JP5882788B2 - Toner production method - Google Patents

Description

  The present invention relates to a toner manufacturing method for developing an electrostatic latent image in an image forming method such as an electrophotographic method, an electrostatic recording method, or a toner jet method.

In recent years, electrophotographic apparatuses are required to achieve both high image quality and energy saving. One means for achieving this is to perform image formation with a small amount of toner. As an example, the amount of applied toner is set to 0.35 mg / cm ² or less, the toner consumption is reduced, and defects (blisters, etc.) that occur during fixing are suppressed, and a stable and wide color reproduction range is achieved. There is a proposal to form a quality color image (Patent Document 1).
According to this proposal, it is described that the content of the colorant is preferably 8% by mass or more in order to achieve a sufficient coloring power even when the amount of applied toner is reduced (low TMA). There is.
It is also known from other known literatures that it is essential to increase the content of the colorant in order to form an image with a smaller amount of applied toner than in the past (Patent Document 2).
When such a toner with an increased amount of colorant is used in a conventional electrophotographic system, a certain effect can be expected in terms of fixing characteristics, but the saturation of the image and the color gamut may be narrowed. This is presumably because, as a result of increasing the amount of the colorant, in the step of dispersing the colorant, the colorant concentration in the treatment liquid is increased and the viscosity is increased, thereby reducing the dispersibility of the colorant. Even if the dispersion of the colorant is sufficiently dispersed, the colorant may aggregate at the stage of producing the toner. As a result, the dispersion state of the colorant in the toner becomes insufficient, the hue changes, the saturation of the image is lowered, and the color gamut is narrowed.
Therefore, in order to form an image with a smaller amount of toner than before, it is necessary to improve the dispersibility of the colorant while suppressing the increase in viscosity even in a high concentration colorant dispersion. In addition, there is a production method that can provide a toner having high coloration power and high dispersibility of the colorant in the toner even when the content of the colorant is finally high, without agglomeration even at the stage of producing the toner. Long-awaited.
A number of methods using a pigment dispersant have been proposed as means for improving the dispersibility of the colorant. As an example, there is a proposal of using a pigment dispersant having a basic skeleton compatible with a binder resin and at least one aromatic skeleton (Patent Document 3). However, when a low molecular weight pigment dispersant having a weight average molecular weight (Mw) of 2500 or less as described in the examples of this proposal is used, the ability to inhibit aggregation of pigments due to the molecular chain of the pigment dispersant. May become weaker. In that case, in order to suppress aggregation and increase dispersion stability, it is necessary to use a large amount of a pigment dispersant with respect to the colorant, which is not preferable. If the amount of the pigment dispersant used is large, not only will the chargeability be adversely affected by the polarity of the pigment dispersant, but also when a low molecular weight pigment dispersant is used, the pigment dispersant will ooze out to the toner surface. As a result, the storage stability may be lowered and the member may be contaminated.
There is also a proposal to use a polymer pigment dispersant as a means for enhancing the dispersibility of the colorant (Patent Document 4). In the case of using a polymer dispersant as exemplified in this proposed example, the force to inhibit aggregation between pigments does not work sufficiently due to the polymer chain, and a large amount of pigment dispersant is used to compensate for this. There is a need. There is a demand for a production method that uses a pigment dispersant exhibiting a high adsorptive power with respect to a colorant, and can realize a decrease in viscosity and an improvement in dispersibility in a colorant dispersion step with a small amount.
Quinacridone colorants and naphtholazo colorants used as magenta colorants have strong cohesive strength and the colorants themselves are hard, making it difficult to disperse and use at the same time. It is known that when it is dispersed with, it is easy to thicken (Patent Document 5).
Also, Pigment Yellow 155, which is a yellow colorant, is a colorant that has a strong cohesiveness in the colorant itself and is easily thickened in a liquid medium.
In particular, when these colorants are used to produce a toner having a high colorant content, there has been a problem of further increase in viscosity and deterioration of dispersibility in the step of dispersing the colorant.
As a method for dispersing the hardly dispersible colorant in a liquid medium, a disperser using media particles is generally used. However, in order to produce a toner having a high content of colorant, if the colorant dispersion becomes a high concentration and high viscosity in the step of dispersing the colorant, the media particles may cause packing. When packing occurs, not only the dispersion efficiency is lowered, but also the quality is deteriorated due to excessive temperature rise and the apparatus is stopped due to overload. In a media disperser, when small-diameter media particles are used, the collision probability between media increases and the dispersion efficiency is greatly improved. On the other hand, as the particle size of the media particles becomes smaller, adverse effects such as a decrease in dispersibility due to the high-viscosity treatment liquid become prominent.
Further, in the step of dispersing the colorant, a disperser provided with a media separation mechanism has been proposed as a disperser that can disperse the colorant uniformly and finely and can be processed with a large capacity (Patent Document 6).
In particular, the disperser in the dispersion system as shown in FIGS. 1 and 2 of Patent Document 6 is a device that has a high filling rate of media particles and can disperse the colorant efficiently and finely. However, in order to produce a toner with a high content of colorant, when the colorant dispersion becomes a high concentration and high viscosity in the step of dispersing the colorant, a disperser with high dispersibility as described above is used. Even if used, the performance cannot be utilized. This is because the movement of the media particles is hindered by the high-viscosity liquid, and the collision probability is reduced, or packing of the media particles occurs, thereby reducing the dispersion performance.
There is a need for a production method that exhibits high dispersibility without media particle packing even when a high-concentration colorant dispersion is used, even when small-diameter media particles are used. In addition, even if a disperser with high dispersibility is used, there is a demand for a production method that exhibits high dispersibility without hindering packing of media particles and movement of media particles.

JP 2005-195664 A JP 2011-70217 A JP 2010-152208 A JP 2010-020019 A JP 2011-215111 A JP 2011-81220 A

  An object of the present invention is to provide a toner manufacturing method that solves the above-described problems. Specifically, it is possible to increase the dispersibility of the colorant while suppressing thickening even in a high-concentration colorant dispersion, and in the toner generation stage, the colorant does not aggregate in the toner. It is an object of the present invention to provide a production method for efficiently and stably producing a toner having a finer and more homogeneous colorant dispersion, resulting in a higher image density and excellent chargeability and storage stability.

［式（１）中、Ｒ_１、Ｒ_２、及びＡｒのいずれかは、単結合又は連結基を介してポリマー成分が結合する構造を有し、
Ｒ_１は、アルキル基、フェニル基、ＯＲ_４基又はＮＲ_５Ｒ_６基を表し、Ｒ_４乃至Ｒ_６は、それぞれ独立して、水素原子、アルキル基、フェニル基又はアラルキル基を表す。Ｒ_１がポリマー成分と結合する場合、単結合又は連結基を介して結合し、Ｒ_１に結合する連結基は、アミド基、エステル基、ウレタン基、ウレア基、アルキレン基、フェニレン基、−Ｏ−、−ＮＲ_３−及び−ＮＨＣＨ（ＣＨ_２ＯＨ）−からなる群より選ばれる二価の連結基であり、Ｒ_３は、水素原子、アルキル基、フェニル基又はアラルキル基を表す。
Ｒ_２は、アルキル基、フェニル基、ＯＲ_８基、又はＮＲ_９Ｒ_１０基を表し、Ｒ_８乃至Ｒ_１０は、それぞれ独立して、水素原子、アルキル基、フェニル基又はアラルキル基を表す。Ｒ_２がポリマー成分と結合する場合、単結合又は連結基を介して結合し、Ｒ_２に結合する連結基は、アルキレン基、フェニレン基、−Ｏ−、−ＮＲ_７−及び−ＮＨＣＨ（ＣＨ_２ＯＨ）−からなる群より選ばれる二価の連結基であり、Ｒ_７は、水素原子、アルキル基、フェニル基又はアラルキル基を表す。
Ａｒは、アリール基を表し、Ａｒがポリマー成分と結合する場合、単結合又は連結基を介して結合し、Ａｒに結合する連結基は、アミド基、エステル基、ウレタン基、ウレア基、アルキレン基、フェニレン基、−Ｏ−、−ＮＲ_３−及び−ＮＨＣＨ（ＣＨ_２ＯＨ）−からなる群より選ばれる二価の連結基であり、Ｒ_３は、水素原子、アルキル基、フェニル基又はアラルキル基を表す。
前記単結合又は連結基が、Ｒ_１、Ｒ_２、又はＡｒに結合する場合は、Ｒ_１、Ｒ_２、又はＡｒの水素原子と置換して結合する。］
該着色剤がＣ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １２２、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｖｉｏｌｅｔ １９、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ３１、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １５０、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ２６９、及びＣ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ １５５からなる群より選ばれる１種以上を含有し、
該着色剤分散液中の着色剤の濃度が、１０質量％以上２５質量％以下であり、
該着色剤分散工程において、個数平均粒径０．０５ｍｍ以上０．８ｍｍ以下のメディア粒子を使用したメディア分散機を用いて着色剤を分散させることを特徴とするトナーの製造方法。に関する。 The inventors of the present invention have intensively studied to solve the above problems and have completed the present invention.
That is, the present invention performs a colorant dispersion treatment on a colorant mixed solution containing a liquid medium, a colorant, and an azo compound represented by the following general formula (1) using a media disperser to disperse the colorant. A method for producing a toner comprising producing a toner in an aqueous medium, comprising a colorant dispersion step for obtaining a liquid,

[In the formula (1), any one of R ₁ , R ₂ and Ar has a structure in which a polymer component is bonded via a single bond or a linking group,
R ₁ represents an alkyl group, a phenyl group, an OR ₄ group or an NR ₅ R ₆ group, and R _{4 to} R ₆ each independently represent a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. When R ₁ is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to R ₁ is an amide group, ester group, urethane group, urea group, alkylene group, phenylene group, -O A divalent linking group selected from the group consisting of —, —NR ₃ — and —NHCH (CH ₂ OH) —, and R ₃ represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group;
R ₂ represents an alkyl group, a phenyl group, an OR ₈ group, or an NR ₉ R ₁₀ group, and R _{8 to} R ₁₀ each independently represent a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group. When R ₂ is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to R ₂ is an alkylene group, a phenylene group, —O—, —NR ₇ — and —NHCH (CH ₂ R ₇ represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
Ar represents an aryl group, and when Ar is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to Ar is an amide group, an ester group, a urethane group, a urea group, or an alkylene group. , A phenylene group, —O—, —NR ₃ — and —NHCH (CH ₂ OH) —, a divalent linking group selected from the group consisting of R ₃ is a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. Represents.
When the single bond or linking group is bonded to R ₁ , R ₂ , or Ar, it is bonded to a hydrogen atom of R ₁ , R ₂ , or Ar. ]
The colorant is C.I. I. Pigment Red 122, C.I. I. Pigment Violet 19, C.I. I. Pigment Red 31, C.I. I. Pigment Red 150, C.I. I. Pigment Red 269, and C.I. I. Containing one or more selected from the group consisting of Pigment Yellow 155,
The concentration of the colorant in the colorant dispersion is 10% by mass or more and 25% by mass or less,
In the colorant dispersion step, a colorant is dispersed using a media disperser using media particles having a number average particle diameter of 0.05 mm or more and 0.8 mm or less. About.

  According to the present invention, it is possible to improve the dispersibility of the colorant while suppressing thickening even in a high-concentration colorant dispersion, and the colorant does not aggregate even in the toner production stage. As a result, it is possible to provide a production method for efficiently and stably producing a toner having a finer and more uniform colorant dispersion and having a high image density and excellent chargeability and storage stability.

Illustration of a distributed system incorporating a media distribution machine Cross section inside the casing of the media disperser Enlarged view of the media particle separator located inside the media disperser

The method for producing the toner of the present invention (hereinafter also simply referred to as the production method of the present invention) comprises a liquid dispersion medium, a colorant, and a colorant mixture containing the azo compound represented by the above general formula (1). Is a toner production method for producing toner in an aqueous medium, comprising a colorant dispersion step of obtaining a colorant dispersion by carrying out a dispersion treatment of the colorant.
In the production method of the present invention, specifically, the toner is produced by the following method (i) or (ii).
(I) A colorant mixed solution containing a polymerizable monomer, a colorant and the azo compound represented by the above general formula (1) is subjected to a dispersion treatment of the colorant using a media disperser to disperse the colorant. To prepare a colorant dispersion (the colorant dispersion step). A polymerizable monomer, a polar resin, a release agent, and the like are added to and mixed with the obtained colorant dispersion as necessary to prepare a polymerizable monomer composition. The obtained polymerizable monomer composition is granulated in an aqueous medium, and the polymerizable monomer contained in the granulated particles is polymerized to produce toner particles (hereinafter referred to as suspension weight). Also called legal).
(Ii) A colorant mixed solution containing an organic solvent, a colorant and the azo compound represented by the general formula (1) is subjected to a colorant dispersion treatment using a media disperser, and the colorant is dispersed and colored. A colorant dispersion is prepared (the colorant dispersion step). To the resulting colorant dispersion, a binder resin and, if necessary, a release agent are added and dissolved to prepare a toner composition. The obtained toner composition is granulated in an aqueous medium, and an organic solvent contained in the granulated particles is removed to produce toner particles (hereinafter also referred to as a dissolution suspension method).
Therefore, in the case of the suspension polymerization method, the liquid medium used in the colorant dispersion step is preferably a polymerizable monomer for constituting the toner binder resin described later. The organic solvent is preferably an organic solvent capable of dissolving a binder resin for the toner described later.

The colorant used in the present invention is a quinacridone colorant, a naphtholazo colorant, and an acetoacetanilide colorant. These colorants are difficult to disperse and are easy to thicken during dispersion.
Examples of the quinacridone colorant include a pigment composition represented by the following general formula (30), and these can be used alone or in combination.

［式３０中の、Ｘ_１及びＸ_２は、それぞれ独立して、Ｈ、ＣＨ_３、又はＣｌを表す。］

[In Formula 30, X ₁ and X ₂ each independently represent H, CH ₃ , or Cl. ]

Among these, C.I. I. Pigment Red 122, C.I. I. Pigment
Violet 19 (each according to the name described in the color index 4th edition) is used from the viewpoint of physical stability such as hue and light resistance and the high adsorption power of the azo compound.

  Examples of the naphtholazo colorant include pigment compositions represented by the following general formula (31), and these can be used alone or in combination.

［式（３１）中の、Ｒ_２５、Ｒ_２６、及びＲ_２７はそれぞれ、水素原子、アルキル基、アルコキシ基、ハロゲン原子、ニトロ基、アニリド、及びスルファモイル基から選ばれる置換基を示す。Ｒ_２８は下記の群より選ばれ、下記置換基Ｒ_２９乃至Ｒ_３２は水素原子、ハロゲン原子、アルキル基、アルコキシ基、ニトロ基から選ばれる置換基を示す。］

[In the formula (31), R ₂₅ , R ₂₆ and R ₂₇ each represent a substituent selected from a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group, an anilide and a sulfamoyl group. R ₂₈ is selected from the following group, and the following substituents R _{29 to} R ₃₂ represent a substituent selected from a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, and a nitro group. ]

  Among these, C.I. I. Pigment Red 31, C.I. I. Pigment Red 150, C.I. I. Pigment Red 269 (each according to the name described in Color Index 4th edition) is used from the viewpoint of improving color developability and charging characteristics and from the viewpoint of high adsorption power of the azo compound.

  Examples of the acetoacetanilide colorant include C.I. I. Pigment Yellow 155 is used and is represented by the following structural formula (33).

C. I. Pigment Yellow 155 is excellent in light resistance and heat resistance, and is used from the viewpoint of high adsorption power of the azo compound.
As described above, in the production method of the present invention, the colorant is C.I. I. Pigment Red 122 (hereinafter also referred to as PR122), C.I. I. Pigment Violet 19 (hereinafter also referred to as PV19), C.I. I. Pigment Red 31 (hereinafter also referred to as PR31), C.I. I. Pigment Red 150 (hereinafter also referred to as PR150), C.I. I. Pigment Red 269 (hereinafter also referred to as PR269), and C.I. I. 1 or more types selected from the group consisting of Pigment Yellow 155 (hereinafter also referred to as PY155).

