cone-shaped configuration isomer), and a non-magnetic toner 4 was prepared by a blown powder type charge amount measuring device at a temperature of 25 The measurement of the saturated charge amount was carried out in an environment of ° C and a humidity of 50%. The same evaluation was also carried out in the case of mixing with a ferrite carrier (manufactured by POWDERTECH Co., Ltd., F96-150). Further, the environmental stability was evaluated. The results are summarized in Table 2.

[Comparative Example 3] [Comparative Manufacturing and Evaluation of Non-Magnetic Toner 1]

In the production method of Example 5, the composition A was replaced with the composition C, and the comparative non-magnetic toner 1 was prepared, and the mixture was subjected to saturation at a temperature of 25 ° C and a humidity of 50% by a blown powder type charge amount measuring device. Determination of the amount of charge. The same evaluation was also carried out in the case of mixing with a ferrite carrier (manufactured by POWDERTECH Co., Ltd., F96-150). Further, the environmental stability was evaluated. The results are summarized in Table 2.

[Comparative Example 4] [Comparative Manufacturing and Evaluation of Non-Magnetic Toner 2]

In the production method of Example 5, the composition A was replaced with a white plate crystal V (a 1,3-alternating configuration isomer) to prepare a comparative non-magnetic toner 2, which was charged by the blown powder. The measuring device performs the measurement of the saturated charge amount in an environment of a temperature of 25 ° C and a humidity of 50%. The same evaluation was also carried out in the case of mixing with a ferrite carrier (manufactured by POWDERTECH Co., Ltd., F96-150). Further, the environmental stability was evaluated. The results are summarized in Table 2.

From the above results, it was confirmed that in Examples 5 to 8, the charge amount became high, and excellent environmental stability was exhibited.

[Embodiment 9] [Preparation of Resin Dispersion]

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

[Preparation of Charge Control Agent Dispersion]

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

[Preparation of Polymerized Toner]

Into a reaction vessel equipped with a thermometer, a pH meter, and a stirrer, 125 parts of the above resin dispersion, 1.0 part by weight of a 20% by mass aqueous solution of sodium dodecylbenzenesulfonate, and 125 parts of ion-exchanged water were added, and the liquid temperature was controlled at 30. While stirring at °C for 30 minutes at 150 rpm. The pH was adjusted to 3.0 by adding a 1% by mass aqueous solution of nitric acid, and further stirred for 5 minutes. While dispersing by a homogenizer (manufactured by IKA Japan, Ultra Turrax T-25), 0.125 parts of polyaluminum chloride was added, and the liquid temperature was raised to 50 ° C, and further dispersed for 30 minutes. After 62.5 parts of the above resin dispersion and 4.0 parts of the above-mentioned charge control agent dispersion were added, a 1% by mass aqueous solution of nitric acid was added to adjust the pH to 3.0, and further dispersed for 30 minutes. A 5% by mass aqueous sodium hydroxide solution was added while stirring at 400 to 700 rpm using a stirrer. The stirring was continued until the volume average particle diameter of the toner became 9.5 μm. After raising the temperature of the liquid to 75 ° C, the mixture was further stirred for 2 hours, and it was confirmed that the volume average particle diameter was 6.0 μm, and the particle shape was spheroidized, and then rapidly cooled using ice water. It was taken by filtration and subjected to dispersion washing with ion-exchanged water. The dispersion washing was repeated until the conductivity of the filtrate after dispersion was 20 μS/cm or less. Thereafter, it was dried by a dryer at 40 ° C to obtain toner particles. The obtained toner was sieved through a sieve of 166 mesh (mesh 90 μm) as a toner for evaluation.

[Evaluation]

The mixture was mixed and vibrated at a ratio of 100 parts of the obtained evaluation toner to 100 parts of a non-coated ferrite carrier (F-150 manufactured by POWDERTECH Co., Ltd.), and the toner was negatively charged, and then blown out. The powder charge amount measuring device measures the saturated charge amount in an environment of a temperature of 25 ° C and a humidity of 50%. Further, the same evaluation was carried out in the case of mixing with a ferrite carrier (manufactured by POWDERTECH Co., Ltd., F96-150). Further, the environmental stability was evaluated. The results are summarized in Table 3.

[Embodiment 10]

In the production method of Example 9, except that the composition B was used instead of the composition A to prepare a charge control agent dispersion, a toner was prepared under the same conditions as in Example 9, and the saturation charge amount was measured. Further, the environmental stability was evaluated. The results are summarized in Table 3.

[Example 11]

In the production method of Example 9, a toner was prepared and saturated under the same conditions as in Example 9 except that white crystal III (conical isomer of cone type) was used instead of composition A to prepare a charge control agent dispersion. Determination of the amount of charge. Further, the environmental stability was evaluated. The results are summarized in Table 3.

