JP6173125B2 - toner - Google Patents

Description

  The present invention relates to a toner used in an electrophotographic method, an electrostatic recording method or a toner jet method.

In recent years, there has been an increasing demand to make a copier or printer small and excellent in energy saving.
In response to the above requirements, there is a need for a toner that is more excellent in low-temperature fixability, and that can achieve high coloring power and high image quality.
In response to this requirement, there is a method for obtaining a toner having excellent low-temperature fixability by incorporating a polyester resin having a specific dialcohol component as a monomer and a specific range of solubility parameters into the toner.
However, some problems still exist with respect to tinting strength and fogging in long-term use under high-temperature and high-humidity environments or low-temperature and low-humidity environments.

Further, there is a method for obtaining a toner by polymerizing using a specific peroxide-based polymerization initiator in the presence of a polymerizable monomer and a crystalline polyester resin in an aqueous medium (for example, Patent Document 1). ). The toner obtained by such a method can be used for long-term and high-temperature and high-humidity environments, such as fogging, thin density, image unevenness, filming, and the surface of the latent image carrier and developer carrier of toner and inorganic fine particles. There is no problem of member contamination, poor cleaning, etc. Further, by using such a toner, an image excellent in transfer efficiency, low-temperature fixability, and offset resistance can be obtained.
However, since the pigment is not sufficiently dispersed in the toner, the coloring power of the toner is not sufficient, and there are still some problems regarding fogging when used for a long time in a high temperature and high humidity environment or a low temperature and low humidity environment. ing.

In addition, the toner contains at least a crystalline polyester and an amorphous polyester as a binder resin, and has a predetermined physical property value within a specific range, thereby obtaining a toner having good low-temperature fixability, heat-resistant storage stability, and separation performance. There exists a method (for example, patent document 2).
However, since the pigment is not sufficiently dispersed in the toner, the coloring power of the toner is not sufficient, and there are still some problems regarding fogging when used for a long time in a high temperature and high humidity environment or a low temperature and low humidity environment. ing.

JP 2009-63969 A JP 2012-108462 A

Solubleity Parameters: ALLAN F. M.M. BARTON Chemistry Department, Victoria University of Wellington, Private Bag, Wellington, New Zealand Received June 19, 1974 (Revised Manduced 74)

  Therefore, an object of the present invention is excellent in low-temperature fixability, a sufficient image density can be obtained even with a small amount, and in use for a long period of time, or in a high-temperature and high-humidity environment or a low-temperature and low-humidity environment. Another object of the present invention is to provide a toner that is free from image defects such as fogging.

The present invention is a toner having toner particles containing a binder resin, a pigment, a pigment dispersant, and a crystalline polyester, wherein the binder resin is an amorphous polyester resin, and the pigment dispersant is the following: The present invention relates to a toner satisfying (i) to (iv).
(I) The difference (A−B) between the SP value (A) of the pigment dispersant and the SP value (B) of the crystalline polyester resin is −0.90 or more and +1.00 or less.
(Ii) The difference (A−C) between the SP value (A) of the pigment dispersant and the SP value (C) of the binder resin is −2.00 or more and +2.00 or less.
(Iii) The pigment dispersant has a polymer component and an adsorption component having an adsorption rate of 30% or more to the pigment, and the polymer component has a partial structure represented by a vinyl polymer.
(Iv) The number average molecular weight (Mn) of the polymer component of the pigment dispersant is 3000 to 20000.

  According to the present invention, it has excellent low-temperature fixability and a sufficient image density can be obtained even in a small amount, and it can be used for a long time, or in a high-temperature and high-humidity environment or in a low-temperature and low-humidity environment. A toner free from image defects such as fogging can be obtained.

It is a figure showing the tautomer which the azo compound which is a pigment dispersant shown by General formula (1) can take.

Hereinafter, the present invention will be described in detail.
The toner of the present invention is a toner having toner particles containing a binder resin, a pigment, a pigment dispersant, and crystalline polyester.
The binder resin is an amorphous polyester resin,
The pigment is carbon black, C.I. I. Pigment red 122, C.I. I. Pigment red 150, and C.I. I. A pigment selected from the group consisting of CI Pigment Yellow 185;
Meets the pigment dispersing agent is less than the (i) ~ (iv), and by having a partial structure represented by the following general formula (2), the effect of the invention described above.
(I) The difference (A−B) between the SP value (A) of the pigment dispersant and the SP value (B) of the crystalline polyester resin is −0.90 or more and +1.00 or less,
(Ii) The difference (A−C) between the SP value (A) of the pigment dispersant and the SP value (C) of the binder resin is −2.00 or more and +2.00 or less,
(Iii) The pigment dispersant has a polymer component and an adsorption component having an adsorption rate of 30% or more to the pigment, and the polymer component has a partial structure represented by a vinyl polymer,
(Iv) The number average molecular weight (Mn) of the polymer component of the pigment dispersant is 3000 to 20000.
The reason why the effect of the present invention is manifested is not necessarily clear, but the present inventors consider as follows.

The difference (A−C) between the SP value (A) of the pigment dispersant and the SP value (C) of the binder resin is −2.00 or more and +2.00 or less. More preferably, it is −2.00 or more and +0.05 or less.
When the difference (A−C) between the SP value (A) of the pigment dispersant and the SP value (C) of the binder resin is −2.00 or more and +2.00 or less, the dispersion group site of the pigment dispersant The molecules of the polymer component are not contracted in the binder resin, the steric repulsion effect is not reduced, and the dispersion state of the pigment is not deteriorated.

In addition, when the difference between the SP value of the pigment dispersant and the SP value of the crystalline polyester resin is large, the affinity for each other is low when contacting the crystalline polyester resin during toner production. The molecule of the polymer component corresponding to the dispersion group of the polymer shrinks, and the pigment dispersion effect is reduced.
In order not to reduce the pigment dispersion effect, the difference (A−B) between the SP value (A) of the pigment dispersant and the SP value (B) of the crystalline polyester resin is set to −0.90 or more and +1.00 or less. It is more preferably −0.78 or more and +0.78 or less, and further preferably −0.78 or more and +0.60 or less.

Further, when the number average molecular weight (Mn) of the polymer component which is a dispersing group of the pigment dispersant is 3000 or more, the steric repulsion effect is not weakened, and the dispersed state of the pigment can be favorably maintained.
When the number average molecular weight (Mn) is 20000 or less, the distance between the pigment particles is reduced without cross-linking the pigment particles or restricting the movement of the pigment particles, and the uniform dispersion of the pigment particles is inhibited. Do not do. Further, the viscosity of the pigment dispersion does not become too high, and there is no disadvantage in sharpening the particle size distribution in the granulation process at the time of toner particle production.
Therefore, the number average molecular weight (Mn) of the polymer component which is the dispersing group of the pigment dispersant is set to 3000 or more and 20000 or less. It is more preferably 6000 or more and 20000 or less, and further preferably 9000 or more and 20000 or less.

When the adsorption rate of the pigment dispersant to the pigment is 30% or more, the pigment dispersant is not easily detached from the pigment particles in the toner production process, and the dispersed state of the pigment can be maintained well.
Therefore, the adsorption rate of the pigment dispersant to the pigment is set to 30% or more. It is more preferably 50% or more, even more preferably 70% or more, and even more preferably 85% or more.

The structure of the pigment dispersant preferably has an adsorbing component that adsorbs to the surface of the pigment and a polymer component that is a dispersing group that produces a steric repulsion effect. If the adsorbing group and the dispersing group are not clearly present, the pigment dispersant is not preferable because it has a small adsorptive power to the pigment and weak steric repulsion effect. Further, when the dispersing group is not a polymer component, that is, a low molecular weight component, the steric repulsion effect is weak, and the repulsion effect due to polarity is not preferable in an organic solvent, which is not preferable.
The polymer component which is a dispersing group of the pigment dispersant has a partial structure represented by a vinyl polymer in order to adjust the affinity with a crystalline polyester resin and a polyester resin which is a binder resin.
The polymer component which is a dispersing group of the pigment dispersant preferably has a monomer unit represented by the following general formula (1).

一般式（１）中、Ｒ_１は、アルキル基、アラルキル基、水素原子を示し、Ｒ_２は、炭素原子４〜２２のアルキル基を示す。

In the general formula (1), R ₁ represents an alkyl group, an aralkyl group, or a hydrogen atom, and R ₂ represents an alkyl group having 4 to 22 carbon atoms.