Hereinafter, the azo compound used in the present invention will be described in detail.
First, the structure represented by the general formula (1) has tautomers represented by the general formulas (T1) and (T2) as shown below. These tautomers are also within the scope of the present invention.

［式（Ｔ１）及び（Ｔ２）中のＲ_１、Ｒ_２、及びＡｒは、式（１）におけるＲ_１、Ｒ_２、及びＡｒと各々同意義である。］

_[R 1, _{R 2,} and Ar in formula (T1) and (T2) are as defined respectively for _R 1, _{R 2,} and Ar in Formula (1). ]

The azo compound represented by the general formula (1) will be described in detail.
In the general formula (1), any one of R ₁ , R ₂ , and Ar has a structure in which a polymer component is bonded via a single bond or a linking group,
R ₁ represents an alkyl group, a phenyl group, an OR ₄ group or an NR ₅ R ₆ group, and R _{4 to} R ₆ each independently represent a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. When R ₁ is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to R ₁ is an amide group, ester group, urethane group, urea group, alkylene group, phenylene group, -O A divalent linking group selected from the group consisting of —, —NR ₃ — and —NHCH (CH ₂ OH) —, and R ₃ represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group;
R ₂ represents an alkyl group, a phenyl group, an OR ₈ group or an NR ₉ R ₁₀ group, and R _{8 to} R ₁₀ each independently represent a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. When R ₂ is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to R ₂ is an alkylene group, a phenylene group, —O—, —NR ₇ — and —NHCH (CH ₂ R ₇ represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
Ar represents an aryl group, and when Ar is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to Ar is an amide group, an ester group, a urethane group, a urea group, or an alkylene group. , A phenylene group, —O—, —NR ₃ — and —NHCH (CH ₂ OH) —, a divalent linking group selected from the group consisting of R ₃ is a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. Represents.
When the single bond or linking group is bonded to R ₁ , R ₂ , or Ar, it is bonded to a hydrogen atom of R ₁ , R ₂ , or Ar.

R ₁ and R ₂ in the general formula (1) are not particularly limited as long as they do not inhibit the resonance structure of the tautomer, and can be arbitrarily selected from the substituents and hydrogen atoms listed above.
In the present invention, as the alkyl group in R ₁ and R ₂ in the general formula (1),
For example, straight chain such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclohexyl group, etc. And a branched or cyclic alkyl group.
In the present invention, examples of the aralkyl group in R _{1 to} R ₂ in the general formula (1) include a benzyl group and a phenethyl group.
In the present invention, R ₁ is an alkyl group having 1 to 6 carbon atoms, a phenyl group, an NH ₂ group, an OCH ₃ group, or an OCH ₃ C ₆ H ₅ group from the viewpoint of affinity for the colorant. Can be suitably exemplified. In addition, when R ₁ is bonded to the polymer component, it is bonded through a single bond or a linking group. Examples of the linking group include an amide group, an ester group, a urethane group, a urea group, an alkylene group, a phenylene group, and —O—. A divalent linking group selected from the group consisting of, -NH- and -NHCH (CH ₂ OH)-can be preferably exemplified.
Incidentally, the single bond or a linking group, when bound to R ₁ is bonded is replaced with a hydrogen atom of R _1.
Furthermore, the substituent of R _{1 in} the general formula (1) may be further substituted with a substituent as long as the affinity for the colorant is not significantly impaired. In this case, the substituent which may be substituted is a halogen atom, a nitro group, an amino group, a hydroxyl group, a cyano group, a trifluoromethyl group, or the like.

In the present invention, from the viewpoint of affinity for the colorant, a case where R ₂ is an NR ₉ R ₁₀ group, R ₉ is a hydrogen atom, and R ₁₀ is a phenyl group can be preferably exemplified. This is because the effect of the π-electron interaction is improved without inhibiting the effect of the polarity of the azo compound. Specifically, a π plane that causes a π electron interaction is formed by an intramolecular hydrogen bond between a hydrogen atom of R ₉ and an oxygen atom derived from a carbonyl group adjacent to R ₁ , and further derived from a phenyl group of R ₂ There is also a π plane, and there are two π planes. This is because the effect of π electron interaction is improved.
In particular, a naphthol azo colorant is composed of a π plane formed by each of a naphthyl group and a phenyl group existing across the azo bond of the colorant, and two π planes present between the azo bond of the azo compound and an Ar group. Since the origin π plane has a very similar positional relationship, it is adsorbed by a strong π electron interaction. As for the acetoacetanilide colorant, when R ₂ in the azo compound is an NR ₉ R ₁₀ group, R ₉ is a hydrogen atom, and R ₁₀ is a phenyl group, for example, a part of PY155 and an azo compound Have similar structures, the mutual π planes adsorb with strong interaction. Further, regarding the quinacridone colorant, when R ₂ in the azo compound is an NR ₉ R ₁₀ group, R ₉ is a hydrogen atom, and R ₁₀ is a phenyl group, the azo compound forms a wide π plane, It strongly adsorbs by the π plane and π electron interaction of quinacridone colorants.
As described above, the azo compound is strongly adsorbed to the naphtholazo colorant, quinacridone colorant, or acetoacetanilide colorant (particularly PY155), thereby reducing the viscosity and improving the dispersibility in the colorant dispersion step. realizable. Further, the colorant does not agglomerate in the toner production stage, and the colorant dispersion in the toner becomes finer and more uniform. As a result, it is possible to produce a toner having a high image density and excellent chargeability and storage stability.

On the other hand, when R ₂ is bonded to the polymer component, it is bonded through a single bond or a linking group. The linking group bonded to R ₂ is preferably a divalent linking group selected from the group consisting of an alkylene group, a phenylene group, —O—, —NH—, and —NHCH (CH ₂ OH) —.
Further, in the case _{where R 2} is bound to the polymer component, _{R 2} is _NR 9 _{R 10} group, and _{R 9} is a hydrogen _atom, and _{R 10} is a phenyl group, the phenyl group is a divalent linking group Thus, the mode of binding to the polymer component can be suitably exemplified. Furthermore, the aspect whose said coupling group is -NH- or -O- can be illustrated suitably.
This is because, in particular, the π-electron interaction of the azo compound including Ar is stronger than when Ar in the general formula (1) is bonded to the polymer component. That is, when Ar is bonded to the polymer component, the polymer component interferes with the electron cloud of π electrons of Ar, and the π electron, polarity, and the above three resonances of the azo skeleton partial structure in the general formula (1) This is because the effect of the structure is not maximized. On the other hand, when R ₂ is an NR ₉ R ₁₀ group, R ₉ is a hydrogen atom, R ₁₀ is a phenyl group, and the phenyl group is bonded to the polymer component via a divalent linking group The π electron of the phenyl group of R ₁₀ can reduce the influence of the azo skeleton portion of the polymer component in the general formula (1) on the electron cloud. That is, the effects of the three resonance structures of the general formulas (1), (T1), and (T2) can be substantially reduced without the π electron and polarity of the azo skeleton partial structure in the general formula (1). . Therefore, the effect of the present invention is maximized.
The above linking group, when bound to R ₂ is bonded through substitution of the hydrogen atom of R _2.

In the present invention, Ar in the general formula (1) represents an aryl group, and examples thereof include a phenyl group and a naphthyl group.
Ar in the general formula (1) may be further substituted with a substituent as long as it does not inhibit the resonance structure and does not significantly inhibit the affinity for the colorant. In this case, examples of the substituent that may be substituted include an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group, a cyano group, a trifluoromethyl group, a carboxyl group, a carboxylic acid ester group, and a carboxylic acid amide group. It is done.
Further, when Ar is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to Ar is an amide group, ester group, urethane group, urea group, alkylene group, phenylene group, -O. A divalent linking group selected from the group consisting of —, —NH— and —NHCH (CH ₂ OH) — can be preferably exemplified.
As described above, when a single bond or a linking group is bonded to R ₁ , R ₂ , or Ar, the bond is bonded to a hydrogen atom of R ₁ , R ₂ , Ar, or a hydrogen atom of a substituent of Ar. To do.

  In the present invention, the azo compound represented by the general formula (1) is preferably an azo compound represented by the following general formula (2) from the viewpoint of affinity for the colorant.

In the present invention, in the general formula (2), any of R ₁ , R ₂ , R _{11 to} R ₁₅ has a structure in which a polymer component is bonded through a single bond or a linking group.
In addition, R ₁ and R ₂ , and the linking group bonded to R ₁ and R ₂ are the same as those represented by the general formula (1).
R _{11 to} R ₁₅ each independently represent a hydrogen atom, a COOR ₁₆ group or a CONR ₁₇ R ₁₈ group. R _{16 to} R ₁₈ each independently represents a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group.
The alkyl group in R _{16 to} R ₁₈ is preferably an alkyl group having 1 to 6 carbon atoms. For example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, n -Linear, branched or cyclic alkyl groups such as hexyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclohexyl group and the like. Among these, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are preferable from the viewpoint of preventing a decrease in affinity with the colorant due to steric hindrance.
Examples of the aralkyl group in R _{16 to} R ₁₈ include a benzyl group and a phenethyl group.
In the general formula (2), any one of R ₁ , R ₂ , R _{11 to} R ₁₅ is bonded to the polymer component via a single bond or a linking group. When R _{11 to} R ₁₅ are bonded to a polymer component, they are bonded through a single bond or a linking group, and the linking group bonded to R _{11 to} R ₁₅ is an amide group, an ester group, a urethane group, a urea group, an alkylene group. Preferred examples include a divalent linking group selected from the group consisting of a group, a phenylene group, —O—, —NH—, and —NHCH (CH ₂ OH) —.
When the _single bond or linking group is bonded to R ₁ , R ₂ , R _{11 to} R ₁₅ , it is bonded to the hydrogen atom of R ₁ , R ₂ , R _{11 to} R ₁₅ .

R _{11 to} R ₁₅ in the general formula (2) can be selected from a hydrogen atom, a COOR ₁₆ group, and a CONR ₁₇ R ₁₈ group. From the viewpoint of affinity for the colorant, at least one of R _{11 to} R ₁₅ It is preferable that one is a COOR ₁₆ group or a CONR ₁₇ R ₁₈ group.
For example, in the case of a quinacridone colorant also known as a colorant having a strong hydrogen bonding property, at least one of R _{11 to} R ₁₅ is a COOR ₁₆ group or a CONR ₁₇ R ₁₈ group, Since the azo compound of the present invention is hydrogen-bonded to the carbonyl group of the agent or the hydrogen atom of the secondary amine, it is more strongly adsorbed. In the case of PY155, in addition to the π-electron interaction between PY155 and the azo compound of the present invention, two ester groups substituted with the phenyl group at the end of PY155 interact with COOR ₁₆ group and CONR ₁₇ R ₁₈ group. As a result, the adsorption power is further increased.
On the other hand, in the case of a naphthol azo colorant having an amide bond site (PR31, PR150, PR269), when at least one of R _{11 to} R ₁₅ of the azo compound of the present invention is a CONR ₁₇ R ₁₈ group, the colorant These amide bond sites are preferable because they cause an interaction and further increase the adsorptive power.

R _{16 to} R ₁₈ in the general formula (2) can be arbitrarily selected from the substituents and hydrogen atoms listed above, but from the viewpoint of affinity for the colorant, R ₁₆ is a methyl group, _It is preferable that ₁₇ and R ₁₈ are a hydrogen atom or a methyl group. At this time, not only steric hindrance does not occur, but also the presence of an ester bond or amide bond increases the hydrogen bond to the colorant and the adsorptive power due to polarity.

  Examples of the combination of substituents in the general formula (1) will be described with reference to examples, but are not limited thereto. In the case where the general formula (1) is represented by the following general formula (3) or (4), the affinity for the colorant is further improved.

For quinacridone colorants, the position of the azo bond site and amide group bonded to the phenyl group that does not bond to the polymer component via the linking group are in the m-position as shown in general formula (3). However, it may be o-position or p-position.
When the position of the amide group is at the m-position, it is most effective because it is in an optimal positional relationship for hydrogen bonding to the carbonyl group of the quinacridone colorant and the hydrogen atom of the secondary amine.
In the above general formula (4), the positions of the azo bond site bonded to the phenyl group not bonded to the polymer component via the linking group and the two COOCH ₃ groups are in the o-position and the m-position. However, it may be the case where two COOCH ₃ groups are present at an arbitrary position.
In the said General formula (3) and (4), L represents the bivalent coupling group for couple | bonding with a polymer component. The linking group L is not particularly limited as long as it is a divalent linking group, but from the group consisting of an alkylene group, a phenylene group, —O—, —NH—, and —NHCH (CH ₂ OH) —. The bivalent coupling group chosen is illustrated suitably.
The bonding position of L in the above general formulas (3) and (4) (substitution position with the hydrogen atom of the phenyl group) is any position in the o-position, m-position, or p-position with respect to the amide group. But you can. The affinity for the colorant due to the difference in these substitution positions is the same.

In order for the azo compound of the present invention to maintain a good dispersion state of the colorant in the toner, the polymer component must be maintained in a state where the molecular chain is sufficiently expanded in the binder resin of the toner. For this purpose, the polymer component of the azo compound must be compatible with the binder resin used in the toner. Here, the compatibility with the binder resin means compatibility with the binder resin and ease of familiarity. If the compatibility between the azo compound and the binder resin used in the toner is poor, the azo compounds will aggregate together and the molecular chain of the polymer component will contract, and the molecular chain will not expand sufficiently, so that sufficient three-dimensional A repulsive effect cannot be obtained, and aggregation of the colorant cannot be suppressed.
Therefore, for example, when the binder resin is a vinyl resin, the polymer component of the azo compound is preferably composed mainly of a vinyl resin. On the other hand, when the binder resin is a polyester resin, the polymer component of the azo compound is preferably a polyester resin as a main component.
In the case of producing a toner by the dissolution suspension method, it is preferable to select a polymer component of the azo compound having a structure having an affinity for the organic solvent used in the production of the toner.

  As described above, in the polymer component in the present invention, when the binder resin used in the toner is a vinyl resin, the polymer component of the azo compound is preferably composed mainly of the vinyl resin. Examples of the polymer component having the vinyl resin as a main component include a polymer or copolymer containing a monomer unit represented by the following general formula (5) as a constituent component. In the present invention, a copolymer is preferable.

［式（５）中、Ｒ_１９は水素原子又は炭素原子数が１若しくは２のアルキル基を表す。Ｒ_２０はフェニル基、カルボキシル基、カルボン酸エステル基、カルボン酸アラルキルエステル基又はカルボン酸アミド基を表す。］

[In Formula (5), R ₁₉ represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms. R ₂₀ represents a phenyl group, a carboxyl group, a carboxylic acid ester group, a carboxylic acid aralkyl ester group or a carboxylic acid amide group. ]

R ₁₉ in the general formula (5) is preferably a hydrogen atom or a methyl group from the viewpoint of polymerizability of the monomer unit.
R ₂₀ in the general formula (5) is preferably a carboxylic acid ester group, a carboxylic acid amide group, a phenyl group, or a carboxyl group, but the dispersibility and compatibility of the azo compound in the binder resin constituting the toner. From the viewpoint, a phenyl group, a carboxylic acid ester group, or a carboxylic acid amide group is preferable.
Although it does not specifically limit as said carboxylic acid ester group or carboxylic acid aralkyl ester group, For example, methyl ester group, ethyl ester group, n-propyl ester group, isopropyl ester group, n-butyl ester group, isobutyl Examples of ester groups include ester groups, sec-butyl ester groups, tert-butyl ester groups, dodecyl ester groups, 2-ethylhexyl ester groups, stearyl ester groups, phenyl ester groups, benzyl ester groups, and 2-hydroxyethyl ester groups. .
Examples of the carboxylic acid amide group include amide groups such as N-methylamide group, N, N-dimethylamide group, N, N-diethylamide group, N-isopropylamide group, N-tert-butylamide group, and N-phenylamide group. Is mentioned.
In addition, the substituent of R ₂₀ in the general formula (5) may be further substituted, and it must inhibit the polymerizability of the monomer unit or significantly reduce the solubility of the azo compound. There is no particular limitation. In this case, examples of the substituent that may be substituted include an alkoxy group, an amino group, and an acyl group.