[Embodiment 12]

In the production method of Example 9, except that the white crystal IV (partial tapered configuration isomer) was used instead of the composition A to prepare a charge control agent dispersion, the same strip as in Example 9 was used. The toner was produced and the saturation charge amount was measured. Further, the 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 composition C was used instead of the composition A to prepare a charge control agent dispersion, and the measurement of the saturated charge amount was carried out. Further, the environmental stability was evaluated. The results are summarized in Table 3.

[Comparative Example 6]

In the production method of Example 9, except that the white plate crystal V (the 1,3-alternating configuration isomer) was used instead of the composition A to prepare a charge control agent dispersion, the same conditions as in Example 9 were carried out. The toner was measured for the saturation charge amount. Further, the environmental stability was evaluated. The results are summarized in Table 3.

[Comparative Example 7]

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

From the above results, it is clear that a compound represented by the general formula (1) containing a configurational isomer having a conical stereo configuration or a partial conical stereo configuration of 50 mol% or more is used. The polymerized toner which is a charge control agent of an active ingredient has a high charge amount and exhibits excellent environmental stability.

[Industrial availability]

The charge control agent of the present invention has significantly higher chargeability and superior environmental stability than previous charge control agents. It is completely colorless and is most suitable as a color toner, especially as a polymerized toner. Further, it is possible to provide an extremely useful toner which does not contain a heavy metal such as a chromium compound which is a concern in environmental problems.

Claims (11)

A charge control agent containing at least one of the compounds represented by the following formula (1) as an active ingredient, and 50 mol% or more of the above compound is a configuration of a conical stereo configuration or a partial conical stereo configuration Isomer, [In the formula (1), R ₁ , R ₂ , R ₃ and R ₄ may be the same or different from each other, and represent a substituted or unsubstituted linear or branched alkane having 1 to 20 carbon atoms; a group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group, and R ₅ , R ₆ , R ₇ and R ₈ may be the same or different from each other, and represent a substituted or unsubstituted group. a substituted linear 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 or different from each other, and represent a sulfur atom, a sulfinyl group or a sulfonyl group]. The charge control agent of claim 1, wherein in the above formula (1), all of X ₁ , X ₂ , X ₃ and X ₄ are a sulfur atom. The charge control agent according to claim 1 or 2, wherein, in the above formula (1), R ₁ , R ₂ , R ₃ and R ₄ may be the same or different from each other, and are selected from the group consisting of aromatic hydrocarbon groups or aromatic impurities. The ring group is a group of a linear or branched alkyl group having 1 to 4 carbon atoms as a substituent. A charge control agent containing at least one of the compounds represented by the following formula (2) as an active ingredient, and 50 mol% or more of the above compound is a configuration of a conical stereo configuration or a partial conical stereo configuration Isomer, [In the formula (2), R ₁ , R ₂ , R ₃ and R ₄ may be the same or different from each other, and represent an unsubstituted alkyl group having a linear or branched alkyl group having 10 to 20 carbon atoms; a linear or branched alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted alkyl group having an aromatic hydrocarbon group or an aromatic heterocyclic group as a substituent The aromatic heterocyclic group, R ₅ , R ₆ , R ₇ and R ₈ may be the same or different from each other, and represents a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms; The substituted or unsubstituted aromatic hydrocarbon group, or the substituted or unsubstituted aromatic heterocyclic group, all of X ₁ , X ₂ , X ₃ and X ₄ represent a sulfur atom]. A charge control agent containing at least one of the compounds represented by the following formula (3) as an active ingredient, and 50 mol% or more of the above compound is a configuration of a conical stereo configuration or a partial conical stereo configuration Isomer, [In the formula (3), R ₁ , R ₂ , R ₃ and R ₄ may be the same or different from each other, and represent a straight chain having 1 to 4 carbon atoms having an aromatic hydrocarbon group or an aromatic heterocyclic group as a substituent. a branched or branched alkyl group, and R ₅ , R ₆ , R ₇ and R ₈ may be the same or different from each other, and represent an unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms. X ₁ , X ₂ , X ₃ and X ₄ all represent a sulfur atom]. The charge control agent according to any one of claims 1 to 5, wherein 60 mol% or more of the above compound is a conformational isomer of a conical stereo configuration or a partial conical stereo configuration. The charge control agent according to any one of claims 1 to 5, wherein 70 mol% or more of the above compound is a conformational isomer of a conical stereo configuration or a partial conical stereo configuration. The charge control agent according to any one of claims 1 to 5, wherein 80 mol% or more of the above compound is a conformational isomer of a conical stereo configuration or a partial conical stereo configuration. The charge control agent according to any one of claims 1 to 5, wherein 90 mol% or more of the above compound is a conformational isomer of a conical stereo configuration or a partial conical stereo configuration. A toner containing one or two or more of the charge control agents according to any one of claims 1 to 9, a colorant, and a binder resin. A polymerized toner containing one or two or more of the charge control agents according to any one of claims 1 to 9, a colorant, and a binder resin.