This is because the toner of the present invention contains a crystalline polyester resin. A crystalline polyester resin has crystallinity and thus has low solubility. Moreover, compared with an amorphous polyester resin, hydrophobicity is strong. In particular, when the toner is produced by granulating it in a state dissolved in an organic solvent and then passing through a solvent removal step, the affinity between the crystalline polyester resin and the pigment is low during the granulation step. Easy to aggregate.
Further, in the solvent removal step, as the solvent moves out of the system, the crystalline polyester resin is precipitated. At this time, the pigment has a low affinity with the crystalline polyester resin, and thus the above-mentioned The pigment tends to aggregate. In order to suppress the aggregation of the pigment with the pigment dispersant, the pigment dispersant needs to cover the surface of the pigment, and the pigment dispersant needs to have high affinity with the crystalline polyester resin.
Therefore, the hydrophobicity of the dispersing group is increased by the polymer component that is the dispersing group of the pigment dispersant having the structure represented by the general formula (1). Moreover, the dispersibility of the pigment can be maintained even in the presence of the crystalline polyester resin by increasing the structural similarity with the monomer composition of the crystalline polyester and improving the steric repulsion effect.

In order to express the above effect, in general formula (1), R ₂ is preferably an alkyl group having 4 to 22 carbon atoms. It is preferable that the alkyl group of R ₂ has 4 or more carbon atoms since the hydrophobicity of the dispersing group is sufficient and the steric repulsion effect is not weak. When the carbon number of the alkyl group of R ₂ is 22 or less, the adsorption group portion of the pigment dispersant does not cause steric hindrance when adsorbing to the pigment, and the adsorption rate does not decrease. Moreover, since the crystallinity of the said crystalline polyester resin is not inhibited, it is preferable.
In general formula (1), R ₁ is preferably an alkyl group, an aralkyl group, or a hydrogen atom. It is preferable that R ₁ is an alkyl group, an aralkyl group, or a hydrogen atom because the affinity with the crystalline polyester resin does not decrease due to steric hindrance or the like.

More preferably, the pigment dispersant has a partial structure represented by a polyester resin.
This is because the binder resin of the toner of the present invention is an amorphous polyester resin. Since the binder resin is a polyester resin, when the pigment dispersant has a partial structure represented by a polyester resin, the affinity of the pigment dispersant for the binder resin is increased. For this reason, the pigment dispersant is preferably dissolved in the toner and distributed in a state where the molecular chain is widened, so that the steric repulsion effect is large and the dispersion stability of the pigment is improved.

The pigment dispersant that have a partial structure represented by the following general formula (2).
This is because the partial structure represented by the following general formula (2) exhibits high ability as an adsorbing group to the pigment.
The adsorptive power of the adsorbing group of the pigment dispersant to the surface of the pigment is determined approximately by the π-π interaction by π electrons, hydrogen bonding, and polarity. For example, when the pigment dispersant has a structure including an aromatic ring, an interaction due to π electrons in the aromatic ring occurs, and it is considered that the adsorptive power of the adsorption group of the pigment dispersant to the surface of the pigment is increased.

  However, since the toner is a composite of various materials, it is considered that there are factors that affect the adsorptive power other than the π-π interaction caused by the π electrons in the aromatic ring of the pigment dispersant. In general, the binder resin constituting the toner is often polyester, polyurethane, or styrene-acrylic resin. However, since any binder resin has an aromatic ring, the aromatic ring in the binder resin is used. In this case, a π-π interaction occurs. As a result, the pigment dispersant interferes with the binder resin, and the π-π interaction effect of the pigment dispersant with respect to the pigment is weakened. Therefore, it is considered that the adsorptive power of the pigment dispersant adsorbing group to the pigment surface is weakened. .

Here, the pigment dispersant represented by the general formula (2) used in the present invention includes a tautomer represented by the following general formula (T1) and the following general formula (T2), as shown below. There exists a tautomer represented by Therefore, in addition to the π-π interaction in the aryl group in the azo compound represented by the general formula (2), it is considered that an even stronger π-π interaction can be obtained by the following resonance structure.
A resonance structure comprising an azo bond directly connected to an aryl group in an azo skeleton partial structure, and a carbonyl group disposed so as to influence and resonate with the azo bond.
Further, it is considered that the adsorptive power to the pigment of the pigment dispersant represented by the general formula (2) is enhanced by the action of the amine structure in the azo skeleton partial structure and the polarities of the hydroxyl group and the carbonyl group. Furthermore, it is thought that the action of hydrogen bonding is also manifested between the polar group of the azo skeleton partial structure and the pigment, and the adsorptive power is further increased.
In addition, the polymer component of the pigment dispersant acts as a dispersing group, and the dispersion state of the pigment can be well maintained by suppressing aggregation of the pigment particles due to steric hindrance or the like.
Therefore, these tautomers are also within the scope of the present invention.

As seen in commercially available pigment dispersants, the above pigment dispersant has less influence on the chargeability of the toner compared to the case where only polar groups such as amine structure and carboxyl group are used as the adsorption group to the pigment. . This is because the azo skeleton partial structure is a tautomer as shown below, so that there is little bias with respect to the distribution of electrons and there is no strong positive or negative with respect to chargeability.
In addition, because of the above-described three effects of π-π interaction, polarity and hydrogen bond, the adsorptive power to the pigment is stronger than in the case of only a polar group, so that the dispersion state of the pigment is maintained well, and The release of the pigment dispersant from the pigment is also suppressed. For this reason, not only the coloring power of the toner but also an excellent effect is exhibited in terms of chargeability.

［式（Ｔ１）および（Ｔ２）中のＲ_３、Ｒ_４およびＡｒは、それぞれ式（２）におけるＲ_３、Ｒ_４およびＡｒと同義である。］

_[R 3, _{R 4} and Ar in Formula (T1) and (T2) has the same meaning as _R 3, _{R 4} and Ar in each formula (2). ]

(Pigment dispersant)
The pigment dispersant represented by the following general formula (2) will be described in detail.

In the general formula (2), any of R ₃ , R ₄ and Ar is bonded to the polymer component via a single bond or a linking group,
R ₃ represents an alkyl group, a phenyl group, an OR ₆ group or an NR ₇ R ₈ group.
R _{6 to} R ₈ each independently represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
When R ₃ is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to R ₃ 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 ₅ — and —NHCH (CH ₂ OH) —;
R ₅ represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.

R ₄ represents an alkyl group, a phenyl group, an OR ₁₀ group or an NR ₁₁ R ₁₂ group.
R ₁₀ to R ₁₂ each independently represent a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
When R ₄ is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to R ₄ is an alkylene group, a phenylene group, a carboxylic acid ester group, a carboxylic acid amide group, or a sulfonic acid ester group. , A sulfonic acid amide group, —O—, —NR ₉ —, and —NHCH (CH ₂ OH) —.
R ₉ 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) —.
The single bond or a linking _group, when bound to R 3, _{R 4} or Ar _is bonded substituted with R 3, _{R 4} or Ar hydrogen atoms.
Examples of the aralkyl group in R ₃ and R ₄ in the general formula (2) include a benzyl group and a phenethyl group.
From the viewpoint of the affinity for the pigment, R ₃ is preferably an alkyl group having 1 to 6 carbon atoms, a phenyl group, an NH ₂ group, an OCH ₃ group, or an OC H ₂ C ₆ H ₅ group.

Further, when R ₃ is bonded to the polymer component, it is bonded via a single bond or a linking group, and the linking group bonded to R ₃ is an amide group, an ester group, a urethane group, a urea group, an alkylene group, a phenylene group, A divalent linking group selected from the group consisting of —O—, —NH— and —NHCH (CH ₂ OH) — is preferable. In addition, when the said single bond or a coupling group couple | bonds with R < ₃ >, it substitutes and substitutes for the hydrogen atom of R < ₃ >.
Further, R ₃ in the general formula (2) as long as it does not inhibit significantly the affinity of the pigment may be substituted by further substituents. In this case, examples of the substituent include a halogen atom, a nitro group, an amino group, a hydroxyl group, a cyano group, and a trifluoromethyl group.