Although the copolymer which contains the monomer unit represented by the said General formula (5) as a structural component is illustrated more concretely, it is not limited to these.
The polymer component in the present invention is a copolymer containing a monomer unit selected from the group consisting of the following general formulas (6-1), (6-2), (6-3) and (6-4) as a constituent component. Preferred examples include coalescence.

［式（６−１）中、Ｒ_２１は、水素原子又は炭素原子数が１乃至２のアルキル基を表し、Ｒ_２２は、炭素原子数が１乃至２２のアルキル基又は炭素原子数が７乃至８のアラルキル基を表す。ｌは、０又は正の整数値を表す。］

[In Formula (6-1), R ₂₁ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R ₂₂ represents an alkyl group having 1 to 22 carbon atoms or 7 to 7 carbon atoms. 8 represents an aralkyl group. l represents 0 or a positive integer value. ]

R ₂₁ in the general formula (6-1) is preferably a hydrogen atom or a methyl group from the viewpoint of polymerizability of the monomer unit.
The alkyl group represented by R ₂₂ in the general formula (6-1) is an alkyl group having 1 to 22 carbon atoms, or the number of carbon atoms from the viewpoint of dispersibility and compatibility with the binder resin constituting the toner. Is preferably an aralkyl group having 7 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 7 to 8 carbon atoms. In addition, this alkyl group may take any structure of a linear structure, a branched structure, or a cyclic structure.
On the other hand, examples of the aralkyl group in R ₂₂ include a benzyl group, an α-methylbenzyl group, and a phenethyl group.

［式（６−２）中、Ｒ_３３は、水素原子、又は炭素原子数が１乃至２のアルキル基を表す。ｍは、０又は正の整数値を表す。］

[In the formula (6-2), R ₃₃ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. m represents 0 or a positive integer value. ]

［式（６−３）中、Ｒ_３４は、水素原子、又は炭素原子数が１乃至２のアルキル基を表す。ｎは、０又は正の整数値を表す。］

[In the formula (6-3), R ₃₄ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. n represents 0 or a positive integer value. ]

［式（６−４）中、Ｒ_３５は、水素原子、又は炭素原子数が１乃至２のアルキル基を表し、Ｒ_３６及びＲ_３７は、それぞれ独立して、水素原子、炭素原子数１乃至４のアルキル基、又はフェニル基を表す。ｐは、０又は正の整数値を表す。］

[In the formula (6-4), R ₃₅ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R ₃₆ and R ₃₇ each independently represent a hydrogen atom, or 1 to 2 carbon atoms. 4 represents an alkyl group or a phenyl group. p represents 0 or a positive integer value. ]

The polymer component is a binder resin constituting the toner by changing the ratio of the monomer units represented by the general formula (5) or the general formulas (6-1) to (6-4). And the compatibility of the azo compound can be controlled. For example, when the main resin constituting the binder resin is a styrene resin, R ₂₀ in the general formula (5) is a monomer unit represented by a phenyl group (for example, the general formula (6-2) ), The compatibility of the binder resin and the azo compound can be improved.
Similarly, when the binder resin constituting the toner is a polyester resin, the compatibility of the binder resin and the azo compound can be improved if the polymer component is a polymer containing a polyester resin. As described above, when the compatibility between the polymer component and the binder resin constituting the toner is high, the polymer chain in the azo compound can be maintained in a sufficiently widened state, and thus the steric repulsion effect is large. The dispersion state of the colorant can be maintained in a good state.
The polymer component in the azo compound is a vinyl polymer resin, polyester, polyurethane, polyamide resin, or a hybrid resin in which a plurality of them are chemically bonded as long as the compatibility with the binder resin constituting the toner is not significantly impaired. Any polymer can be used.
Examples of the polymerization form of the polymer component in the azo compound include a random copolymer, an alternating copolymer, a periodic copolymer, and a block copolymer. The polymer component may have any of a linear structure, a branched structure, or a structure having a crosslinked structure.

In the present invention, the case where the polymer component has a polyester skeleton will be described in detail below.
When the binder resin constituting the toner is a polyester resin, from the viewpoint of compatibility with the binder resin, the polymer component is at least a monomer represented by the following general formula (7) and the following general formula (8). It is preferable to contain a polycondensation polymer containing units as constituent components. Or it is preferable to contain the polycondensation polymer which contains the monomer unit represented by following General formula (22) as a structural component.

L ₂ in the general formula (7) represents a divalent linking group, and preferably L ₂ is an alkylene group, an alkenylene group, or an arylene group.
Examples of the alkylene group in L ₂ include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a hexamethylene group, a neopentylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, and an undecamethylene group. , A linear, branched or cyclic alkylene group such as a dodecamethylene group, 1,3-cyclopentylene, 1,3-cyclohexylene, or 1,4-cyclohexylene group.
Examples of the alkenylene group in L ₂ include a vinylene group, a propenylene group, and a 2-butenylene group.
Examples of the arylene group in L ₂ include 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 2,6-naphthylene group, 2,7-naphthylene group, and 4,4′-. Biphenylene group is mentioned.
The substituent of L ₂ may be further substituted with a substituent as long as the affinity for the dispersion medium is not significantly impaired. In this case, examples of the substituent that may be substituted include a methyl group, a halogen atom, a carboxyl group, a trifluoromethyl group, and combinations thereof.
The L ₂ can be arbitrarily selected from the substituents listed above, but is preferably an alkylene group having 6 or more carbon atoms or a phenylene group from the viewpoint of affinity for a dispersion medium, particularly a nonpolar solvent. Or a combination thereof.

L ₃ in the general formula (8) represents a divalent linking group. From the viewpoint of affinity for the dispersion medium, L ₃ is an alkylene group or a phenylene group, or the general formula (8). Is represented by the following general formula (23).

［式（２３）中、Ｒ_２４はエチレン基、又はプロピレン基を表す。ｘ及びｙは、それぞれ０以上の整数であり、且つｘ＋ｙの平均値は２乃至１０である。］

[In the formula (23), R ₂₄ represents an ethylene group or a propylene group. x and y are each an integer of 0 or more, and the average value of x + y is 2 to 10. ]

As the alkylene group in L ₃ in the general formula (8), a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a hexamethylene group, a neopentylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, Examples include a linear, branched, or cyclic alkylene group such as a decamethylene group, an undecamethylene group, a dodecamethylene group, a 1,3-cyclopentylene group, a 1,3-cyclohexylene group, or a 1,4-cyclohexylene group. .
Examples of the phenylene group in L ₃ include a 1,4-phenylene group, a 1,3-phenylene group, and a 1,2-phenylene group.
The substituent of L ₃ may be further substituted with a substituent as long as the affinity for the dispersion medium is not significantly impaired. In this case, examples of the substituent that may be substituted include a methyl group, an alkoxy group, a hydroxyl group, a halogen atom, and combinations thereof.
L ₃ can be arbitrarily selected from the substituents listed above, but from the viewpoint of affinity for a dispersion medium, particularly a nonpolar solvent, an alkylene group having 6 or more carbon atoms, a phenylene group, or the above general formula ( 8) is preferably a bisphenol A derivative of the above general formula (23), and may be a combination thereof.

L ₄ in the general formula (22) represents a divalent linking group, and preferably L ₄ is an alkylene group or an alkenylene group.
Examples of the alkylene group in L ₄ include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a hexamethylene group, a neopentylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, and an undecamethylene group. , A linear, branched or cyclic alkylene group such as a dodecamethylene group or a 1,4-cyclohexylene group.
Examples of the alkenylene group in L ₄ include a vinylene group, a propenylene group, a butenylene group, a butadienylene group, a pentenylene group, a hexenylene group, a hexadienylene group, a heptenylene group, an octanylene group, a decenylene group, an octadecenylene group, an eicosenylene group, or a triacontenylene group. Is mentioned. These alkenylene groups may have any of linear, branched, and cyclic structures. In addition, the position of the double bond may be any location as long as it has at least one double bond.
The substituent of L ₄ may be further substituted with a substituent as long as the affinity for the dispersion medium is not significantly impaired. In this case, examples of the substituent that may be substituted include an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, and combinations thereof.
The L ₄ can be arbitrarily selected from the substituents listed above, but is preferably an alkylene group having 6 or more carbon atoms or an alkenylene group from the viewpoint of affinity for a dispersion medium, particularly a nonpolar solvent, A combination thereof may be used.

In the above azo compound, the larger the number of azo skeleton partial structures bonded to the polymer component via a single bond or a linking group, the higher the affinity for the colorant, but if it is too much, the binder resin constituting the toner. There is a tendency for the affinity for to decrease. Therefore, the number of the azo skeleton partial structures is preferably in the range of 0.5 to 30 and in the range of 0.5 to 15 with respect to the number of monomers 100 forming the polymer component. Is more preferable.

  In the present invention, the content of the azo compound in the colorant dispersion prepared in the colorant dispersion step may be 3 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the total amount of the colorant. preferable. When the content of the azo compound is less than 3 parts by mass, the effect of the present invention tends to be reduced. On the other hand, when the amount exceeds 15 parts by mass, there is a tendency that the azo compound released without adsorbing to the colorant tends to increase, so that the possibility of affecting the chargeability of the toner increases.

  The adsorption rate of the azo compound to the colorant is preferably 30% or more, more preferably 50% or more, and further preferably 70% or more. When the adsorption rate of the azo compound to the colorant is 30% or more, the other materials constituting the toner overcome the interference with the colorant and the azo compound continues to be adsorbed to the colorant, thereby dispersing the colorant. The state can be maintained well.

The acid value of the azo compound is preferably 30 mgKOH / g or less, and more preferably 10 mgKOH / g or less. When the acid value of the azo compound is 30 mgKOH / g or less, the chargeability is further improved in use in a high temperature and high humidity environment. In addition, it is preferable that the acid value of the said azo compound is 0 mgKOH / g or more.
In particular, when the toner is produced in an aqueous medium, if the acid value of the azo compound is 30 mg KOH / g or less, the probability that the azo compound is present on the surface of the toner tends to be low, and as a result, the colorant is also near the toner surface. Probability of existing tends to decrease. Therefore, the exposure of the colorant on the toner surface can be reduced. That is, since the toner surface becomes homogeneous, the release from the toner of inorganic fine powder such as silica that is used by adhering to the toner surface in normal toner can be reduced. Therefore, it is possible to improve member contamination such as filming.

In the present invention, when the toner particles are produced using the suspension polymerization method, the polarity is determined when preparing the polymerizable monomer composition from the viewpoint of allowing the polymerization reaction of the polymerization monomer to be performed without hindrance. It is one of the preferable embodiments that a resin is added. Examples of the polar resin include a copolymer of styrene and (meth) acrylic acid, unsaturated carboxylic acid such as acrylic acid or methacrylic acid, other unsaturated dibasic acid and unsaturated dibasic acid anhydride, or monomers thereof. Preferred examples include copolymers of styrene monomers and polyester resins, and epoxy resins. The polar resin preferably has no unsaturated group capable of reacting with the monomer in the molecule. As addition amount of these polar resins, 0.1-30 mass% of a polymerizable monomer is preferable, and it is more preferable in it being 0.5-20 mass%. The polar resin preferably has an acid value of 5.0 mgKOH / g or more and 30.0 mgKOH / g or less from the viewpoint of environmental stability.
The acid value of the azo compound is preferably smaller than the acid value of the polar resin. This is because if the acid value of the azo compound is smaller than the acid value of the polar resin, the azo compound hardly exists on the surface of the toner, and as a result, the exposure of the colorant to the toner surface can be reduced. .

  The azo compound may have an amine value, and the amine value of the azo compound is preferably 10 mgKOH / g or less, and more preferably 5 mgKOH / g or less. When the amine value of the azo compound is 10 mg KOH / g or less, the chargeability is further improved in use in a high temperature and high humidity environment. In particular, in the case of a negatively chargeable toner, when the amine value of the azo compound exceeds 10 mgKOH / g, the chargeability tends to decrease. The amine value of the azo compound is preferably 0 mgKOH / g or more.

The number average molecular weight (Mn) of the azo compound measured using a size exclusion chromatograph (SEC) is preferably 2000 or more and 200000 or less, more preferably 3500 or more and 45000 or less, and 5000 or more and 30000 or less. More preferably.
When the number average molecular weight (Mn) of the azo compound is 2000 or more, the effect of improving the dispersibility of the colorant is high, and the storage stability is excellent. On the other hand, when it is 200,000 or less, there is no problem in the affinity for the binder resin constituting the toner, and the fixing property is not hindered. Further, when the number average molecular weight (Mn) of the azo compound is 200,000 or less, the colorant particles are bridged to prevent aggregation of the colorant. Further, when the toner is produced in an aqueous medium, the toner composition or polymerizable monomer composition does not have a high viscosity, and a toner having a sharp particle size distribution can be obtained.

The azo compound can be synthesized according to a known method.
Examples of the method for synthesizing the azo compound include the methods shown in the following (i) to (iv).
First, the method (i) will be described in detail with an example of the scheme shown below.

［式（１０）及び（１１）中のＲ_１、Ｒ_２は上記一般式（１）中のＲ_１、Ｒ_２と各々同義である。式（９）及び（１１）中のＡｒ_１はアリーレン基を表す。Ｐ_１は、ポリマー成分であり、例えば、上記一般式（５）等で表される単量体単位を構成成分として含む共重合体等である。式（９）及び（１１）中のＱ_１は、Ｐ_１と反応して、単結合又は二価の連結基を形成する置換基を表す。］

_[R 1, _{R 2} in the formula (10) and (11) are each the same meaning as _R 1, _{R 2} in the general formula (1). Ar ₁ in the formulas (9) and (11) represents an arylene group. P ₁ is a polymer component, for example, a copolymer containing a monomer unit represented by the general formula (5) or the like as a constituent component. Q ₁ in the formulas (9) and (11) represents a substituent that reacts with P ₁ to form a single bond or a divalent linking group. ]

In the scheme of the method (i) exemplified above, Step 1 for synthesizing the azo skeleton partial structure (11) by diazo coupling the compound (10) with the aniline derivative represented by the formula (9), the azo skeleton moiety The azo compound can be synthesized by Step 2 in which the structure (11) and the polymer component P ₁ are bonded by a condensation reaction or the like.
The polymer component represented by P ₁ can control the molecular weight distribution and the molecular structure using a known method. For example, a polymer component with a controlled molecular weight distribution or molecular structure can be produced by using a method using an addition-cleavage type chain transfer agent, NMP method, ATRP method, RAFT method, MAGIX method, DT method, etc. it can.
Next, step 2 will be described. In step 2, a known method can be used. Specifically, for example, by using a polymer component P ₁ having a carboxyl group and an azo skeleton partial structure (11) in which Q ₁ is a substituent having an amino group, P ₁ and Q ₁ are carboxylic acids. The azo compound linked by an amide bond can be synthesized. Specific examples include a method using a dehydrating condensing agent, such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, the Schotten-Baumann method, and the like.

［式（１１）中のＲ_１、Ｒ_２、Ａｒ_１、及びＱ_１は、上記方法（ｉ）のスキーム中の式（１１）中のＲ_１、Ｒ_２、Ａｒ_１、及びＱ_１と各々同義である。式（１２）中のＱ_２は、式（１１）中のＱ_１と反応して、式（１３）中のＱ_３を形成する置換基を表す。式（１２）及び（１３）中のＲ_２３は、水素原子、アルキル基を表し、Ｑ_３は式（１１）中のＱ_１及び式（１２）中のＱ_２が反応し、形成する二価の連結基を構成する置換基を表す。］ Next, the method (ii) will be described in detail by showing an example of the scheme below.

[R ₁ , R ₂ , Ar ₁ , and Q ₁ in the formula (11) are the same as R ₁ , R ₂ , Ar ₁ , and Q ₁ in the formula (11) in the scheme of the method (i), respectively. It is synonymous. Q ₂ in formula (12) represents a substituent that reacts with Q ₁ in formula (11) to form Q ₃ in formula (13). R _{23 in} formulas (12) and (13) represents a hydrogen atom or an alkyl group, and Q ₃ is a divalent formed by the reaction of Q ₁ in formula (11) and Q ₂ in formula (12). Represents a substituent constituting the linking group. ]

In the scheme of the method (ii) exemplified above, the azo skeleton having a polymerizable functional group by reacting the azo skeleton partial structure represented by the formula (11) with the vinyl group-containing compound represented by the formula (12). Step 3 for synthesizing the partial structure (13), Step 4 for copolymerizing the azo skeleton partial structure (13) having a polymerizable functional group with a monomer unit represented by the general formula (5), Azo compounds can be synthesized.
For example, a vinyl group-containing compound (12) having an isocyanate group (for example, 2-isocyanatoethyl methacrylate [trade name: Karenz MOI] manufactured by Showa Denko KK) and an azo compound in which Q ₁ is a substituent having a hydroxyl group By using the skeleton partial structure (11), it is possible to synthesize the azo skeleton partial structure (13) having the polymerizable functional group, in which the linking group is a urethane group.

［式（１１）中のＲ_１、Ｒ_２、Ａｒ_１、及びＱ_１は上記方法（ｉ）のスキーム中の式（１１）中のＲ_１、Ｒ_２、Ａｒ_１、及びＱ_１と各々同義である。式（１４）中のＱ_４は、式（１１）中のＱ_１と反応して、式（１５）中のＱ_５を形成する置換基（例えば、カルボキシル基）を表す。Ａは塩素原子、臭素原子、又はヨウ素原子を表す。式（１５）中のＲ_１、Ｒ_２、及びＡｒ_１は、上記式（１１）中のＲ_１、Ｒ_２、及びＡｒ_１と同意義を表し、Ｑ_５は式（１１）中のＱ_１及び式（１４）中のＱ_４が反応し、形成する連結基を表す。］ Next, method (iii) will be described in detail with reference to an example of the scheme shown below.

[R ₁ , R ₂ , Ar ₁ , and Q ₁ in Formula (11) are the same as R ₁ , R ₂ , Ar ₁ , and Q ₁ in Formula (11) in the scheme of the method (i), respectively. It is. Q ₄ in the formula (14) represents a substituent (for example, a carboxyl group) that reacts with Q ₁ in the formula (11) to form Q ₅ in the formula (15). A represents a chlorine atom, a bromine atom, or an iodine atom. R ₁ , R ₂ , and Ar _{1 in} formula (15) represent the same meaning as R ₁ , R ₂ , and Ar ₁ in formula (11), and Q ₅ represents Q _{1 in} formula (11). And Q ₄ in formula (14) represents a linking group formed by reaction. ]

In the scheme of the method (iii) exemplified above, the azo skeleton partial structure represented by the formula (11) is reacted with the halogen atom-containing compound represented by the formula (14) to have a halogen atom-containing azo skeleton partial structure. Step 5 for synthesizing (15), Step 6 for copolymerizing with a monomer unit represented by the above formula (5) or the like using the azo skeleton partial structure (15) having a halogen atom as a polymerization initiator, Compounds can be synthesized.
As the halogen atom-containing compound (14) having a carboxyl group, acid halides and acid anhydrides thereof can also be used in the present invention.
In Step 6, the monomer unit is used in the presence of a metal catalyst and a ligand by using the ATRP method in the above method (i), using the halogen atom-containing azo skeleton partial structure (15) as a polymerization initiator. The compound having the azo skeleton partial structure can be synthesized by polymerizing with.

［式（１６）、（１８）、（２０）及び（２１）中のＡｒ_２はアリーレン基を表す。式（１７）、（１８）、（２０）及び（２１）中のＲ_１は上記一般式（１）中のＲ_１と同義である。式（１７）中のＱ_６は、式（１６）のアミノ基と反応して、式（１８）中のアミド基を形成する際に脱離する置換基を表す。Ｐ_１は上記方法（ｉ）のスキーム中のＰ_１と同義である。］ When R ₂ in the general formula (1) is an NR ₉ R ₁₀ group, R ₉ is a hydrogen atom, and R ₁₀ is a phenyl group, the azo compound is synthesized by, for example, the following method (iv) can do.

[Ar ₂ in Formulas (16), (18), (20) and (21) represents an arylene group. Equation (17), (18), _{R 1} in (20) and (21) has the same meaning as _{R 1} in the general formula (1). Q ₆ in formula (17) represents a substituent that is eliminated when reacting with the amino group in formula (16) to form an amide group in formula (18). P ₁ has the same meaning as P _{1 in} the scheme of the method (i). ]

In the scheme of the method (iv) exemplified above, an aniline derivative represented by the formula (16) and a compound (17) are amidated to obtain a compound represented by the compound (18), step 7, a compound (18) and Step 8 of coupling the diazo component of the aniline analog represented by the formula (19) to obtain the azo skeleton partial structure represented by the formula (20), the azo skeleton partial structure represented by the formula (20) Step 9 for obtaining an azo skeleton partial structure represented by the formula (21) by reducing the nitro group to an amino group with a reducing agent, separately synthesized with the amino group of the azo skeleton partial structure represented by the formula (21) The azo compound can be synthesized by the step 10 in which the carboxyl group of the polymer component represented by P ₁ is bonded by amidation.
Further, when R ₁ in the compound (17) is a methyl group, it can also be synthesized by a method using diketene instead of the compound (17).
In step 10, using the same method as in step 2 in method (i) above, the amino group of the azo skeleton partial structure represented by formula (21) and the carboxyl group of the polymer component represented by P ₁ are used. The above-mentioned azo compound can be synthesized by bonding such as by amidation. In addition, even if the polymer component represented by P ₁ has an epoxy group (for example, a copolymer of 2,3-epoxypropyl methacrylate), the azo skeleton partial structure represented by the formula (21) It is possible to react and bind with an amino group.
The compound obtained in each step of the exemplified synthesis method can be purified by using a normal organic compound isolation and purification method. Examples of isolation and purification methods include recrystallization methods and reprecipitation methods using organic solvents, column chromatography using silica gel, and the like. By purifying these methods singly or in combination of two or more, it is possible to obtain a highly pure compound.

The colorant dispersion step in the production method of the present invention will be specifically described below.
In the colorant dispersion step, the liquid before and during the treatment is expressed as a colorant mixture, and the liquid after the treatment is expressed as a colorant dispersion.
The concentration of the colorant in the colorant mixture and the colorant dispersion in the colorant dispersion step is 10% by mass or more and 25% by mass or less. When the concentration of the colorant is less than 10% by mass, the amount of the colorant that can be included in the toner decreases, and a sufficient coloring power may not be obtained. On the other hand, when the density | concentration of a coloring agent is higher than 25 mass%, since the dispersibility of a coloring agent falls, it is unpreferable. In order to reduce the viscosity so as not to reduce the dispersion efficiency of the media disperser, it is necessary to increase the amount of the azo compound added in accordance with the amount of the colorant added. Compared with conventional dispersants, the adsorbing power to the colorant is high, and the amount of the azo compound added can be reduced, so that there is little adverse effect on the toner. However, as the amount of the azo compound added is increased, the effect on the charging property is not so small, which is not preferable.
The concentration of the colorant in the colorant mixture and the colorant dispersion is preferably 12% by mass or more and 20% by mass or less.

In the colorant dispersion step of the present invention, the colorant is dispersed using a media disperser using media particles having a number average particle size of 0.05 mm or more and 0.80 mm or less. When media particles having a minute particle size within the above range are used, the amount of media particles per volume of the disperser increases, so the number of collisions between the media particles increases. As a result, the final reached particle diameter of the colorant becomes fine and the dispersion efficiency increases. When the number average particle size of the media particles is less than 0.05 mm, the number of collisions between the media particles further increases, and the final reached particle size of the colorant becomes finer. On the other hand, the centrifugal force generated in the media particles becomes smaller in inverse proportion to the weight. Therefore, when coarse particles are contained in the colorant or when the cohesive force of the colorant is large, the dispersion time is increased and the dispersion efficiency is remarkably lowered. In addition, since the centrifugal force decreases as the media particles become smaller in size, the media particles are pushed away into the processed material, and if the media particles in the disperser have a mechanism for separating the processed material, packing becomes easy in the vicinity of the mechanism. . Therefore, in order to prevent packing, it is necessary to limit the amount of the liquid to be processed so that the media particles are not packed, and the dispersion time increases and the dispersion efficiency is remarkably lowered. When the number average particle diameter of the media particles exceeds 0.80 mm, the dispersion is sufficiently dispersible even when coarse particles are contained in the colorant due to the centrifugal force generated in the media particles or the cohesive force of the colorant is large. It is. However, since the amount of media particles per volume of the disperser decreases, the number of collisions between the media particles also decreases, and the time required until the final reached particle size of the colorant increases. As described above, the use of a small media particle size increases the efficiency, but on the other hand, it tends to induce adverse effects. Accordingly, the number average particle diameter of the media particles is preferably 0.10 mm or more and 0.80 mm or less.
In the present invention, the number average particle diameter of the media particles was determined by measuring 100 media particles with a caliper, and taking the average value as the number average particle diameter of the media particles.

Examples of the material for the media particles include glass, steel, chromium alloy, alumina, zirconia, zircon, and titania. Among the above materials, zirconia or titania is preferable from the viewpoint of wear resistance.
Further, when the colorant dispersion liquid has a high concentration and a high viscosity in order to produce a toner having a high colorant content, the movement of the media particles is hindered by the high viscosity liquid, and the dispersion efficiency is significantly reduced. In particular, when the liquid viscosity exceeds 6000 mPa · s, the reduction in dispersion efficiency is significant. In the present invention, the viscosity of the colorant dispersion is preferably suppressed to 6000 mPa · s or less by containing the azo compound.
The media disperser used in the present invention is preferably an apparatus that can use media particles of 0.05 mm or more and 0.80 mm or less.

A distributed system incorporating a media distributor (hereinafter also simply referred to as a “distributor”) used in the present invention will be described with reference to the drawings, but is not limited thereto.
FIG. 1 shows a distribution system 1 incorporating a media disperser (1), and FIG. 2 shows a cross-sectional view inside the casing of the media disperser (1). FIG. 3 is an enlarged view of the media particle separation separator located inside the disperser.
Hereinafter, a distributed system incorporating a disperser will be described.
In FIG. 1, a disperser 41 includes a cylindrical vessel, a rotatable cylindrical rotor 69 arranged coaxially with the vessel in the vessel, and media particles 72 and a colorant mixture so as to be surrounded by the rotor. Is provided with a media particle separation separator 70 (hereinafter also referred to as a centrifugal separation screen). The media particles filled in the crushing chamber 75 are implanted so as to project radially outward on the inner surface of the vessel and the rotor pin 73 implanted so as to project radially outward on the outer surface of the rotating cylindrical rotor 69. Vigorous stirring is performed by the action of the provided vessel pin 74. The colorant mixture introduced into the main body of the disperser from the treatment liquid inlet 76 provided on the one end side in the axial direction passes through the pulverization chamber 75 to further promote fine dispersion and pulverization. Thereafter, the colorant mixture that has passed through the pulverization chamber 75 passes through the centrifugal separation screen 70, is on the other end side in the axial direction, and is positioned at a position along the rotation axis so as to be surrounded by the rotor having the media particle discharge port. The liquid is discharged from the screen-shaped processing liquid discharge port 77 provided. At this time, the media particles 72 that have flowed in the vicinity of the centrifugal separation screen 70 together with the flow of the colorant mixture liquid pass through the media particle discharge port due to the centrifugal force generated by the rotation of the cylindrical rotor 69 and are returned to the grinding chamber 75. . This centrifugal separation action enables circulation of the colorant mixture at a large flow rate and achieves efficient dispersion of the colorant. The colorant mixture discharged from the treatment liquid discharge port returns to the holding tank 61 via the cooling means 51. The colorant mixed solution in the holding tank 61 is uniformly and efficiently dispersed while repeating the cycle circulation between the disperser and the holding tank 61. In the present invention, it is preferable to use the above dispersion system and disperse the colorant for about 180 minutes or more to obtain a colorant dispersion.
The peripheral speed of the cylindrical rotor of the disperser in the present invention is preferably in the range of 8 to 15 m / s. When the peripheral speed that deviates from the above range is less than 8 m / s, the collision probability between the medium and the colorant is lowered, so that the dispersion efficiency tends to be lowered. In addition, the ability to separate media in the vicinity of the screen may be reduced, and media packing may occur. Therefore, a large flow rate cannot be circulated and the dispersion efficiency tends to decrease. Further, when the peripheral speed exceeds 15 m / s, the wear between the media particles and the wear between the media particles and the apparatus become severe, so that the image performance is likely to deteriorate due to the mixing of the media particle fragments.
The back pressure of the disperser in the present invention is preferably 0.4 MPa or less. When the back pressure exceeds 0.4 MPa, packing of media particles tends to occur. As a result, image performance may be degraded due to mixing of media particle fragments due to excessive wear. In addition, due to poor separation between the colorant mixture and the media particles, the filling rate of the media particles in the grinding chamber tends to decrease, and the dispersion efficiency of the colorant tends to decrease.
The filling rate of the media particles of the disperser in the present invention is preferably 60 to 90%. Here, the filling rate of media particles refers to the ratio of the total volume of media particles to the volume of the grinding chamber. The total volume of media particles can be accurately measured by putting the media particles into a graduated cylinder.
When the filling rate of the media particles is smaller than 60%, the dispersion efficiency tends to decrease due to a decrease in frictional force between the media particles. On the other hand, when the filling rate exceeds 90%, packing of media particles tends to occur.
The material of the cylindrical rotor and vessel in the disperser is preferably stainless steel, carbide, carbon steel, alumina, ceramic, or zirconia from the viewpoint of strength. Further, from the viewpoint of wear, it is preferable to use stainless steel or carbide. In addition, since the heat generated during dispersion tends to adversely affect the colorant mixture, it is preferable to install a heat exchanger as a cooling means in the circulation system line and perform heat exchange. You may install a heat exchanger in the path | route after passing a disperser.
The liquid temperature of the colorant mixture is preferably adjusted to 10 to 50 ° C. When the liquid temperature is lower than 10 ° C., moisture due to condensation may be mixed in the colorant mixture, which may reduce the dispersion efficiency. On the other hand, when the liquid temperature exceeds 50 ° C., the colorant may be deteriorated, which may affect image characteristics.
The media disperser preferably used in the present invention is a media disperser having an external circulation path as shown in the disperser, and repeatedly introduces and discharges the media disperser while filling the disperser with the colorant mixture. However, it is preferable that the colorant is dispersed. If it is this dispersion method, it is not limited to a disperser.
Dispersers that can be used in the present invention are dyno mill (manufactured by Shinmaru Enterprise), apex mill (manufactured by Kotobuki Giken Kogyo), SC mill (manufactured by Mitsui Mining), star mill LMZ, star mill ZRS (manufactured by Ashizawa Finetech), Pico Glen Mill and Eco Mill (manufactured by Asada Tekko) are listed.
Batch type dispersers represented by Attritor use media particles with a number average particle size of 0.05 mm or more and 0.80 mm or less. When the viscosity increases, the media particles co-rotate immediately and the dispersion does not proceed. Therefore, it is not suitable for the present invention. Also, an external circulation path is attached to the attritor, the colorant mixture is discharged from the lower part of the attritor through a screen that separates the media particles and the colorant mixture, and the liquid is returned to the space above the attritor via the circulation pump. There are also dispersers. However, since the opening of the screen becomes smaller as the media becomes finer and the colorant mixture cannot be discharged from the screen and cannot be circulated, it is not suitable for the present invention.
Therefore, as described in the disperser, it is preferable that the disperser is filled with the colorant mixed solution, and is pumped with a circulation pump to discharge the colorant mixed solution from the media separation screen having a small opening.