In the present invention, from the viewpoint of affinity for the pigment, R ₄ is preferably an NR ₁₁ R ₁₂ group, R ₁₁ is a hydrogen atom, and R ₁₂ is a phenyl group. This is because the effect of π-π interaction (π electron interaction) by π electrons is improved without inhibiting the effect of polarity of the azo skeleton partial structure.
Specifically, a π-plane that causes π-electron interaction is formed by an intramolecular hydrogen bond between a hydrogen atom of R ₁₁ and an oxygen atom derived from a carbonyl group adjacent to R ₃ , and further derived from a phenyl group of R ₄ The π plane also exists. For this reason, the effect of π electron interaction is improved by these two π planes.
Further, it is preferable that R ₄ is an NR ₁₁ R ₁₂ group, R ₁₁ is a hydrogen atom, and R ₁₂ is a phenyl group. This is because the amine of NR ₁₁ forms a π plane that causes π electron interaction by intramolecular hydrogen bonding, and thus has little influence on the charging property, and does not increase the positive property even in the charging property of the toner.

On the other hand, when R ₄ is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to R ₄ is an alkylene group, a phenylene group, a carboxylic acid ester group, a carboxylic acid amide group, a sulfonic acid A divalent linking group selected from the group consisting of an ester group, a sulfonic acid amide group, —O—, —NH— and —NHCH (CH ₂ OH) — is preferable.
Further, in the case _{where R 4} is bound to the polymer component, _{R 4} is _NR 11 _{R 12} groups, _{and, R 11} is a hydrogen _{atom, R 12} is a phenyl group, the linking group is -NH- It is more preferable.
This is because the π-electron interaction of the azo compound, including the Ar, is stronger than in the case where 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. This is because the effect of the two resonance structures is not maximized.

On the other hand, when R ₄ is an NR ₁₁ R ₁₂ group, R ₁₁ is a hydrogen atom, R ₁₂ is a phenyl group, and the phenyl group is bonded to the polymer via a divalent linking group, The influence of the polymer component on the electron cloud of the azo skeleton partial structure in the above formula (2) is reduced. This is due to the action of π electrons of the phenyl group of R ₁₂ . As a result, the effects of the three resonance structures of the π-electron and polarity of the azo skeleton partial structure in the general formula (2) and the general formulas (2), (T1), and (T2) are hardly reduced. The effect of the present invention is maximized.
Incidentally, the single bond or a linking group may bind to R _4, and bind to replace the hydrogen atom of R _4.
In the present invention, Ar represents an aryl group, such as a phenyl group or a naphthyl group.

On the other hand, 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 —, —NR ₃ — and —NHCH (CH ₂ OH) — is preferred.
Ar may be further substituted with a substituent as long as the resonance structure is not inhibited and the affinity for the pigment is not significantly inhibited. In this case, examples of the substituent 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.
As described above, when a single bond or a linking group is bonded to Ar, it is bonded to a hydrogen atom of Ar or a hydrogen atom of a substituent of Ar.
In the present invention, from the viewpoint of affinity with the pigment, the pigment dispersant represented by the general formula (2) is preferably an azo compound represented by the following general formula (3).

上記一般式（３）中、Ｒ_３、Ｒ_４、Ｒ_１３〜Ｒ_１７のいずれかは、単結合または連結基を介してポリマー成分と結合する。
Ｒ_３およびＲ_４、ならびに、Ｒ_３およびＲ_４に結合する連結基は、それぞれ上記式（２）におけるＲ_３およびＲ_４ 、ならびに、Ｒ _３ およびＲ _４ に結合する連結基と同義である。
Ｒ_１３〜Ｒ_１７はそれぞれ独立して水素原子、ＣＯＯＲ_１８基、ＣＯＮＲ_１９Ｒ_２０基を示す。Ｒ_１８〜Ｒ_２０はそれぞれ独立して水素原子、アルキル基、フェニル基またはアラルキル基を示す。
上記Ｒ_１８〜Ｒ_２０におけるアルキル基は、炭素原子数１〜６のアルキル基であることが好ましい。中でも特にメチル基、エチル基、ｎ−プロピル基およびイソプロピル基が、立体障害による顔料との親和性低下を防止する観点から好ましい。
上記Ｒ_１８〜Ｒ_２０におけるアラルキル基としては、例えば、ベンジル基およびフェネチル基などが挙げられる。
なお、上記単結合または連結基が、Ｒ_３、Ｒ_４、Ｒ_１３〜Ｒ_１７に結合する場合は、Ｒ_３、Ｒ_４、Ｒ_１３〜Ｒ_１７の水素原子と置換して結合する。
上記一般式（３）中のＲ_１３〜Ｒ_１７は、水素原子、ＣＯＯＲ_１８基およびＣＯＮＲ_１９Ｒ_２０基より選択できるが、顔料への親和性の観点から、Ｒ_１３〜Ｒ_１７のうち少なくとも１つがＣＯＯＲ_１８基またはＣＯＮＲ_１９Ｒ_２０基であることが好ましい。
例えば、顔料がカーボンブラック、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ ７４、９３、１３９、１５５、１８０、１８５、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ３１、１２２、１５０、１７０、２５８、２６９、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｖｉｏｌｅｔ １９、または、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ ２５、２６の場合、Ｒ_１３〜Ｒ_１７のうち少なくとも１つがＣＯＯＲ_１８基またはＣＯＮＲ_１９Ｒ_２０基であることで、各顔料のカルボニル基または２級アミンの水素原子へ、本発明のアゾ骨格部分構造が水素結合するため、上記アゾ骨格部分構造と顔料が一層強く吸着する。さらに、顔料が、一次粒径が１４ｎｍ以上８０ｎｍ以下のカーボンブラック、Ｐ．Ｙ．１３９、１５５、１８０、１８５、Ｐ．Ｒ．３１、１２２、１５０、２６９、または、Ｐ．Ｖ．１９の場合、本発明のアゾ骨格部分構造のＲ_１３〜Ｒ_１７のうち少なくとも１つがＣＯＮＲ_１９Ｒ_２０基であることで、各顔料のアミド結合部位が相互作用を起こし、顔料へのアゾ骨格部分構造の吸着基の吸着力が一層強くなるため好ましい。
上記一般式（３）中のＲ_１８〜Ｒ_２０は、上記に列挙した置換基および水素原子から任意に選択できるが、顔料への親和性の観点から、Ｒ_１８がメチル基であり、Ｒ_１９およびＲ_２０が水素原子またはメチル基であることが好ましい。この場合、立体障害が生じないだけでなく、エステル結合またはアミド結合が存在することで、上記顔料への水素結合および極性による吸着力が高まるからである。
上記一般式（３）中の置換基の組み合わせについて、以下に例を挙げて説明するが、本発明はこれらに限定されるものではない。上記一般式（３）は、下記一般式（６−１）〜（９）のいずれかで示される場合、顔料への親和性がより向上する。

In the general formula (3), any of R ₃ , R ₄ , R _{13 to} R ₁₇ is bonded to the polymer component via a single bond or a linking group.
R ₃ and _{R 4,} as well as linking groups attached to the _{R 3} and _{R 4, R 3} and _{R 4} in the formula (2), and is synonymous with the linking group bound to _{R 3} and _{R 4.}
R _{13 to} R ₁₇ each independently represent a hydrogen atom, a COOR ₁₈ group, or a CONR ₁₉ R ₂₀ group. R _{18 to} R ₂₀ each independently represent a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
The alkyl group for R _{18 to} R ₂₀ is preferably an alkyl group having 1 to 6 carbon atoms. Among these, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are particularly preferable from the viewpoint of preventing a decrease in affinity with the pigment due to steric hindrance.
Examples of the aralkyl group in R _{18 to} R ₂₀ include a benzyl group and a phenethyl group.
Incidentally, the single bond or a linking _group, when bound to _{R 3, R 4, R 13} ~R 17 _is, R _{3, R 4,} and bind to replace the hydrogen atom of R 13 _{to R 17.}
R _{13 to} R ₁₇ in the general formula (3) can be selected from a hydrogen atom, a COOR ₁₈ group, and a CONR ₁₉ R ₂₀ group. From the viewpoint of affinity for the pigment, at least one of R _{13 to} R ₁₇ One is preferably a COOR ₁₈ group or a CONR ₁₉ R ₂₀ group.
For example, the pigment is carbon black, C.I. I. Pigment Yellow 74, 93, 139, 155, 180, 185, C.I. I. Pigment Red 31, 122, 150, 170, 258, 269, C.I. I. Pigment Violet 19, or C.I. I. In the case of Pigment Blue 25 and 26, at least one of R _{13 to} R ₁₇ is a COOR ₁₈ group or a CONR ₁₉ R ₂₀ group, so that a carbonyl group of each pigment or a hydrogen atom of a secondary amine is bonded to the azo group of the present invention. Since the skeleton partial structure is hydrogen-bonded, the azo skeleton partial structure and the pigment are more strongly adsorbed. Further, the pigment is carbon black having a primary particle size of 14 nm or more and 80 nm or less, P.I. Y. 139, 155, 180, 185, p. R. 31, 122, 150, 269, or P.I. V. In the case of 19, when at least one of R _{13 to} R ₁₇ of the azo skeleton partial structure of the present invention is a CONR ₁₉ R ₂₀ group, the amide bond site of each pigment causes an interaction, and the azo skeleton moiety to the pigment This is preferable because the adsorptive power of the adsorptive group of the structure becomes stronger.
R _{18 to} R ₂₀ in the general formula (3) can be arbitrarily selected from the substituents and hydrogen atoms listed above, but from the viewpoint of affinity for the pigment, R ₁₈ is a methyl group, and R ₁₉ And R ₂₀ is preferably a hydrogen atom or a methyl group. In this case, not only does the steric hindrance not occur, but also the presence of an ester bond or an amide bond increases the adsorption power due to the hydrogen bond and polarity to the pigment.
Examples of combinations of substituents in the general formula (3) will be described below, but the present invention is not limited to these examples. When the general formula (3) is represented by any of the following general formulas (6-1) to (9), the affinity for the pigment is further improved.

For the pigment used in the present invention, as shown in the above general formulas (6-1) to (8), an amide bond to an azo bond site bonded to a phenyl group that does not bond to a polymer via a linking group. It is most effective when the group or sulfoamide group is in the m-position or p-position. However, it may be o-position.
When the amide group or the sulfoamide group is in the m-position or the p-position, it is in an optimal positional relationship for performing hydrogen bonding to the carbonyl group of the pigment or the hydrogen atom of the secondary amine. The most effective. This is probably because the o-position is difficult to coordinate with the pigment due to steric hindrance.

Further, in the above general formula (9), 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. The most effective. However, two COOCH ₃ groups may be present at any position.
In the general formulas (6-1) to (9), “L” represents a linking group that links the azo skeleton partial structure and the polymer component. The linking group L is not particularly limited as long as it is a divalent linking group, but is an alkylene group, a phenylene group, —O—, —NH—, —NHCH (CH ₂ OH) —, a carboxylate group And a divalent linking group selected from the group consisting of a carboxylic acid amide group, a sulfonic acid ester group and a sulfonic acid amide group.

In the above general formulas (6-1) to (9), the bonding position of the linking group (substitution position of the phenyl group with a hydrogen atom) is the o-position, m-position or p-position with respect to the amide group. Any of these positions may be used, and the influence on the affinity to the pigment due to the difference in these substitution positions is the same.
In order for the pigment dispersant used in the present invention to maintain a good dispersion state of the pigment in the toner, the polymer component must be maintained in a state where the molecular chain is sufficiently expanded in the binder resin constituting the toner. . For this purpose, the polymer component of the pigment dispersant must have good affinity with the binder resin constituting the toner. As used herein, “affinity with the binder resin” indicates compatibility with the binder resin. If the compatibility of the pigment dispersant and the binder resin is poor, the pigment dispersant aggregates and the molecular chain of the polymer component contracts, and the molecular chain does not spread sufficiently. The repulsion effect cannot be obtained, and pigment aggregation cannot be suppressed.

Therefore, when the binder resin is a polyester resin, it is preferable that the polymer component of the pigment dispersant contains the crystalline polyester resin or a polyester resin having an SP value close to that of the binder resin. This is because those having higher structural similarity have higher affinity.
Further, when the toner is produced by the dissolution suspension method (suspension granulation method), the polymer component of the pigment dispersant is selected to have a structure having an affinity with the organic solvent used at the time of toner production. It is preferable. However, since the organic solvent used at this time dissolves both the binder resin and the crystalline polyester resin, the affinity for both is high. Therefore, the influence of the organic solvent is small compared with the binder resin and the crystalline polyester resin.

  The vinyl polymer constituting the polymer component of the pigment dispersant includes the following general formula (10) including the general formula (1) in order to adjust the affinity with the binder resin and crystalline polyester resin of the toner. The polymer or copolymer containing a monomer unit represented by

［一般式（１０）中、Ｒ_２１は水素原子または炭素原子数が１もしくは２のアルキル基を示す。Ｒ_２２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またはカルボン酸アミド基を示す。］

[In General Formula (10), R ₂₁ represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms. R ₂₂ 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 ₂₁ in the general formula (10) is preferably a hydrogen atom or a methyl group from the viewpoint of polymerizability of the monomer unit.
Further, R ₂₂ in the general formula (10) is preferably a carboxylic acid ester group, a carboxylic acid amide group, a phenyl group or a carboxyl group. From the viewpoint of dispersibility and compatibility of the azo compound in the binder resin constituting the toner, a phenyl group, a carboxylic acid ester group or a carboxylic acid amide group is preferable.

Further, the substituent of R ₂₂ in the general formula (10) may be further substituted, which inhibits the polymerizability of the monomer unit or significantly lowers the solubility of the pigment dispersant. Otherwise there is no particular restriction. In this case, examples of the substituent include an alkoxy group, an amino group, and an acyl group.
Although the copolymer which contains the monomer unit shown by the said General formula (10) as a structural component below is illustrated more concretely, it is not limited to these.
The polymer component of the pigment dispersant in the present invention is a monomer unit selected from the group consisting of the following general formulas (11-1), (11-2), (11-3) and (11-4). Preferred examples include a copolymer contained as a constituent component.

［一般式（１１−１）中、Ｒ_２３は水素原子または炭素原子数が１もしくは２のアルキル基を示し、Ｒ_２４は炭素原子数が１〜２２のアルキル基または炭素原子数が７もしくは８のアラルキル基を示す。ｌは、０または正の整数値を示す。］

[In General Formula (11-1), R ₂₃ represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and R ₂₄ represents an alkyl group having 1 to 22 carbon atoms or 7 or 8 carbon atoms. Represents an aralkyl group. l represents 0 or a positive integer value. ]

In the general formula (11-1), R ₂₃ is preferably a hydrogen atom or a methyl group from the viewpoint of polymerizability of the monomer unit.
In the general formula (11-1), the alkyl group represented by R ₂₄ is an alkyl group or carbon atom having 1 to 22 carbon atoms from the viewpoint of dispersibility and compatibility with the binder resin constituting the toner. An aralkyl group having a number of 7 or 8 is preferred. In particular, R ₂₄ is preferably an alkyl group having 4 to 22 carbon atoms from the viewpoint of compatibility with the crystalline polyester resin. The alkyl group may have any structure of a linear structure, a branched structure, or a cyclic structure.
Moreover, examples of the aralkyl group for R ₂₄ include a benzyl group, an α-methylbenzyl group, and a phenethyl group.

［一般式（１１−２）中、Ｒ_２５は、水素原子または炭素原子数が１もしくは２のアルキル基を示す。ｍは、０または正の整数値を示す。］

[In General Formula (11-2), R ₂₅ represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms. m represents 0 or a positive integer value. ]

［一般式（１１−３）中、Ｒ_２６は、水素原子または炭素原子数が１もしくは２のアルキル基を示す。ｎは、０または正の整数値を示す。］

[In General Formula (11-3), R ₂₆ represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms. n represents 0 or a positive integer value. ]

［一般式（１１−４）中、Ｒ_２７は、水素原子または炭素原子数が１もしくは２のアルキル基を示し、Ｒ_２８およびＲ_２９は、それぞれ独立して、水素原子、炭素原子数が１〜４のアルキル基またはフェニル基を示す。ｐは、０または正の整数値を示す。］

[In General Formula (11-4), R ₂₇ represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and R ₂₈ and R ₂₉ each independently represent a hydrogen atom or a carbon atom having 1 carbon atom. -4 alkyl group or phenyl group. p represents 0 or a positive integer value. ]

In the polymer component of the pigment dispersant, the binder resin constituting the toner by changing the proportion of the monomer units represented by the general formula (10) or the general formulas (11-1) to (11-4). In addition, it is possible to improve the compatibility between the crystalline polyester resin and the pigment dispersant.
When the main binder resin constituting the toner is a polyester resin as in the present invention, the polymer component is a polymer containing a polyester resin whose solubility with the binder resin is adjusted. It is possible to further improve the compatibility of the pigment dispersant.