The toner production method of the present invention will be described in more detail.
In the present invention, the weight average particle diameter (D4) of the obtained toner is preferably 4.0 μm or more and 9.0 μm or less, and more preferably 5.0 μm or more and 7.5 μm or less.
When the weight average particle diameter of the toner is less than 4.0 μm, it is easy to cause charge-up, thereby causing problems such as fogging, scattering, and low image density. In addition, the charging member is easily contaminated during long-term image output, making it difficult to provide a stable high-quality image. Furthermore, not only is it difficult to clean the transfer residual toner remaining on the photosensitive member, but also fusion or the like is likely to occur.
On the other hand, if the weight average particle diameter of the toner is larger than 9.0 μm, it tends to cause a reduction in fine line reproducibility of fine characters and a reduction in image scattering.

The toner production method of the present invention is a toner production method for producing toner in an aqueous medium as described above. Specifically, a suspension polymerization method and a dissolution suspension method are preferably exemplified, but not limited thereto.
In the suspension polymerization method, a polymerizable monomer composition is prepared by adding and mixing a polymerizable monomer, a polar resin, a release agent, a polymerization initiator, and the like, if necessary, to the colorant dispersion. To do. Next, the polymerizable monomer composition is dispersed in an aqueous medium to granulate particles of the polymerizable monomer composition. Then, the polymerizable monomer in the particles of the polymerizable monomer composition is polymerized in an aqueous medium to obtain toner particles.
As the polymerizable monomer, a vinyl polymerizable monomer capable of radical polymerization is used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer for constituting a general toner binder resin can be used. A monofunctional polymerizable monomer is used individually or in combination of 2 or more types or in combination with a polyfunctional polymerizable monomer. The polyfunctional polymerizable monomer can also be used as a crosslinking agent.
As a polymerization initiator used in the polymerization of the polymerizable monomer, a known oil-soluble polymerization initiator and / or a water-soluble polymerization initiator is used. In order to control the degree of polymerization of the polymerizable monomer, a chain transfer agent, a polymerization inhibitor and the like can be further added and used.
The addition amount of the polymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer. The kind of the polymerizable initiator is slightly different depending on the polymerization method, but may be selected with reference to a 10-hour half-life temperature. These polymerizable initiators are used alone or in combination.
Furthermore, in the present invention, a crosslinking agent can be used during the synthesis of the binder resin in order to increase the stress resistance of the toner particles and to control the molecular weight of the binder resin. As the crosslinking agent, a compound having two or more polymerizable double bonds is used. The addition amount of these cross-linking agents is preferably 0.05 to 10 parts by mass, more preferably 0, with respect to 100 parts by mass of the polymerizable monomer in terms of toner fixability and offset resistance. .1 to 5 parts by mass.

The aqueous medium used in the suspension polymerization method preferably contains a dispersion stabilizer. As the dispersion stabilizer, known inorganic and organic dispersion stabilizers can be used.
In the present invention, it is preferable to use a poorly water-soluble inorganic dispersion stabilizer that is soluble in an acid. In the present invention, when preparing an aqueous medium using a hardly water-soluble inorganic dispersion stabilizer, the dispersion stabilizer is added in an amount of 0.2 to 2. It is preferable to use the polymerizable monomer composition in the range of 0 part by mass in terms of droplet stability in the aqueous medium. Moreover, in this invention, it is preferable to prepare an aqueous medium using the water of the range of 300 to 3000 mass parts with respect to 100 mass parts of polymerizable monomer compositions. In the present invention, when preparing an aqueous medium in which the poorly water-soluble inorganic dispersion stabilizer is dispersed, a commercially available dispersion stabilizer may be used as it is, but a dispersion stabilizer having a fine and uniform particle size. In order to obtain particles, it is preferable to prepare by preparing the poorly water-soluble inorganic dispersion stabilizer under high-speed stirring in water. For example, when calcium phosphate is used as a dispersion stabilizer, a preferable dispersion stabilizer can be obtained by mixing a sodium phosphate aqueous solution and a calcium chloride aqueous solution under high speed stirring to form calcium phosphate fine particles.

In the present invention, a suitable toner can be obtained even when the toner is produced by the dissolution suspension method. Since the manufacturing process of the dissolution suspension method does not have a heating step, it suppresses the compatibilization of the binder resin and the release agent that occurs when a low-melting-point release agent is used, and the toner glass resulting from the compatibility The transition temperature can be prevented from lowering. Further, the dissolution suspension method has a wide range of options for the toner material used as the binder resin, and it is easy to use a polyester resin, which is generally advantageous for fixing properties, as a main component.
In the dissolution suspension method, a toner composition is prepared by dissolving and mixing a colorant dispersion, a binder resin, and, if necessary, a release agent in an organic solvent. Next, the toner composition is dispersed in an aqueous medium and particles of the toner composition are granulated to obtain a toner particle suspension. The obtained suspension is heated or the organic solvent is removed by decompression to obtain toner particles.
The toner composition in the above step is preferably prepared by mixing a colorant dispersion in which a colorant is dispersed in a first organic solvent with a second organic solvent. That is, after the colorant is sufficiently dispersed in the first organic solvent, the colorant can be present in the toner particles in a better dispersion state by mixing with the second organic solvent together with other toner materials. .
As the organic solvent that can be used in the dissolution suspension method, since the organic solvent in the toner particle suspension is easily removed, the boiling point is low and the binder resin can be sufficiently dissolved. The organic solvent is not particularly limited as long as it has a high affinity with the azo compound, but esters such as methyl acetate, ethyl acetate, and butyl acetate are preferably used.
The amount of the organic solvent used is preferably in the range of 50 to 5000 parts by mass, more preferably in the range of 120 to 1000 parts by mass with respect to 100 parts by mass of the binder resin.
The aqueous medium used in the dissolution suspension method preferably contains a dispersion stabilizer. As the dispersion stabilizer, known inorganic and organic dispersion stabilizers can be used.
The amount of the dispersant used is in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the binder resin, from the viewpoint of droplet stability in the aqueous medium of the solvent composition. preferable.
In the suspension polymerization method, a polar resin is added to the polymerizable monomer composition, and in the dissolution suspension method, a polar resin is added to produce toner particles. ) Can be obtained with a core-shell structure coated with a polar resin (shell portion).
For this reason, the toner obtained by using the above production method has little exposure to the toner surface even when a relatively large amount of the release agent is contained, for example, by encapsulating the release agent in the toner. In addition, toner deterioration in continuous printing can be suppressed.
Examples of the polar resin for forming the shell portion are given below, but other resins may be used.
Examples of the polar resin include polyester, polycarbonate, phenol resin, epoxy resin, polyamide, and cellulose. Polyester is preferred because of the variety of materials. The amount of the polar resin used is preferably 0.01 to 20.0 parts by mass, more preferably 0.5 to 10.0 parts by mass with respect to 100 parts by mass of the binder resin.

  In the present invention, the toner preferably contains one or more known release agents used for the toner. The content of the release agent is the total amount of the release agent, and is preferably 2.5 parts by mass or more and 25.0 parts by mass or less with respect to 100 parts by mass of the toner, 4.0 parts by mass or more, 20 More preferably, it is 6.0 parts by mass or more and 18.0 parts by mass or less.

In the present invention, a charge control agent may be used in order to keep the chargeability of the toner stable regardless of the environment.
As the charge control agent other than the resin-based charge control agent, a metal-containing salicylic acid compound can be suitably exemplified, and the metal is particularly preferably aluminum or zirconium. A particularly preferred control agent is an aluminum salicylate compound.
Examples of the resin charge control agent include a polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group.
The polymer having a sulfonic acid group contains a sulfonic acid group-containing acrylamide monomer or methacrylamide monomer in a copolymerization ratio of 2% by mass or more, preferably 5% by mass or more, and has a glass transition temperature (Tg). From styrene and / or styrene acrylic acid copolymer and / or styrene methacrylic acid copolymer having a molecular weight of 40 to 90 ° C., a peak molecular weight of 10,000 to 30,000, and a weight average molecular weight of 25,000 to 40,000. The high molecular compound which becomes.
A polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group has a large polarity, and can be localized in the shell portion when the toner is produced in an aqueous medium, and can be efficiently Charging characteristics can be imparted to the toner.
The preferred blending amount of these charge control agents is preferably 0.01 to 20.00 parts by mass, more preferably 0.05 to 100.00 parts by mass of the binder resin or polymerizable monomer. Parts by mass to 10.00 parts by mass.

In the present invention, it is preferable that an inorganic fine powder is externally added to the surface of the obtained toner particles to produce a toner. The inorganic fine powder is added to and mixed with toner particles to improve the fluidity of the toner and make the charge uniform, and the added inorganic fine powder exists in a state of being uniformly attached to the surface of the toner particles.
The inorganic fine powder in the present invention preferably has a number average particle diameter (D1) of primary particles of 4 nm or more and 500 nm or less.
Examples of the inorganic fine powder used in the present invention include an inorganic fine powder selected from silica, alumina, and titania, or a composite oxide thereof. Examples of the composite oxide include silica aluminum fine powder and strontium titanate fine powder. These inorganic fine powders are preferably used after hydrophobizing the surface.
Further, the toner particles may further contain other additives, for example, a lubricant powder such as Teflon (registered trademark) powder, zinc stearate powder, polyvinylidene fluoride powder, or cerium oxide powder within a range that does not substantially adversely affect the toner particles. In addition, abrasives such as silicon carbide powder and strontium titanate powder, anti-caking agents, and organic and / or inorganic fine particles having reverse polarity can also be used in small amounts as a developability improver. These additives can also be used after hydrophobizing the surface.
The toner of the present invention is a toner for a developing system in which a toner for a high speed system, a toner for an oilless fixing system, a toner for a cleanerless system, a carrier in a developing device deteriorated by long-term use is sequentially collected and a fresh carrier is replenished. Can be used as Further, the present invention can be applied to an image forming method using a known one-component development method or two-component development method.
When the toner of the present invention is used as a two-component developer, it can be used regardless of whether it is full color or monochrome. Two-component developer for auto-refresh image forming method, two-component developer for high-speed system image forming method, two-component developer for oilless fixing image forming method, two-component developer for cleanerless image forming method, TACT The present invention can be applied to known development methods such as a two-component developer for an image forming method and a two-component developer for an image forming method that supplies a replenishment developer to a developing device using an air flow.

Hereinafter, the measurement method used in the present invention will be described.
<Measurement method of adsorption rate of azo compound to colorant>
The adsorption rate of the azo compound to the colorant was measured as follows.
[Create calibration curve]
(A) Mass ratio of a liquid monomer and an azo compound in a polymerizable monomer or toner composition having the same formulation as the toner actually manufactured (however, an azo compound corresponding to 10% by mass is added to the colorant) 5 ml of “solution of liquid medium and azo compound” prepared in (Solution 1) is prepared. Further, a liquid medium is added to the solution 1 to prepare solutions in which the content ratio of the azo compound is diluted to 1/5 and 1/10 (hereinafter referred to as the solution 2 and the solution 3, respectively).
(B) Solutions 1, 2, and 3, which were allowed to stand at 25 ° C. for 24 hours, were filtered through a solvent-resistant membrane filter having a pore diameter of 0.2 μm as a sample solution. The compound was measured, and a calibration curve of the azo compound concentration (g / ml) in the liquid medium was prepared.
・ High-speed GPC device: “HLC-8220GPC” [manufactured by Tosoh Corporation]
-Column: Duplex of LF-804-Eluent: THF
・ Flow rate: 1.0 ml / min
・ Oven temperature: 40 ℃
・ Sample injection amount: 0.025 ml
[Measurement of adsorption rate]
(A) A colorant composition, a polymerizable monomer composition or a toner composition having the same formulation as the toner actually manufactured (excluding azo compounds), corresponding to 10.0% by mass with respect to the colorant After preparing a solution in which the azo compound to be added was added and the colorant was dispersed, the solution was allowed to stand at 25 ° C. for 24 hours and centrifuged under the following conditions.
・ Kokusan Co., Ltd .: High-speed centrifuge H-9R
・ Centrifuge tube: PPT-010
・ Sample: A composition equivalent to about 80% of the volume of the centrifuge tube is added. ・ Centrifuge condition: 3 minutes at 10000 rpm (25 ° C.)
(B) The supernatant of the centrifuged composition is collected, filtered through a filter (Nippon Millipore, Mirex LH, pore diameter 0.45 μm, diameter 13 mm), and the supernatant is obtained using the GPC under the same conditions as the calibration curve. The concentration of the azo compound in the liquid was measured.
(C) From the above measurement results, the adsorption rate (%) was calculated by the following equation.
Adsorption rate (%) = {Azo compound concentration in solution 1 (g / ml) −Azo compound concentration in composition supernatant (g / ml)} / {Azo compound concentration in solution 1 (g / ml)} × 100

<Method for measuring acid value of azo compound, etc.>
The acid value of the azo compound and the polar resin can be measured as follows.
The number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids and the like contained in 1 g of a sample is referred to as an acid value.
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value of the azo compound or resin used in the present invention is measured according to JIS K 0070-1992.
(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95 vol%), and ion exchanged water is added to make 100 ml to obtain a phenolphthalein solution.
7 g of special grade potassium hydroxide is dissolved in 5 ml of water, and ethyl alcohol (95 vol%) is added to make 1 l. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.1 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. Determined from the amount of potassium solution. As the 0.1 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
(2) Operation (A) Main test 2.0 g of a sample is precisely weighed into a 200 ml Erlenmeyer flask, 100 ml of a mixed solution of toluene / ethanol (2: 1) is added and dissolved over 5 hours. Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) The acid value is calculated by substituting the obtained result into the following formula.
AV = [(B−A) × f × 5.61] / S
Here, AV: acid value (mgKOH / g), A: addition amount (ml) of potassium hydroxide solution in blank test, B: addition amount (ml) of potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

<Method for measuring amine value of azo compound>
The amine value is the number of mg of perchloric acid necessary for neutralizing all amines contained in 1 g of sample and an equivalent amount of potassium hydroxide.
In the present invention, the method for measuring the amine value conforms to JIS K 7237-1995. Specifically, it is as follows.
(1) Preparation of reagent Crystal violet 0.1 g is dissolved in acetic acid 100 ml to obtain a crystal violet solution. 8.5 ml of perchloric acid is slowly added into a solution prepared by mixing 500 ml of acetic acid and 200 ml of acetic anhydride in advance and mixed. Acetic acid is added thereto to make the total volume 1 l, and then left for 3 days to obtain a perchloric acid acetic acid solution. The factor of the perchloric acid acetic acid solution is determined by the following procedure. First, 0.1 g of potassium hydrogen phthalate is weighed to 1 mg, dissolved in 20 ml of acetic acid, 90 ml of o-nitrotoluene is added, and several drops of the crystal violet solution are added. This is determined by titration with the perchloric acid acetic acid solution.
(2) Operation (A) Main test 2.0 g of a sample is precisely weighed in a 200 ml beaker, 100 ml of a mixed solution of o-nitrotoluene / acetic acid (9: 2) is added and dissolved over 3 hours. Next, several drops of the crystal violet solution are added and titrated with the perchloric acid acetic acid solution. The end point of the titration is when blue of the indicator changes to green and green continues for about 30 seconds.
(B) Blank test A test similar to the above operation is performed except that no sample is used (that is, only a mixed solution of o-nitrotoluene / acetic acid (9: 2) is used).
(3) Calculation of total amine value The obtained result is substituted into the following formula to calculate the amine value AmV.
AmV = [(D−C) × f × 5.61] / S
Here, AmV: amine value (mg KOH / g), C: addition amount of perchloric acid acetic acid solution in blank test (ml), D: addition amount of perchloric acid acetic acid solution in this test (ml), f: excess Factor of chloracetic acid solution, S: sample (g).