As described above, when the compatibility of the polymer component of the pigment dispersant and the binder resin constituting the toner is high, the polymer chain-derived polymer chain in the pigment dispersant can maintain a sufficiently expanded state, The steric repulsion effect is large, and the dispersion state of the pigment can be maintained well.
As long as the compatibility with the binder resin constituting the toner is within an appropriate range, the polymer component in the pigment dispersant is chemically bonded to a vinyl polymer resin, polyester, polyurethane, polyamide resin, or a plurality thereof. It is possible to use any polymer such as hybrid resin.

Examples of the polymerization form of the polymer component in the pigment dispersant include a random copolymer, an alternating copolymer, a periodic copolymer, and a block copolymer. The polymer component may have any structure of a linear structure, a branched structure, or a crosslinked structure.
In the present invention, the case where the polymer component in the pigment dispersant has a polyester skeleton will be described in detail below.
When the binder resin constituting the toner is a polyester resin, the polymer component in the pigment dispersant is at least a monomer represented by the following general formulas (12) and (13) from the viewpoint of compatibility with the binder resin. 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 shown by following General formula (14) as a structural component.

In the general formula (12), the divalent linking group represented by L ₂ is preferably an alkylene group, an alkenylene group or an arylene group.
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, A combination thereof may also be used.
Further, the above substituent of L ₂ may be further substituted with a substituent as long as the affinity to the dispersion medium is not significantly impaired. In this case, examples of the substituent include a methyl group, a halogen atom, a carboxyl group, a trifluoromethyl group, and combinations thereof.
L ₃ in the general formula (13) 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 (13) is The case represented by the general formula (15) is preferable.

［一般式（１５）中、Ｒ_３０はエチレン基またはプロピレン基を示す。ｘおよびｙは、それぞれ０以上の整数であり、ｘ＋ｙの平均値は２〜１０である。］

[In General Formula (15), R ₃₀ 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. ]

L ₃ can be arbitrarily selected from the substituents listed above, but is preferably an alkylene group or a phenylene group having 6 or more carbon atoms from the viewpoint of affinity with a dispersion medium, particularly a nonpolar solvent. Alternatively, it is preferable that the general formula (13) is a bisphenol A derivative of the general formula (15), and a combination thereof may be used.
The substituent of L ₃ may be further substituted with a substituent as long as the affinity to the dispersion medium is not significantly impaired. In this case, examples of the substituent include a methyl group, an alkoxy group, a hydroxyl group, a halogen atom, and combinations thereof.

L ₄ in the general formula (14) represents a divalent linking group, and is preferably an alkylene group or an alkenylene group.
These alkenylene groups may have any structure of a linear structure, a branched structure, and a cyclic structure. Moreover, what is necessary is just to have at least 1 or more double bond, and the position of a double bond may exist in any location.
Further, the substituent of L ₄ may be further substituted with a substituent as long as the affinity to the dispersion medium is not significantly impaired. In this case, examples of the substituent include an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, and combinations thereof.
The above 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 of these may be used.

  In the above pigment dispersant, one or more blocks are formed at one end even if the positions where the adsorbing component adsorbing to the pigment bonded to the polymer component via a single bond or a linking group is randomly scattered And may be unevenly distributed. Further, the larger the number of adsorbing components, the higher the affinity for the pigment. However, if the number is too large, the affinity for the binder resin constituting the toner tends to decrease. Therefore, the number of the adsorbing components is preferably 0.5 to 30, more preferably 0.5 to 15 with respect to 100 monomers forming the polymer component, and 1.0 to 6.0 is even more preferable, and 1.0 to 4.0 is even more preferable.

  In the pigment dispersant, the number of adsorbing group components per molecule of the pigment dispersant is preferably 1.0 or more and 6.0 or less, and more preferably 1.0 or more and 3.0 or less. This is preferable when the number of adsorbing group components per molecule of the pigment dispersant is 1.0 or more, because there is a sufficient amount of molecules that the pigment dispersant molecules adsorb to the pigment. Conversely, when the number of adsorbing group components per molecule of the pigment dispersant is 6.0 or less, the probability that the adsorbing groups in the same molecule of the pigment dispersant associate and aggregate is low, and the adsorptivity to the pigment is low. This is preferable because it is sufficient.

  In the present invention, the content of the pigment dispersant is preferably 0.5% by mass or more and 30% by mass or less, and 1.0% by mass or more and 15.15% by mass or less with respect to the total amount of pigments contained in the toner. It is more preferably 0% by mass or less. More preferably, it is 4.0 mass% or more and 15.0 mass% or less. When the content of the pigment dispersant is 0.5% by mass or more based on the total amount of the pigment, the effect of the present invention does not decrease. On the other hand, in the case of 30% by mass or less, the pigment dispersant released without adsorbing to the pigment does not increase, and the chargeability of the toner does not decrease.

The content of the pigment dispersant is preferably 0.01% by mass or more and 10.00% by mass or less, and preferably 0.01% by mass or more and 5.00% by mass or less with respect to the toner mass. More preferred. When the content of the pigment dispersant is 0.01% by mass or more based on the toner mass, the effect of the present invention does not deteriorate. On the other hand, when the amount is 10.00% by mass or less, the chargeability of the toner does not decrease.
The glass transition temperature (Tg) of the pigment dispersant is preferably 50 ° C. or higher and 150 ° C. or lower, and more preferably 55 ° C. or higher and 120 ° C. or lower. When the glass transition temperature (Tg) of the pigment dispersant is 50 ° C. or higher, the storage stability of the toner does not deteriorate. On the other hand, when the temperature is 150 ° C. or lower, the toner fixability does not deteriorate.

  The adsorption rate of the pigment dispersant to the pigment is 30% or more. It is more preferably 50% or more, further preferably 70% or more, and further preferably 85% or more. When the adsorption rate of the pigment dispersant to the pigment is 30% or more, the pigment dispersant continues to be adsorbed to the pigment by overcoming the interference of the other materials constituting the toner with respect to the pigment. It can be maintained well.

The acid value of the pigment dispersant is preferably 30.0 mgKOH / g or less, and more preferably 10.0 mgKOH / g. When the acid value of the pigment dispersant is 30.0 mgKOH / g or less, the chargeability is further improved in use in a high temperature and high humidity environment from the viewpoint of hygroscopicity. The acid value of the pigment dispersant is preferably 0.0 mgKOH / g or more.
In particular, when a toner is produced in an aqueous medium such as a suspension granulation method (dissolution suspension method), the acid value of the pigment dispersant is 30.0 mgKHO / g or less, and the toner binder resin. It is preferable that it is smaller than the acid value. In that case, the probability that the pigment dispersant is present on the surface of the toner particle is low, and as a result, the probability that the pigment is also present in the vicinity of the surface of the toner particle tends to decrease. Therefore, the exposure of the pigment on the surface of the toner particle can be reduced. That is, since the surface of the toner particles becomes uniform, it is possible to reduce the release of inorganic fine particles such as silica used by adhering to the surface of the toner particles in a normal toner. Therefore, it is possible to improve member contamination such as filming.

The difference (A−C) between the SP value (A) of the pigment dispersant and the SP value (C) of the binder resin is −2.00 or more and +0.05 or less, and the acid value of the pigment dispersant is It becomes more remarkable when it is 30.0 mgKHO / g or less and is smaller than the acid value of the binder resin of the toner. In the amorphous polyester resin used as the binder resin of the present invention, when the SP value is high, the polarity of the resin is high. The same applies to the crystalline polyester resin used in the present invention. Therefore, if the following two conditions are satisfied, the exposure of the pigment on the surface of the toner particles can be considerably reduced, which is more preferable in terms of member contamination such as filming.
(1) The difference (A−C) between the SP value (A) of the pigment dispersant and the SP value (C) of the binder resin is −2.00 or more and +0.05 or less,
(2) The acid value of the pigment dispersant is 30.0 mgKHO / g or less, and is smaller than the acid value of the binder resin of the toner.

  The pigment dispersant may have an amine value, and the amine value of the pigment dispersant is preferably 30.0 mgKOH / g or less, more preferably 10.0 mgKOH / g or less. More preferably, it is 0.0 mgKOH / g or less. When the amine value of the pigment dispersant is 30.0 mgKOH / g or less, the chargeability is improved in use in a high temperature and high humidity environment. In particular, in a negatively chargeable toner, when the amine value of the pigment dispersant exceeds 30.0 mgKOH / g, the chargeability tends to decrease. The amine value of the pigment dispersant is preferably 0.0 mgKOH / g or more.

In the present invention, the number average molecular weight (Mn) of the pigment dispersant measured using gel permeation chromatography (GPC) is set to 3000 or more and 20000 or less. More preferably, it is 6000 or more and 20000 or less, and further preferably 8000 or more and 20000 or less.
When the number average molecular weight (Mn) of the pigment dispersant is 3000 or more, the steric repulsion effect by the polymer portion of the pigment dispersant is large. Therefore, the effect of improving the dispersibility of the pigment is high, and the storage stability is excellent. On the other hand, when it is 20000 or less, there is no problem in the affinity with the binder resin constituting the toner, and the fixing property is not hindered. Further, when the number average molecular weight (Mn) of the pigment dispersant is 20000 or less, the probability that the pigment dispersant crosslinks the pigment particles is low, and aggregation of the pigment is suppressed. 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.

When the pigment dispersant is an azo compound represented by the formula (2), it 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).
An example of the scheme of method (i) is shown below and will be described in detail.

［一般式（１７）および（１８）中のＲ_３およびＲ_４は、それぞれ上記一般式（２）中のＲ_３およびＲ_４と同義である。一般式（１６）および（１８）中のＡｒ_１は、アリーレン基を示す。Ｐ_１は、ポリマー成分であり、例えば、上記一般式（１０）などで示される単量体単位を構成成分として含む共重合体などである。一般式（１６）および（１８）中のＱ_１は、Ｐ_１と反応して単結合または２価の連結基を形成する置換基を示す。］

[Formula (17) and (18) _{R 3} and _{R 4} in is the same meaning as _{R 3} and _{R 4} in the general formula (2). Ar ₁ in the general formulas (16) and (18) represents an arylene group. P ₁ is a polymer component, such as a copolymer containing a monomer unit represented by the general formula (10) as a constituent component. Q ₁ in the general formulas (16) and (18) 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, the azo compound can be synthesized by Step 1 and Step 2. In step 1, the aniline derivative represented by the general formula (16) and the compound represented by the general formula (17) are diazo-coupled to form an azo skeleton partial structure represented by the general formula (18) (hereinafter referred to as “azo skeleton moiety”). Structure (18) ") is synthesized. In step 2, the azo skeleton moiety structure (18) a polymer component P ₁ is coupled by such a condensation reaction.

The polymer component represented by P ₁ can control the molecular weight distribution and the molecular structure using a known method. For example, a method using an addition-cleavage type chain transfer agent, an NMP method (nitroxide polymerized polymerization), an ATRP method (atom transfer radical polymerization method), a RAFT method (reversible addition fragmentation chain transfer), and others, a MADIx method (ultimate chain transfer). By using of Xanthate), DT method (Degenerative transfer), or the like, a polymer component having a controlled molecular weight distribution or molecular structure can be produced.

Next, the step 2 will be described. In step 2, a known method can be used. For example, by using the polymer component P ₁ having a carboxyl group and the azo skeleton partial structure (18) in which Q ₁ is a substituent having an amino group, P ₁ and Q ₁ are connected by a carboxylic acid amide bond. The above azo compound can be synthesized. Specifically, a method of generating a carboxylic acid amide bond using a dehydrating condensing agent such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, a Schotten-Baumann method, and the like can be used.
Next, the method (ii) will be described in detail by showing an example of the scheme below.

［一般式（１８）中のＲ_３、Ｒ_４、Ａｒ_１およびＱ_１は、それぞれ上記方法（ｉ）のスキームにおける一般式（１８）中のＲ_３、Ｒ_４、Ａｒ_１およびＱ_１と同義である。一般式（１９）中のＱ_２は、一般式（１８）中のＱ_１と反応して、式（２０）中のＱ_３を形成する置換基を示す。一般式（１９）および（２０）中のＲ_３１は、水素原子またはアルキル基を示し、Ｑ_３は一般式（１８）中のＱ_１および一般式（１９）中のＱ_２が反応して形成する２価の連結基を構成する置換基を示す。］

[R ₃ , R ₄ , Ar ₁ and Q ₁ in the general formula (18) have the same meanings as R ₃ , R ₄ , Ar ₁ and Q ₁ in the general formula (18) in the scheme of the method (i), respectively. It is. Q ₂ in the general formula (19) represents a substituent that reacts with Q ₁ in the general formula (18) to form Q ₃ in the formula (20). R ₃₁ in the general formulas (19) and (20) represents a hydrogen atom or an alkyl group, and Q ₃ is formed by the reaction of Q ₁ in the general formula (18) and Q ₂ in the general formula (19). The substituent which comprises the bivalent coupling group to do is shown. ]

  In the scheme of the method (ii) exemplified above, the azo compound can be synthesized by Step 3 and Step 4. In step 3, the azo skeleton partial structure represented by the general formula (18) is reacted with the vinyl group-containing compound represented by the general formula (19) (hereinafter, also referred to as “vinyl group-containing compound (19)”). An azo skeleton partial structure having a polymerizable functional group represented by the formula (20) is synthesized. The azo skeleton partial structure having a polymerizable functional group represented by the general formula (20) is hereinafter also referred to as “azo skeleton partial structure (20)”. In step 4, the azo skeleton partial structure (20) having a polymerizable functional group is copolymerized with a monomer unit represented by the general formula (10) or the like.

For example, an isocyanate group-containing vinyl group-containing compound (19) (for example, 2-isocyanatoethyl methacrylate [manufactured by Showa Denko KK, trade name “Karenz MOI”]) and Q ₁ is a substituent having a hydroxyl group. An azo skeleton partial structure (18) is used. In this way, an azo skeleton partial structure (20) having a polymerizable functional group in which the linking group is a urethane group can be synthesized.
Next, method (iii) will be described in detail with reference to an example of the scheme shown below.

［一般式（１８）中のＲ_３、Ｒ_４、Ａｒ_１およびＱ_１は、それぞれ上記方法（ｉ）のスキームにおける一般式（１８）中のＲ_３、Ｒ_４、Ａｒ_１およびＱ_１と同義である。一般式（２１）中のＱ_４は、一般式（１８）中のＱ_１と反応して、一般式（２２）中のＱ_５を形成する置換基（例えば、カルボキシル基）を示す。Ａは、塩素原子、臭素原子またはヨウ素原子を示す。一般式（２２）中のＲ_３、Ｒ_４およびＡｒ_１は、一般式（１８）中のＲ_３、Ｒ_４およびＡｒ_１と同義であり、Ｑ_５は一般式（１８）中のＱ_１および一般式（２１）中のＱ_４が反応して形成する連結基を示す。］

[R ₃ , R ₄ , Ar ₁ and Q ₁ in the general formula (18) have the same meanings as R ₃ , R ₄ , Ar ₁ and Q ₁ in the general formula (18) in the scheme of the method (i), respectively. It is. Q ₄ in the general formula (21) represents a substituent (for example, a carboxyl group) that reacts with Q ₁ in the general formula (18) to form Q ₅ in the general formula (22). A represents a chlorine atom, a bromine atom or an iodine atom. _R 3, _{R 4} and Ar ₁ in the general formula (22), formula (18) in a _R 3, the same meaning as _{R 4} and Ar ₁ of, _{Q 5} is _{Q 1} and in the general formula (18) A linking group formed by the reaction of Q ₄ in formula (21) is shown. ]

  In the scheme of the method (iii) exemplified above, the azo compound can be synthesized by Step 5 and Step 6. In step 5, the azo skeleton partial structure represented by the general formula (18) is reacted with the halogen atom-containing compound represented by the general formula (21) to have the azo skeleton partial structure represented by the general formula (22). (22) is synthesized. The halogen atom-containing compound represented by the general formula (21) is hereinafter also referred to as “halogen atom-containing compound (21)”. The azo skeleton partial structure (22) having a halogen atom represented by the general formula (22) is hereinafter also referred to as “azo skeleton partial structure (22)”. In step 6, the azo skeleton partial structure (22) having a halogen atom is used as a polymerization initiator to copolymerize with a monomer unit represented by the above general formula (10) or the like.