<Method for measuring number average molecular weight (Mn) of polymer component and azo compound>
In the present invention, the number average molecular weight of the polymer component and the azo compound is calculated in terms of polystyrene by size exclusion chromatography (SEC). Measurement of molecular weight by SEC was performed as follows.
The sample solution was added to tetrahydrofuran (THF) so that the sample concentration was 1.0%, and the solution was allowed to stand at room temperature for 24 hours, and filtered through a solvent-resistant membrane filter having a pore diameter of 0.2 μm. The measurement was performed under the following conditions.
Equipment: High-speed GPC equipment “HLC-8220GPC” [manufactured by Tosoh Corporation]
Column: Duplex of LF-804 Eluent: THF
Flow rate: 1.0 ml / min
Oven temperature: 40 ° C
Sample injection amount: 0.025 ml
In calculating the molecular weight of the sample, standard polystyrene resin [TSO Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, manufactured by Tosoh Corporation] F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500] were used.

<Measurement of gloss (glossiness) of colorant dispersion>
The dispersion state of the colorant in the colorant dispersion in the colorant dispersion step was measured by measuring the gloss (glossiness) of the colorant dispersion. The gloss of the colorant dispersion is applied on a straight line on top of super art paper [Kanato 180 kg 80 × 160 (manufactured by SEVENDO)], and then uniformly applied on the art paper using a wire bar (# 10). After sufficiently drying, the coated sample was placed on a smooth glass plate and measured. In the measurement, three points were measured using GLOSS CHECKER IG320 manufactured by HORIBA, and the average value was defined as the gloss (glossiness) of the colorant dispersion.

<Measurement of viscosity of colorant dispersion>
The colorant dispersion whose liquid temperature was adjusted to 30 ± 1 ° C. was measured under the following conditions using a Viscocoater VT550 (manufactured by HAAKE).
Sensor: MV-DIN
Shear rate: 1.075 (1 / s) <1 min> → 1.29 (1 / s) <1 min> → 4.3 (1 / s) <1 min> → 12.9 (1 / s) <1 min> → 21.5 (1 / s) <1 min>
In addition, the measured value when 1 min passed at a shear rate of 12.9 (1 / s) was taken as the viscosity of the colorant dispersion.

<Method for Measuring Weight Average Particle Size (D4) and Number Average Particle Size (D1) of Toner>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner can be measured by various methods such as Coulter Counter TA-III type or Coulter Multisizer (Coulter). In the present invention, a Coulter counter TA-III type (manufactured by Coulter) is used to calculate the number distribution and the weight distribution. The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are calculated as follows. As the measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the included dedicated software “Beckman Coulter Mul
“size 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
Prior to measurement and analysis, the dedicated software is set as follows.
On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.
In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.
The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) having an electrical output of 120 W is prepared. A predetermined amount of ion-exchanged water is placed in a water tank of an ultrasonic disperser, and about 2 ml of the contamination N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Also, when confirming the granulation properties of toner particles, in the case of suspension polymerization, the toner particle suspension after the completion of the polymerization reaction is used. In the case of dissolution suspension, the toner suspension after granulation is used. The suspension is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker (1) installed in the sample stand, the electrolytic solution (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. When the graph / volume% is set in the dedicated software, the “average diameter” on the “Analysis / Weight Statistics (Arithmetic Average)” screen is the weight average particle size (D4). The “average diameter” on the “analysis / number statistics (arithmetic mean)” screen is the number average particle diameter (D1).
About the granulation property in a granulation process, it investigated by D50 weight% / D50 number% measured with the Coulter counter. D50 wt% / D50 number% is (50% particle size based on weight distribution) / (50% particle size based on number distribution).

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but this does not limit the present invention in any way. Note that “parts” and “%” in the following examples and the like are based on mass unless otherwise specified.

Production examples of the azo compound used in the present invention will be described.
<Production Example of Polymer Component (A-1) of Azo Compound>
Heat 100 parts of propylene glycol monomethyl ether while purging with nitrogen and reflux at a liquid temperature of 120 ° C. or higher. To this, 159.0 parts of styrene, 10 parts of acrylic acid, 35.6 parts of n-butyl acrylate (styrene / acrylic acid) / N-butyl acrylate = 11.00 / 1.00 / 2.00 [mol ratio]), and tert-butyl peroxybenzoate [Organic peroxide polymerization initiator, manufactured by NOF Corporation, trade name : Perbutyl Z] A mixture of 1.25 parts was added dropwise over 3 hours. After completion of the dropwise addition, the solution was stirred for 3 hours and then distilled at atmospheric pressure while raising the liquid temperature to 170 ° C. After reaching the liquid temperature of 170 ° C., it was distilled for 1 hour under reduced pressure at 1 hPa to remove the solvent. Obtained. The solid was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was separated by filtration to obtain a polymer component (A-1). Table 1 shows the physical properties of the obtained polymer component (A-1).

<Production Examples of Polymer Components (A-2) to (A-7) and (A-9) of Azo Compound>
The polymer components (A-2) to (A-7) and (A-9) are the same as the polymer component (A-1) except that the type and composition ratio of the polymerizable monomer are changed as shown in Table 1. Manufactured. The total mass of the polymerizable monomers was the same as that of the polymer component (A-1).
The physical properties of the obtained polymer components (A-2) to (A-7) and (A-9) are shown in Table 1.

<Production Example of Polymer Component (A-8) of Azo Compound>
Heat 100 parts of propylene glycol monomethyl ether while purging with nitrogen and reflux at a liquid temperature of 120 ° C. or higher, to which 216.8 parts of styrene, 10 parts of acrylic acid, 10.7 parts of n-butyl acrylate (styrene / acrylic acid) / N-butyl acrylate = 15.00 / 1.00 / 0.60 [mol ratio]), trimethylolpropane tris (3-mercaptopropionate) [manufactured by Sakai Chemical Co., Ltd.] (β-mercaptopropionic acids) 10 parts and 20 parts of tert-butyl peroxybenzoate [organic peroxide polymerization initiator, manufactured by NOF Corporation, trade name: Perbutyl Z] were added dropwise over 3 hours. After completion of the dropwise addition, the solution was stirred for 3 hours and then distilled at atmospheric pressure while raising the liquid temperature to 170 ° C. After reaching the liquid temperature of 170 ° C., it was distilled for 1 hour under reduced pressure at 1 hPa to remove the solvent. Obtained. The solid was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was filtered off to obtain a polymer component (A-8). The physical properties of the obtained polymer component (A-8) are shown in Table 1.

<Production Example of Polymer Part (A-10) of Azo Compound>
Trimethylolpropane tris (3-mercaptopropionate) [manufactured by Sakai Chemical Co., Ltd.] (β-mercaptopropionic acids) was changed to 0.15 part by the same method as the polymer component (A-8) of the azo compound. A polymer component (A-10) of the compound was produced. Table 1 shows the physical properties of the polymer component (A-10) obtained.

<Production Example of Polymer Component (A-11) of Azo Compound>
The monomer ratio was 216.8 parts of styrene, 10 parts of acrylic acid, 10.7 parts of n-butyl acrylate (styrene / acrylic acid / n-butyl acrylate = 15.00 / 1.00 / 0.60 [mol ratio]). The polymer component (A-11) was produced in the same manner as the polymer component (A-1) except that perbutyl Z was changed to 0.70 parts by mass. Table 1 shows the physical properties of the obtained polymer component (A-11).

<Production Example of Polymer Component (A-12) of Azo Compound>
In the above general formula (7), L2 is a monomer unit represented by a p-phenylene group, and a monomer unit represented by the general formula (23) (wherein R ₂₄ is an ethylene group, x and y are each 1) was prepared according to the following method.
In a four-necked flask, 31.6 g of oxyethylenated bisphenol A, 14.8 g of terephthalic acid, 5.5 g of glycerin as a crosslinking agent, 0.5 mg of di-n-butyltin oxide as a catalyst, and nitrogen gas as an inert gas were introduced. While stirring, the mixture was heated and melted at 200 ° C. After the outflow of by-product water was completed, the temperature was raised to 230 ° C. over about 1 hour, heated and stirred for 2 hours, and the resin was taken out in a molten state. The polymer component (A-12) was obtained by cooling at normal temperature and washing with water. The physical properties of the obtained polymer component (A-12) are shown in Table 1.

<Production Example of Azo Compound 1 [Compound (27)]>
First, a compound (26) having an azo skeleton partial structure represented by the following structure was produced according to the following scheme.

First, 3.11 parts of 4-nitroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 30 parts of chloroform, and ice-cooled to 10 ° C. or less, and 1.89 parts of diketene (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. Then, it stirred at 65 degreeC for 2 hours. After completion of the reaction, the mixture was extracted with chloroform and concentrated to obtain compound (24).
Next, 40.0 parts of methanol and 5.29 parts of concentrated hydrochloric acid were added to 4.25 parts of dimethyl 2-aminoterephthalate (manufactured by Merck & Co., Inc.), and the mixture was ice-cooled to 10 ° C. or lower. To this solution, 2.10 parts of sodium nitrite dissolved in 6.00 parts of water was added and reacted at the same temperature for 1 hour.
Next, 0.990 parts of sulfamic acid was added and stirred for another 20 minutes (diazonium salt solution). 4.51 parts of compound (24) was added to 70.0 parts of methanol, and the mixture was ice-cooled to 10 ° C. or lower and the diazonium salt solution was added. Thereafter, a solution obtained by dissolving 5.83 parts of sodium acetate in 7.00 parts of water was added and reacted at 10 ° C. or lower for 2 hours. After completion of the reaction, 300 parts of water was added and stirred for 30 minutes, and then the solid was filtered off and purified by recrystallization from N, N-dimethylformamide to obtain compound (25). Next, 8.58 parts of the compound (25) and 0.4 parts of palladium-activated carbon (palladium 5%) are added to 150 parts of N, N-dimethylformamide, and the reaction is performed under a hydrogen gas atmosphere (reaction pressure 0.1 to 0). And 4 MPa) at 40 ° C. for 3 hours. After completion of the reaction, the solution was filtered off and concentrated to obtain compound (26).
Next, an azo compound (27) was produced according to the following scheme by binding the amino group of the compound (26) having an azo skeleton partial structure to the carboxyl group of the polymer component (A-1) by amidation.

［上記構造式中で、「ｃｏ」とは、共重合体を構成する各単量体単位の配列が無秩序であることを示す記号である。］

[In the above structural formula, “co” is a symbol indicating that the arrangement of the monomer units constituting the copolymer is disordered. ]

  First, 1.98 parts of compound (26) was added to 500 parts of tetrahydrofuran, and the mixture was heated to 80 ° C. and dissolved. After dissolution, the temperature is lowered to 50 ° C., 15 parts of polymer component (A-1) is added and dissolved, and 1.96 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC · HCl) After stirring at 50 ° C. for 5 hours, the liquid temperature was gradually returned to room temperature, and the reaction was completed by stirring overnight. After completion of the reaction, the solution was filtered and concentrated, and purified by reprecipitation with methanol to obtain Compound (27) (Azo Compound 1). Table 2 shows the physical properties of the azo compound.

<Production Examples of Azo Compounds 2 to 5>
As shown in Table 2, azo compounds 2 to 5 were obtained in the same manner as azo compound 1 except that the azo skeleton partial structure and the polymer component were changed. The physical properties of the obtained azo compounds 2 to 5 are shown in Table 2.

<Production Example of Azo Compound 6>
Production of azo compound 1 was carried out in the same manner as azo compound 1 except that compound (26) was changed to the following compound (28) to obtain azo compound 6. The physical properties of azo compound 6 are shown in Table 2.

<Production Examples of Azo Compounds 7 to 18>
As in Table 2, azo compounds 7 to 18 were obtained in the same manner as azo compound 6 except that the azo skeleton partial structure and the polymer component were changed. The physical properties of the obtained azo compounds 7 to 18 are shown in Table 2.

［上記構造式中で、「ｃｏ」とは、共重合体を構成する各単量体単位の配列が無秩序であることを示す記号である。］

１．９８部の化合物（２６）を、１．９８部の４−フェニルアゾ−１−ナフチルアミン（東京化成工業株式会社製）に変えた以外はアゾ化合物１の後工程と同様にして、アゾ化合物１９を得た。得られたアゾ化合物１９の物性は表２に示す。 <Production Example of Azo Compound 19>
A compound (29) having an azo skeleton partial structure represented by the following structure was produced according to the following scheme.

[In the above structural formula, “co” is a symbol indicating that the arrangement of the monomer units constituting the copolymer is disordered. ]

In the same manner as in the subsequent step of azo compound 1, except that 1.98 parts of compound (26) was changed to 1.98 parts of 4-phenylazo-1-naphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), azo compound 19 Got. The physical properties of the obtained azo compound 19 are shown in Table 2.

<Production Example of Azo Compound 20>
1.27 parts by mass of compound (26) was added to 200 parts of dehydrated tetrahydrofuran, and the mixture was heated to 80 ° C. and dissolved. After dissolution, the temperature was lowered to 50 ° C., 18.8 parts of the polymer component (A-12) dissolved in 30 parts of dehydrated tetrahydrofuran was added, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide / hydrochloride (EDC. HCl) (3.0 parts) was added and the mixture was stirred at 50 ° C. for 5 hours. The liquid temperature was gradually returned to room temperature, and the reaction was completed by stirring overnight. After completion of the reaction, the solution was concentrated, extracted with chloroform, the organic phase was washed with water, the solution was concentrated, and purification by reprecipitation with methanol gave azo compound 20. Table 2 shows the physical properties of the azo compound 20.

上記表中、「ｐｈ」は「フェニル基」を表し、「Ｅｔ」は「エチル基」を表す。

In the above table, “ph” represents “phenyl group”, and “Et” represents “ethyl group”.

［式（Ｗ１）中、Ｒ_１、Ｒ_２、Ｒ_１１乃至Ｒ_１５は、それぞれ表２中にあらわされる置換基を表す。Ｒ_１−１、Ｒ_２−１乃至Ｒ_２−２は下記構造を表す。］ The azo skeleton partial structure shown in Table 2 will be described below.