As the halogen atom-containing compound (21) having a carboxyl group, acid halides and acid anhydrides thereof can also be used in the present invention.
In Step 6, the ATRP method in the method (i) is used, and the azo skeleton partial structure (22) having a halogen atom is used as a polymerization initiator in the presence of a metal catalyst and a ligand. The azo compound can be synthesized by polymerizing with the monomer unit represented by 10).
Moreover, when R ₄ in the general formula (2) is an NR ₁₁ R ₁₂ group, R ₁₁ is a hydrogen atom, and R ₁₂ is a phenyl group, the azo compound is obtained by, for example, the following method (iv): Can be synthesized.

［一般式（２３）、（２５）、（２７）および（２８）中のＡｒ_２は、アリーレン基を示す。式（２４）、（２５）、（２７）および（２８）中のＲ_３は上記一般式（２）中のＲ_３と同義である。一般式（２４）中のＱ_６は、一般式（２３）のアミノ基と反応して、式（２５）中のアミド基を形成する際に離脱する置換基を示す。Ｐ_１は、上記方法（ｉ）のスキーム中のＰ_１と同義である。］

[Ar ₂ in the general formulas (23), (25), (27) and (28) represents an arylene group. Equation (24), (25), (27) and _{R 3} in (28) are the same as _{R 3} in the general formula (2). Q ₆ in the general formula (24) represents a substituent that is removed when the amide group in the formula (25) is formed by reacting with the amino group in the general formula (23). 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, the azo compound can be obtained by Step 7, Step 8, Step 9 and Step 10. In Step 7, the aniline derivative represented by the general formula (23) and the compound represented by the general formula (24) are amidated to obtain a compound represented by the general formula (25). In step 8, the compound represented by the general formula (25) and the diazo component of the aniline analog represented by the general formula (26) are coupled to obtain an azo skeleton partial structure represented by the general formula (27). In step 9, the nitro group of the azo skeleton partial structure represented by the general formula (27) is reduced to an amino group with a reducing agent to obtain the azo skeleton partial structure represented by the general formula (28). In step 10, the amino group of the azo skeleton partial structure represented by the general formula (28) and the carboxyl group of the polymer component represented by P ₁ separately synthesized are bonded by amidation.

When R ₃ in the general formula (24) is a methyl group, the azo compound can be synthesized also by a method using diketene instead of the compound represented by the general formula (24).
In step 10, using the same method as in step 2 in the scheme of method (i), the amino group of the azo skeleton partial structure represented by general formula (28) and the carboxyl of the polymer component represented by P ₁ are used. The group is bonded by amidation or the like. In this way, the azo compound can be synthesized. In addition, even if the polymer component represented by P ₁ has an epoxy group (for example, a copolymer of 2,3-epoxypropyl methacrylate), in the azo skeleton partial structure represented by the general formula (28) It can be bonded by reacting with an amino group.

  The compound obtained in each step of the synthesis method exemplified above can be purified using a normal organic compound isolation / purification method. Examples of the isolation / purification method include a recrystallization method and a reprecipitation method using an organic solvent, and 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 toner of the present invention uses crystalline polyester in order to improve low temperature fixability.
In the toner of the present invention, a crystalline polyester is added to impart low temperature fixability.
In the present embodiment, “crystallinity” means having a clear endothermic peak in the differential scanning calorimetry (DSC) measurement described later. On the other hand, a resin that does not have a clear endothermic peak means amorphous.
The melting point Tm (C) of the crystalline polyester used in the present invention is preferably 55 ° C. or higher and 90 ° C. or lower, and more preferably 60 ° C. or higher and 85 ° C. or lower. When the temperature is 55 ° C. or higher, toner blocking (toner-to-toner fusion) hardly occurs and storage stability does not deteriorate. On the other hand, when the melting point is 90 ° C. or lower, the fixability does not deteriorate.

The crystalline polyester of the present invention is composed of a polycondensation resin of an aliphatic dicarboxylic acid and an aliphatic diol.
Tm (C) can be adjusted according to the kind of aliphatic dicarboxylic acid or aliphatic diol used, the degree of polymerization, and the like.
The aliphatic dicarboxylic acid and the aliphatic diol are more preferably a linear dealiphatic dicarboxylic acid represented by the following formula (4) and a linear aliphatic diol represented by the following formula (5).

HOOC- (CH2) m-COOH Formula (4)
[In Formula (4), m shows the integer of 4-16. ]
HO— (CH 2) n —OH Formula (5)
[In Formula (5), n shows the integer of 4-16. ]

The linear type is excellent in the crystallinity of the polyester resin and has an appropriate crystal melting point, and thus is excellent in toner blocking resistance, image storage stability, and low-temperature fixability. Further, when the number of carbon atoms is 4 or more, the melting point (Tm) is appropriate, and thus toner blocking resistance, image storage stability, and low-temperature fixability are excellent. Further, when the number of carbon atoms is 16 or less, it is easy to obtain practical materials. The number of carbon atoms is more preferably 14 or less.
Of the polycarboxylic acid component, the content of the aliphatic dicarboxylic acid is preferably 80 mol% or more, more preferably 90 mol% or more, and more preferably 100 mol% in terms of crystallinity of the crystalline polyester. More preferably it is.

From the viewpoint of crystallinity of the crystalline polyester, the content of the aliphatic diol component in the polyol component is preferably 80 mol% or more, more preferably 90 mol% or more, and preferably 100 mol%. More preferably it is.
If necessary, monovalent acids such as acetic acid and benzoic acid and monovalent alcohols such as cyclohexanol benzyl alcohol are also used for the purpose of adjusting the acid value and the hydroxyl value.
The crystalline polyester resin used in the present invention can be produced by an ordinary polyester synthesis method. For example, it can be obtained by subjecting a dicarboxylic acid component and a dial alcohol component to an esterification reaction or a transesterification reaction, followed by a polycondensation reaction under reduced pressure or by introducing nitrogen gas according to a conventional method.

Moreover, the acid value of crystalline polyester can also be controlled by sealing the carboxyl group of the polymer terminal. Monocarboxylic acid and monoalcohol can be used for end-capping.
In this embodiment, a copolymer obtained by copolymerizing (modifying) other components in a proportion of 60% by weight or less with respect to the crystalline polyester portion is also referred to as crystalline polyester (hybrid crystalline polyester).
When the crystalline polyester has a copolymer site obtained by polymerizing other components, the copolymer site is preferably an amorphous vinyl copolymer.

Since the copolymer part is an amorphous vinyl copolymer, the compatibility of the crystalline polyester with the polyester resin as the binder resin becomes appropriate. Further, it can be finely dispersed. Thereby, it is possible to obtain excellent low-temperature fixability and durability.
When the weight ratio of the amorphous vinyl moiety in the crystalline polyester is 60% by weight or less, the crystallinity of the crystalline polyester does not decrease too much, so that a sufficient sharp melt property can be exhibited in the fixing step. .
In the crystalline polyester of the present invention, it is also preferable to adjust the ester group concentration of the crystalline polyester in order to adjust the compatibility with the binder resin. That is, by adjusting the ester group concentration of the crystalline polyester, the compatibility with the binder resin that is a polyester resin can be adjusted, and the same effect as the above-described effect of the amorphous vinyl portion can be obtained. .

By increasing the ester group concentration, the Tm (C) of the crystalline polyester is lowered, and the toner blocking resistance and image storage stability may be deteriorated. Therefore, the ester group concentration should be adjusted in consideration of the glass transition temperature (Tg). It needs to be adjusted.
The crystalline polyester preferably has a weight average molecular weight (Mw) of 10,000 to 80,000, and more preferably 13,000 to 40,000. When Mw is 10,000 or more and 80,000 or less, it is possible to quickly obtain a plastic effect by the crystalline polyester in the fixing step while maintaining a high degree of crystallinity of the crystalline polyester in the toner production step. Therefore, it is possible to achieve both excellent heat-resistant storage stability and excellent fixability under low temperature conditions and high speed conditions.
The weight average molecular weight (Mw) of the crystalline polyester can be controlled by various production conditions of the crystalline polyester. A method for measuring the weight average molecular weight (Mw) of the crystalline polyester will be described later.