[In Formula (W1), R ₁ , R ₂ , R _{11 to} R ₁₅ each represent a substituent represented in Table 2. R ₁ -1, R ₂ -1 to R ₂ -2 represent the following structures. ]

[上記Ｒ_１−１、Ｒ_２−１乃至Ｒ_２−２中の「＊」はポリマー成分中に化学結合により
組み込まれ、ポリマーと結合していることを表す。また、Ｒ_２−３の「＊」は、ポリマー成分であるポリエステル由来のカルボキシル基の炭素原子との結合部位を表す。一方、上記「＊＊」又は「＊＊＊」は下記一般式の「＊＊」又は「＊＊＊」と結合していることを示す。］

[“*” In the above R ₁ -1, R ₂ -1 to R ₂ -2 indicates that it is incorporated into the polymer component by a chemical bond and is bonded to the polymer. Further, "*" in R 2 _-3 represents a bonding site to the carbon atom of the carboxyl groups of the polyester from a polymer component. On the other hand, the above “***” or “***” indicates that it is combined with “**” or “***” in the following general formula. ]

The production of a colorant dispersion in the colorant dispersion step is described below.
<Example of production of colorant dispersion 1>
A colorant dispersion was prepared using the dispersion system of FIG. FIG. 2 is a cross-sectional view inside the casing of the media dispersing machine. FIG. 3 is an enlarged view of a media particle separation separator that is located inside the media disperser and separates the media particles and the colorant mixture.
A star mill LMZ type 2 (manufactured by Ashizawa Finetech Co., Ltd.) that employs a media dispersion method was used as a media dispersion machine.
First, in the holding tank 61,
-Styrene monomer 365 parts-PR122 80 parts-Charge control agent (Bontron E88, manufactured by Orient Chemical Co., Ltd.) 2.5 parts-Azo compound 6 7.2 parts, coloring containing PR122 as a colorant While introducing 40 kg of the colorant mixture and stirring, a colorant mixture was prepared. At that time, the temperature of the colorant mixture was adjusted to about 13 ° C. by introducing and discharging cooling water into the jacket. Dispersion was carried out by repeating the circulation of the holding tank, circulation pump, and media disperser by sending the prepared colorant mixture with a circulation pump.
The device configuration and distribution conditions of the media distribution device in the distribution system of FIG. 1 are as follows.
・ Rotating rotor peripheral speed: 15 m / s
Media diameter (number average particle diameter): 0.50 mm media particles (material: zirconia)
・ Media filling rate: 85%
・ Disperser back pressure: 0.1 MPa
・ Circulating flow rate: 5L / min
・ Dispersion time: 180 min
Dispersion was performed under the above conditions to prepare Colorant Dispersion Liquid 1. The colorant concentration in the obtained colorant dispersion was 17.6% by mass, and the content of the azo compound relative to 100 parts by mass of the colorant was 9 parts by mass. Thereafter, the colorant dispersion 1 was fed to the next step. Table 3 shows the physical properties and dispersion conditions of the colorant dispersion 1.

<Example of production of colorant dispersion 2>
Dispersion was performed with the same apparatus configuration and conditions as in the production example of the colorant dispersion 1 except that PR122 was changed to a mixed body of PR122 and PV19 (mass ratio of PR122: PV19 = 75: 25). . Table 3 shows the physical properties and dispersion conditions of the colorant dispersion 2.

<Production example of colorant dispersions 3 to 5>
Dispersion was performed in the same apparatus configuration and conditions as in the production example of the colorant dispersion 1 except that PR122 was changed to PR31, PR150, or PR269, respectively. Table 3 shows the physical properties and dispersion conditions of the colorant dispersions 3 to 5.

<Production Example of Colorant Dispersion 6>
The colorant dispersion process was prepared using the dispersion system of FIG. A star mill LMZ type 2 (manufactured by Ashizawa Finetech Co., Ltd.) that employs a media dispersion method was used as a media dispersion machine.
First, in the holding tank 61,
-Styrene monomer 365 parts-PY155 50 parts-Charge control agent (Bontron E88, manufactured by Orient Chemical Co., Ltd.) 2.5 parts-Azo compound 6 A coloring agent mixture containing 5 parts of azo compound as a coloring agent While introducing 40 kg and stirring, a colorant mixture was prepared. At that time, the temperature of the colorant mixture was adjusted to about 13 ° C. by introducing and discharging cooling water into the jacket. Dispersion was carried out by repeating the circulation of the holding tank, circulation pump, and media disperser by sending the prepared colorant mixture with a circulation pump.
The device configuration and distribution conditions of the media distribution device in the distribution system of FIG. 1 are as follows.
・ Rotating rotor peripheral speed: 15 m / s
Media diameter (number average particle diameter): 0.50 mm media particles (material: zirconia)
・ Media filling rate: 85%
・ Disperser back pressure: 0.1 MPa
・ Circulating flow rate: 5L / min
-Dispersion time: 180 min.
Dispersion was performed under the above conditions to prepare Colorant Dispersion Liquid 6. The colorant concentration in the obtained colorant dispersion was 11.8% by mass, and the content of the azo compound relative to 100 parts by mass of the colorant was 10 parts by mass. Thereafter, the colorant dispersion 6 was fed to the next step. Table 3 shows the physical properties and dispersion conditions of the colorant dispersion liquid 6.

<Production Examples of Colorant Dispersions 7 to 11>
Dispersion was performed under the same apparatus configuration and conditions as in the production example of the colorant dispersion 6 except that the azo compound 6 was changed to azo compounds 1 to 5, respectively. Table 3 shows the physical properties and dispersion conditions of the colorant dispersions 7 to 11.

<Example of production of colorant dispersion 12>
Dispersion was performed in the same apparatus configuration and conditions as in the production example of the colorant dispersion 1 except that the azo compound 6 was changed to the azo compound 8. Table 3 shows the physical properties and dispersion conditions of the colorant dispersion 12.

<Example of production of colorant dispersion 13>
Dispersion was carried out under the same apparatus configuration and conditions as in the production example of Colorant Dispersion Liquid 1 except that PR122; 80 parts were changed to two types of pigment combination system of PR122; 54 parts and PR150; 26 parts. Table 3 shows the physical properties and dispersion conditions of the colorant dispersion 13.

<Example of production of colorant dispersion 14>
Dispersion was performed under the same apparatus configuration and conditions as in the production example of the colorant dispersion 13 except that the azo compound 6 was changed to the azo compound 7. Table 3 shows the physical properties and dispersion conditions of the colorant dispersion 14.

<Example of production of colorant dispersion 15>
Dispersion was performed in the same apparatus configuration and conditions as in the production example of the colorant dispersion 13 except that PR122; 27.6 parts and PR150; 14 parts. Azo compound 6; 3.7 parts. In addition, the coloring agent density | concentration in the obtained coloring agent dispersion liquid was 10.1%, and content of the azo compound with respect to 100 mass parts of coloring agents was 8.9 mass parts. Table 3 shows the physical properties and dispersion conditions of the colorant dispersion 15.

<Example of production of colorant dispersion 16>
PR122; 83 parts and PR150; 42 parts Azo compound 6; Dispersion was carried out under the same apparatus configuration and conditions as in the production example of the colorant dispersion 13 except that it was changed to 11.3 parts. In addition, the colorant density | concentration in the obtained colorant dispersion liquid was 24.8%, and content of the azo compound with respect to 100 mass parts of colorants was 9.0 mass parts. Table 3 shows the physical properties and dispersion conditions of the colorant dispersion liquid 16.

<Production Example of Colorant Dispersion 17>]
Media diameter (number average particle diameter): Dispersion was performed under the same apparatus configuration and conditions as in the production example of the colorant dispersion 13 except that the media diameter (material: zirconia) was changed to 0.05 mm. Table 3 shows the physical properties and dispersion conditions of the colorant dispersion liquid 17.

<Example of production of colorant dispersion 18>
Media diameter (number average particle diameter): Dispersion was performed in the same apparatus configuration and conditions as in the production example of the colorant dispersion 13 except that the media diameter (material: zirconia) was changed to 0.80 mm. Table 3 shows the physical properties and dispersion conditions of the colorant dispersion liquid 18.

<Example of production of colorant dispersion 19>
1 except that the media disperser used in the dispersion system of FIG. 1 is changed to a wet bead mill (SC mill 100; manufactured by Nippon Coke Kogyo Co., Ltd.) and the media filling rate is changed to 85%. Dispersion was performed with the same apparatus configuration and conditions as in. Table 3 shows the physical properties and dispersion conditions of the colorant dispersion 19.

<Production Examples of Colorant Dispersions 20 to 26>
Dispersion was performed using the same apparatus configuration and conditions as in the production example of the colorant dispersion 13 except that the azo compound 6 was changed to azo compounds 9, 10, 11, 13 to 16, respectively. Table 3 shows the physical properties and dispersion conditions of the colorant dispersions 9 to 16.

<Production Examples of Colorant Dispersions 27 to 29>
Dispersion was performed in the same apparatus configuration and conditions as in the production example of the colorant dispersion 24 except that 7.2 parts of the azo compound 14 were changed to 3 parts, 15 parts, and 20 parts, respectively. Table 3 shows the physical properties and dispersion conditions of the colorant dispersions 27 to 29.

<Example of production of colorant dispersion 30>
Without using the dispersion system of FIG. 1, using Handy Mill HM-5 (manufactured by Nippon Coke Industries Co., Ltd.), using media particles (material: zirconia) having a media diameter (number average particle size) of 0.80 mm, Dispersion was performed under the same apparatus configuration and conditions as in the production example of the colorant dispersion 13 except that the dispersion was performed under the condition of the agitator rotation speed of 800 rpm and the media filling rate was changed to 85%. . Table 3 shows the physical properties and dispersion conditions of the colorant dispersion 30.

<Production Examples of Colorant Dispersions 31 to 33>
Dispersion was performed in the same apparatus configuration and conditions as in the production example of the colorant dispersion 13 except that the azo compound 6 was changed to azo compounds 12, 17, and 18, respectively. Table 3 shows the physical properties and dispersion conditions of the colorant dispersions 31 to 33.

<Example of production of colorant dispersion 34>
The colorant dispersion process was prepared using the dispersion system of FIG. A star mill LMZ type 2 (manufactured by Ashizawa Finetech Co., Ltd.) that employs a media dispersion method was used as a media dispersion machine.
First, in the holding tank 61,
・ Introducing 180 parts of ethyl acetate, 26 parts of PR122, 13.2 parts of PR150, and 20 parts of azo compound 20 and introducing 40 kg of a colorant mixture containing PR122 and PR150 as colorants, while stirring, A colorant mixture was prepared. At that time, the temperature of the colorant mixture was adjusted to about 13 ° C. by introducing and discharging cooling water into the jacket. Dispersion was carried out by repeating the circulation of the holding tank, circulation pump, and media disperser by sending the prepared colorant mixture with a circulation pump.
The device configuration and distribution conditions of the media distribution device in the distribution system of FIG. 1 are as follows.
・ Rotating rotor peripheral speed: 15 m / s
Media diameter (number average particle diameter): 0.50 mm media particles (material: zirconia)
・ Media filling rate: 85%
・ Disperser back pressure: 0.1 MPa
・ Circulating flow rate: 5L / min
・ Dispersion time: 180 min
Dispersion was performed under the above conditions to prepare a colorant dispersion liquid. The colorant concentration in the obtained colorant dispersion was 17.6% by mass, and the content of the azo compound relative to 100 parts by mass of the colorant was 8.9 parts by mass. Thereafter, the colorant dispersion liquid 34 was fed to the next step. Table 3 shows the physical properties and dispersion conditions of the colorant dispersion liquid 34.

<Example of production of colorant dispersion 35>
Dispersion was performed in the same apparatus configuration and conditions as in the production example of the colorant dispersion 6 except that the azo compound was not used and 365 parts of the styrene monomer was changed to 370 parts. When 60 minutes had elapsed, the media particles caused packing in the disperser and stopped due to overloading of the rotating rotor. Since the operation became impossible, the operation was terminated in a dispersion time of 60 minutes. Table 3 shows the physical properties and dispersion conditions of the colorant dispersion liquid 35.

<Example of production of colorant dispersion 36>
Dispersion was performed in the same apparatus configuration and conditions as in the production example of the colorant dispersion 13 except that the azo compound was not used and 365 parts of the styrene monomer was changed to 372.2 parts. Note that the motor current value of the rotary rotor was higher than that when the colorant dispersion 13 was manufactured. It is thought that the media particles are packed and the dispersion is not sufficiently advanced. Table 3 shows the physical properties and dispersion conditions of the colorant dispersion liquid 36.

[Production Example of Colorant Dispersion Liquid 37]
Dispersion was performed in the same apparatus configuration and conditions as in the production example of the colorant dispersion 13 except that the azo compound 6 was changed to the azo compound 19. Table 3 shows the physical properties and dispersion conditions of the colorant dispersion liquid 37.

<Example of production of colorant dispersion 38>
Media diameter (number average particle diameter): Dispersion was carried out under the same apparatus configuration and conditions as in the production example of the colorant dispersion 16 except that the media diameter (material: zirconia) was changed to 0.03 mm. When 120 minutes passed, the media particles were packed in the disperser and stopped due to overloading of the rotating rotor. Since the operation became impossible, the operation was completed after a dispersion time of 120 minutes. Table 3 shows the physical properties and dispersion conditions of the colorant dispersion 38.

<Production Example of Colorant Dispersion 39>
Media diameter (number average particle diameter): Dispersion was performed in the same apparatus configuration and conditions as in the production example of the colorant dispersion liquid 16 except that the media diameter (material: zirconia) was changed to 1.50 mm. Table 3 shows the physical properties and dispersion conditions of the colorant dispersion liquid 39.

<Example of production of colorant dispersion 40>
Dispersion was performed in the same apparatus configuration and conditions as in the production example of the colorant dispersion 13 except that PR122; 107 parts and PR150; 53 parts, and azo compound 6: 14.4 parts. In addition, the coloring agent density | concentration in the obtained coloring agent dispersion liquid was 29.5 mass%, and content of the azo compound with respect to 100 mass parts of coloring agents was 9.0 mass parts. Further, the motor current value of the rotary rotor was higher than that when the colorant dispersion 13 was produced. It is thought that the media particles are packed and the dispersion is not sufficiently advanced. Table 3 shows the physical properties and dispersion conditions of the colorant dispersion 40.

<Production Example of Colorant Dispersion 41>
Dispersion was carried out under the same apparatus configuration and conditions as in the production example of the colorant dispersion 13 except that PR122; 20 parts and PR150; 10 parts, azo compound 6; 2.7 parts. In addition, the colorant density | concentration in the obtained colorant dispersion liquid was 7.5 mass%, and content of the azo compound with respect to 100 masses of colorants was 9.0 mass parts. Table 3 shows the physical properties and dispersion conditions of the colorant dispersion liquid 41.

<Example 1>
5 parts of Na ₃ PO ₄ · 12H ₂ O was added to 500 parts of ion-exchanged water, heated to 60 ° C., and then stirred at 3,500 rpm using a CLEARMIX (manufactured by M Technique). . To this was added 27 parts of a 1.0 mol / liter-CaCl ₂ aqueous solution to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .
Then, as a dispersoid system,
Styrene monomer 30 parts n-Butyl acrylate 30 parts Saturated polyester resin 5 parts Tg = 68 ° C., Mw = 10000, Mw / Mn = 5.12]
Low molecular weight styrene resin 10 parts (Mw: 3200, Mw / Mn: 1.25, Tg: 53 ° C.)
Fischer-Tropsch wax 12 parts [HNP-51 (Nippon Seiki Co., Ltd.): maximum endothermic peak = 78.0 ° C.]
Polar resin 0.5 part [styrene-2-ethylhexyl acrylate copolymer containing 5% 2-acrylamido-2-methylpropanesulfonic acid, Tg = 81 ° C.]
Colorant dispersion 1 100 parts The above formulation was heated to 60 ° C and dissolved and mixed for 30 minutes. To this, 13 parts of a 70% toluene solution of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate as a polymerization initiator was dissolved to prepare a polymerizable monomer composition.
The polymerizable monomer composition was charged into the aqueous medium, and stirred at 4500 rpm for 15 minutes with Claremix in an N ₂ atmosphere at 60 ° C. to granulate the polymerizable monomer mixture.
Thereafter, while stirring with a full zone stirring blade (manufactured by Shinko Pantech Co., Ltd.), the temperature was raised to 70 ° C. and reacted for 10 hours. After the completion of the polymerization reaction, saturated steam (pure steam / steam pressure 205 kPa / temperature 120 ° C.) was introduced while stirring was continued with a full zone stirring blade. Twenty minutes after the start of the introduction of saturated steam, the temperature of the contents in the container reached 100 ° C., and a distillation fraction began to come out. Residual monomers were distilled off by obtaining a predetermined amount of fractions, and cooled to obtain a toner particle dispersion.
Hydrochloric acid was added to the toner particle dispersion to dissolve the calcium phosphate on the surface of the toner particles, followed by filtration, washing with water, crushing and drying to obtain toner particles. The content of the colorant in the toner particles is 8.9% by mass. With respect to 100 parts by mass of the obtained toner particles, 0.2 parts by mass of rutile-type titanium oxide fine powder surface-treated with 1.5 parts by mass of silica particles (RY200: manufactured by Nippon Aerosil Co., Ltd.) and dimethyl silicone oil (average) Toner 1 was obtained by dry-mixing the primary particle size: 30 nm) with a Henschel mixer (Mitsui Mining Co., Ltd.) for 5 minutes. The toner 1 was evaluated according to the following evaluation method. The evaluation results are shown in Table 4.

<Examples 2 to 33>
Toners 2 to 33 were obtained in the same manner as in Example 1 except that the colorant dispersion 1 was changed to colorant dispersions 2 to 33, respectively. The obtained toner was evaluated according to the following evaluation method. The evaluation results are shown in Table 4.

<Example 34>
The composition of the toner composition is shown below.
Colorant dispersion 34 54.6 parts Binder resin 85.0 parts [saturated polyester resin (polycondensate of propylene oxide modified bisphenol A and phthalic acid, Tg = 75.9 ° C., Mw = 11000, Mn = 4200 , Acid value 11mgKOH / g
]]
Fischer-Tropsch wax 9.0 parts [HNP-51 (manufactured by Nippon Seiki Co., Ltd.): maximum endothermic peak = 78.0 ° C.]
Charge control agent (Bontron E88, manufactured by Orient Chemical Co., Ltd.) 2.0 parts Polar resin 0.3 part [styrene-2-ethylhexyl acrylate copolymer containing 5% 2-acrylamido-2-methylpropanesulfonic acid, Tg = 81 ° C.]
Ethyl acetate (organic solvent) 10.0 parts On the other hand, carboxymethyl cellulose was dissolved by dispersing the following composition in a Starmill LMZ2 type for 3 hours to obtain an aqueous medium.
・ Calcium carbonate (coated with acrylic acid copolymer) 20.0 parts ・ Carboxymethylcellulose 0.5 part [Serogen BS-H, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.]
-Ion-exchanged water 99.5 parts K. Place in a homomixer [manufactured by Primics Co., Ltd.], add 1000 parts of the toner composition while stirring the rotating blade at a peripheral speed of 20 m / sec, and stir for 1 minute while maintaining the temperature constant at 25 ° C. Got. At this time, the weight average particle diameter of the toner particles was 5.8 μm, and D50 wt% / D50 number% was 1.20.
While stirring 2200 parts of the suspension with a full zone blade (manufactured by Shinko Environmental Solution Co., Ltd.) at a peripheral speed of 45 m / min, the liquid temperature was kept constant at 40 ° C. The phase was forcibly aspirated and solvent removal was started. At that time, 75 parts by mass of ammonia water diluted to 1% as an ionic substance was added 15 minutes after the start of solvent removal, and then 25 parts by mass of ammonia water was added 1 hour after the start of solvent removal. Two hours after the start of solvent removal, 25 parts by mass of the ammonia water was added. Finally, 25 parts by mass of the ammonia water was added three hours after the start of solvent removal, so that the total amount added was 150 parts by mass. Further, while maintaining the liquid temperature at 40 ° C., the toner dispersion was maintained for 17 hours from the start of the solvent removal to remove the solvent (ethyl acetate) from the suspended particles.
To 300 parts of the toner dispersion obtained in the solvent removal step, 80 parts of 10 mol / l hydrochloric acid was added, and after neutralization with a 0.1 mol / l sodium hydroxide aqueous solution, filtration, washing, crushing, and drying were performed. Toner particles having a weight average particle diameter (D4) of 5.8 μm were obtained. The content of the colorant in the toner particles is 9.0% by mass. With respect to 100 parts by mass of the obtained toner particles, 0.2 parts by mass of rutile-type titanium oxide fine powder surface-treated with 1.5 parts by mass of silica particles (RY200: manufactured by Nippon Aerosil Co., Ltd.) and dimethyl silicone oil (average) The primary particle size: 30 nm) was dry-mixed with a Henschel mixer (Mitsui Mining Co., Ltd.) for 5 minutes to obtain toner 34. The toner 34 was evaluated according to the following evaluation method. The evaluation results are shown in Table 4.

<Comparative Examples 1-7>
Toners 35 to 41 were obtained in the same manner as in Example 1 except that the colorant dispersion 1 was changed to the colorant dispersions 35 to 41, respectively. The obtained toner was evaluated according to the following evaluation method. The evaluation results are shown in Table 4.

Various image evaluations were performed as follows.
<Evaluation machine>
As an image forming apparatus, a commercially available laser printer LBP-5400 (manufactured by Canon) was used. Unless otherwise specified, the basis weight as an evaluation paper was 23 ° C. and relative humidity 50%. 75 g / m ² of business 4200 (manufactured by Xerox) was used.
The remodeling point of the evaluator was remodeled so that the process speed was 270 mm / sec by changing the gear and software of the evaluator main body.
A commercially available yellow or magenta cartridge was used as the cartridge used for the evaluation. That is, remove the product toner from a commercially available yellow or magenta cartridge,
After the inside was cleaned by air blow, 200 g of yellow or magenta toner according to the present invention was filled and evaluated.

<Granity of toner particles>
In the case of suspension polymerization, the toner particles are granulated using a suspension of toner particles after completion of the polymerization reaction, and in the case of dissolution suspension, a toner dispersion obtained by removing the solvent from the suspension particles is used. Thus, the D50 weight% / D50 number% measured by a Coulter counter was used.
Granulation criteria (D50 wt% / D50 number%)
A: Less than 1.25. The particle size distribution is very sharp and preferable.
B: 1.25 or more and less than 1.30. The particle size distribution is slightly broad, but at a level that is not a problem as a product.
C: 1.30 or more. The particle size distribution is broad and there is a problem as a product.

<Coloring power (image density)>
Using the evaluation machine, several types of solid images with different toner amounts were produced on the transfer paper in the range of 0.1 mg / cm ² to 1.0 mg / cm ² , and the image density thereof was determined as “Macbeth reflection densitometer RD918” ( After measuring the relationship between the amount of toner on the transfer paper and the image density.
In particular, the coloring power was evaluated relatively with the image density corresponding to the case where the toner amount on the transfer paper was 0.5 mg / cm ² .
A: Image density is 1.40 or more B: Image density is 1.35 or more and less than 1.40 C: Image density is 1.20 or more and less than 1.35 D: Image density is less than 1.20

<Image fog>
The durability of the toner was evaluated by performing a durability test using the evaluation machine.
The durability test conditions were as follows: in an environment of high temperature and high humidity (30 ° C, 80% RH; H / H), an original image with a printing ratio of 2% was printed out 3000 sheets a day for 4 days. A total of 12,000 sheets were output.
The evaluation timing was every 1000 sheets, and a solid white image was output on the first sheet on each evaluation day, and the following evaluation criteria were used.
Using “REFLECTMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku Co., Ltd.), the reflectance of the white background portion of the standard paper and the printout image was measured, and the fog (reflectance:%) was calculated by the following formula. The filter was measured with a blue filter attached.
Fog (reflectance;%) = (reflectance of standard paper;%) − (reflectance of sample;%)
In addition, the evaluation criteria judged the worst value through durability with the following criteria.
A: Very good Less than 1.0% B: Good 1.0% or more to less than 2.0% C: No practical problem 2.0% or more to less than 3.0% D: Inferior 3.0% or more

<Evaluation of storage stability of toner>
The storage stability of the toner was evaluated by weighing 10 g of toner in a 100 ml polycup and leaving it in a constant temperature layer at 50 ° C. for 3 days, and then evaluating the sieving property of 200 mesh (opening).
As a measuring apparatus, a powder tester (manufactured by Hosokawa Micron Corporation) having a digital vibrometer (manufactured by DEGITAL VIBRATION METERMODEL 1332 SHOWA SOKKI CORPORATION) was used.
As a measuring method, a toner for evaluation is placed on a set 200 mesh sieve (aperture 75 μm), and the displacement value of the digital vibrometer is adjusted to 0.50 mm (peak-to-peak) for 30 seconds. Vibration was applied. Thereafter, the storage stability was evaluated from the state of the aggregate of toner remaining on each sieve.
A: The toner remaining amount on the mesh is less than 1.0 g, and the fluidity is excellent.
B: The amount of toner remaining on the mesh is 1.0 g or more and less than 2.5 g.
C: The amount of toner remaining on the mesh is 2.5 g or more or there is an agglomerate and cannot be easily loosened.

41: Disperser, 42: Casing, 43: Three-way valve, 44: Disperser inlet pressure adjustment valve, 45: Disperser inlet pressure gauge, 46: Strainer, 47: Disperser inlet thermometer, 48: Disperser outlet thermometer , 49: Back valve, 50: Circulation pump, 51: Cooling means, 52: Disperser outlet pressure gauge, 53: Stirrer motor, 54, 55: Cooling water supply port, 56, 57: Cooling water discharge port, 58: Cooling jacket, 59: Disperser back pressure adjustment valve, 60: Three-way valve, 61: Holding tank, 62: Shaft seal liquid tank, 63: Air pressure gauge, 64: Regulator, 65: Air inlet, 66: Shaft seal liquid Tank pressure gauge, 67 shaft seal liquid injection line, 68: shaft seal liquid return line, 69: cylindrical rotor, 70: media particle separation separator (centrifuge screen), 71: drive shaft, 7 2: media particles, 73: rotor pins, 74: vessel pins, 75: grinding chamber, 76: treatment liquid inlet, 77: treatment liquid outlet, 78: wedge wire, 79: cooling water inlet 80: cooling water outlet

Claims (11)

Colorant dispersion obtained by dispersing a colorant mixture containing a liquid medium, a colorant and an azo compound represented by the following general formula (1) using a media disperser to obtain a colorant dispersion A method for producing a toner comprising producing a toner in an aqueous medium, comprising:

[In the general formula (1), any one of R ₁ , R ₂ , and Ar has a structure in which a polymer component is bonded through a single bond or a linking group,
R ₁ represents an alkyl group, a phenyl group, an OR ₄ group or an NR ₅ R ₆ group, and R _{4 to} R ₆ each independently represent a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. When R ₁ is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to R ₁ is an amide group, ester group, urethane group, urea group, alkylene group, phenylene group, -O A divalent linking group selected from the group consisting of —, —NR ₃ — and —NHCH (CH ₂ OH) —, and R ₃ represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group;
R ₂ represents an alkyl group, a phenyl group, an OR ₈ group or an NR ₉ R ₁₀ group, and R _{8 to} R ₁₀ each independently represent a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. When R ₂ is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to R ₂ is an alkylene group, a phenylene group, —O—, —NR ₇ — and —NHCH (CH ₂ R ₇ represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
Ar represents an aryl group, and when Ar is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to Ar is an amide group, an ester group, a urethane group, a urea group, or an alkylene group. , A phenylene group, —O—, —NR ₃ — and —NHCH (CH ₂ OH) —, a divalent linking group selected from the group consisting of R ₃ is a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. Represents.
When the single bond or linking group is bonded to R ₁ , R ₂ , or Ar, it is bonded to a hydrogen atom of R ₁ , R ₂ , or Ar. ]
The colorant is C.I. I. Pigment Red 122, C.I. I. Pigment Violet 19, C.I. I. Pigment Red 31, C.I. I. Pigment Red 150, C.I. I. Pigment Red 269, and C.I. I. Containing one or more selected from the group consisting of Pigment Yellow 155,
The concentration of the colorant in the colorant dispersion is 10% by mass or more and 25% by mass or less,
In the colorant dispersion step, a colorant is dispersed using a media disperser using media particles having a number average particle diameter of 0.05 mm or more and 0.80 mm or less.   The media disperser is a media disperser having an external circulation path. While the disperser is filled with the colorant mixture, the colorant mixture is repeatedly introduced into and discharged from the media disperser, and the colorant is dispersed while being circulated. The toner production method according to claim 1, wherein a colorant dispersion is obtained. The media disperser includes a cylindrical vessel and a rotor arranged coaxially with the vessel in the vessel and rotatable with respect to the vessel, and a vessel pin protruding radially inward on the inner surface of the vessel A rotor pin protruding radially outward is implanted on the outer surface of the rotor, the media particles are filled inside the vessel, and the colorant mixed solution is placed on one end side in the axial direction. A processing liquid inlet for introducing into the vessel is provided on the other end side at a position along the rotation axis so that a screen-shaped processing liquid outlet is surrounded by a rotor having a media particle outlet. The colorant mixture is introduced from the liquid inlet, and the rotor is rotated with respect to the vessel while being fed toward the treatment liquid outlet, whereby the media particles in the vessel are agitated to finely disperse the colorant. Method for producing a toner according to claim 1 or 2, characterized in.   The content of the azo compound in the colorant dispersion is 3 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the total amount of the colorant. 2. A method for producing a toner according to item 1.   The liquid medium is a polymerizable monomer, the polymerizable monomer composition containing the colorant dispersion obtained in the colorant dispersion step is granulated in an aqueous medium, and the granulated particles 5. The method for producing a toner according to claim 1, wherein a toner particle is obtained by polymerizing a polymerizable monomer contained in the toner. The method for producing a toner according to claim 1, wherein the azo compound represented by the general formula (1) is an azo compound represented by the following general formula (2).

[In the general formula (2), any one of R ₁ , R ₂ , R _{11 to} R ₁₅ has a structure in which a polymer component is bonded via a single bond or a linking group, and R ₁ and R ₂ , and , R ₁ and R ₂ have the same linking group as that represented by the general formula (1). R _{11 to} R ₁₅ each independently represents a hydrogen atom, a COOR ₁₆ group, or a CONR ₁₇ R ₁₈ group. R _{16 to} R ₁₈ each independently represents a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group. When R _{11 to} R ₁₅ are bonded to the polymer component, they are bonded through a single bond or a linking group, and the linking group bonded to R _{11 to} R ₁₅ is an amide group, an ester group, a urethane group, a urea group, or an alkylene group. , A phenylene group, —O—, —NH—, and —NHCH (CH ₂ OH) —. When the single bond or linking group is bonded to R ₁ , R ₂ , R _{11 to} R ₁₅ , it is bonded to a hydrogen atom of R ₁ , R ₂ , R _{11 to} R ₁₅ . ] The R ₂ in the general formula (1) is an NR ₉ R ₁₀ group, the R ₉ is a hydrogen atom, and the R ₁₀ is a phenyl group, 7. Toner production method. In the general formula (1), R ₂ is an NR ₉ R ₁₀ group, R ₉ is a hydrogen atom, R ₁₀ is a phenyl group, and the phenyl group is connected to the polymer component via a divalent linking group. The toner manufacturing method according to claim 1, wherein the toner is bonded to the toner. The azo compound represented by the general formula (1) is an azo compound represented by the following general formula (3) or the following general formula (4). 2. A method for producing the toner according to 1.

[In the general formulas (3) and (4), L represents a divalent linking group for bonding to the polymer component. ] 10. The polymer component according to claim 1, wherein the polymer component is a polymer or copolymer containing a monomer unit represented by the following general formula (5) as a constituent component. Toner manufacturing method.

[In Formula (5), R ₁₉ represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms. R ₂₀ represents a phenyl group, a carboxyl group, a carboxylic acid ester group, a carboxylic acid aralkyl ester group or a carboxylic acid amide group. ]   11. The toner production according to claim 1, wherein the acid value of the azo compound is 30 mg KOH / g or less, and the amine value of the azo compound is 10 mg KOH / g or less. Method.

Images