  Moreover, when crystalline polyester has an amorphous vinyl part, it is preferable that the weight average molecular weights (Mw) of an amorphous vinyl part are 2000-12000. When the weight average molecular weight (Mw) is 2,000 or more and 12,000 or less, the amorphous vinyl part is more uniformly dispersed in the crystalline polyester. As a result, the compatibility between the crystalline polyester and the binder resin becomes appropriate, and the dispersion state of the crystalline polyester resin is good, so that the low-temperature fixability is improved. The weight average molecular weight (Mw) of the amorphous vinyl part can be controlled by various production conditions of the polyester, such as the amount of the bireactive monomer added during the production of the crystalline polyester. In addition, the measuring method of the weight average molecular weight (Mw) of an amorphous vinyl part is mentioned later.

The acid value of the crystalline polyester used in the present invention is preferably 5.0 mgKOH / g or less. Crystalline polyester resin has low resistance from the beginning, and tends to be disadvantageous in terms of toner chargeability. In that case, if the acid value of the crystalline polyester resin is high, moisture absorption is likely to occur, and charging is likely to leak. Therefore, the crystalline polyester resin is preferably set to 5.0 mgKOH / g or less from the viewpoint of chargeability of the toner.
When the acid value of the crystalline polyester used in the present invention is 5.0 mgKOH / g or less, the crystallinity of the crystalline polyester can be increased, and the heat resistance is improved. Further, by reducing the acid value, the adhesion between the toner and the paper during image formation is improved. In particular, when the toner is produced in an aqueous medium, if the acid value is 5.0 mgKOH / g or less, the probability that the crystalline polyester is unevenly distributed near the surface of the toner particles is low. As a result, it is preferable because the exposure of the crystalline polyester is suppressed and the decrease in frictional chargeability and the deterioration in heat resistance can be suppressed.

The acid value of the crystalline polyester can be controlled by the ratio between the alcohol component and the acid component constituting the crystalline polyester, the type of monomer, and the end group treatment of the crystalline polyester. The method for measuring the acid value of the crystalline polyester will be described later.
Further, the content of the crystalline polyester is preferably 3 parts by mass or more and 50 parts by mass or less, and 8 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the amorphous polyester resin that is a binder resin. More preferred.

  When the content of the crystalline polyester is 3 parts by mass or more, the low-temperature fixability is more preferable. Further, since crystalline polyester has low resistance and easily absorbs moisture, the toner content is preferably 50 parts by mass or less with respect to the amorphous polyester resin as the binder resin, which is preferable. Further, it is preferable because an offset due to a decrease in melt viscosity due to the compatibility with the binder resin due to the presence of excess crystalline polyester hardly occurs. Furthermore, in the toner manufactured in an aqueous medium, the smoothness of the surface shape of the toner particles decreases if the content of the crystalline polyester is excessive. Therefore, from the viewpoint of charging characteristics, the content of the crystalline polyester is preferably 50 parts by mass or less with respect to 100 parts by mass of the amorphous polyester resin that is a binder resin.

The dispersion state of the crystalline polyester resin in the toner can also be controlled by physical properties such as the acid value and molecular weight of the crystalline polyester resin and the conditions of the melting point and polymerization temperature of the crystalline polyester resin.
Examples of the method for producing the hybrid crystalline polyester include a method in which a polymerization reaction is allowed to proceed under a pressurized environment when an amorphous vinyl polymer unit is produced. Specifically, transesterification reaction between hydroxyl group contained in polyester and (meth) acrylic ester contained in amorphous vinyl polymer, hydroxyl group contained in polyester and contained in amorphous vinyl polymer To generate a radical in the polyester by an esterification reaction with a carboxyl group, an esterification reaction between a carboxyl group contained in the polyester and a hydroxyl group contained in the amorphous vinyl polymer, a hydrogen abstraction reaction, Examples thereof include a method of adding a monomer and polymerizing under a pressurized environment. At that time, the degree of pressurization is preferably 0.20 MPa or more and 0.45 MPa or less.

A known monofunctional polymerizable monomer or polyfunctional polymerizable monomer can be used as the vinyl polymerizable monomer used when the hybrid resin is produced. Examples of the monofunctional polymerizable monomer include styrene, an acrylic polymerizable monomer; and a methacrylic polymerizable monomer obtained by changing the acrylic polymerizable monomer to methacrylate.
As the vinyl monomer, those having a carboxyl group or a hydroxyl group and those containing (meth) acrylic acid esters are preferable. This is because if a functional group having a strong polarity such as a carboxyl group is present in the vinyl polymer unit of the hybrid resin, the vinyl polymer unit has an appropriate polarity, and toner particles in an aqueous medium This is preferable because the toner particles are stabilized during the production.

Further, it is preferable that the vinyl polymer unit of the hybrid resin is a copolymer with acrylic acid, because the surface of the toner particles becomes strong and excellent in durability due to hydrogen bonding by a carboxyl group of acrylic acid. A content of acrylic acid in the hybrid resin of 3.0% by mass or less is preferable because the hygroscopicity does not increase even in a high temperature and high humidity environment and the triboelectric charging property of the toner does not decrease.
The polymerization initiator used for polymerizing the polymerizable monomer described above when producing the hybrid resin is oil-soluble as long as it does not inhibit the effects of the present invention other than those used in the present invention. Initiators and / or water-soluble initiators can be used as appropriate. For example, examples of the oil-soluble initiator include azo compounds and peroxides.
In particular, it is preferably a peroxide, and when the polyester resin is vinyl-modified by a hydrogen abstraction reaction, the 10-hour half-life temperature is preferably 70 ° C. or higher and 170 ° C. or lower, and 75 ° C. or higher and 130 ° C. or lower. It is more preferable to use one because it has an appropriate reactivity.

<Weight average molecular weight and number average molecular weight of crystalline polyester resin>
After 0.03 g of crystalline polyester is dispersed and dissolved in 10 mL of o-dichlorobenzene, it is shaken with a shaker at 135 ° C. for 24 hours, filtered through a 0.2 μm filter, and the filtrate is used as a sample. Analyze.
[Analysis conditions]
Separation column: Shodex (TSK GMHHR-H HT20) × 2
Column temperature: 135 ° C
Mobile phase solvent: o-dichlorobenzene Mobile phase flow rate: 1.0 mL / min Sample concentration: about 0.3%
Injection volume: 300 μL
Detector: Differential refractive index detector Shodex RI-71
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) are used.

<Weight average molecular weight of amorphous vinyl part in crystalline polyester>
The molecular weight of the amorphous vinyl part in the crystalline polyester is measured by hydrolyzing the polyester portion of the crystalline polyester. Specifically, 5 mL of dioxane and 1 mL of a 10 wt% aqueous potassium hydroxide solution are added to 30 mg of crystalline polyester, and the polyester portion is hydrolyzed by shaking at a temperature of 70 ° C. for 6 hours. Thereafter, the solution was dried to prepare a sample for measuring the molecular weight of the vinyl part.
After 0.03 g of the sample for measurement was dispersed in 10 mL of o-dichlorobenzene and dissolved, it was shaken with a shaker at 135 ° C. for 24 hours, filtered with a 0.2 μm filter, and the filtrate was used as a sample. Analyze.
[Analysis conditions]
Separation column: Shodex (TSK GMHHR-H HT20) × 2
Column temperature: 135 ° C
Mobile phase solvent: o-dichlorobenzene Mobile phase flow rate: 1.0 mL / min Sample concentration: about 0.3%
Injection volume: 300 μL
Detector: Differential refractive index detector Shodex RI-71
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) are used.

<Melting point Tm (C) of crystalline polyester>
The glass transition temperature Tg of the toner and the melting point, endothermic amount, and crystallinity of the crystalline polyester are measured using a differential scanning calorimeter “Q1000” (TA Instruments) according to ASTM D3418-82.
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
Specifically, 5 mg of toner or 1 mg of crystalline polyester is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference. Make modulation measurements in settings.
Temperature rising rate 1 ° C./min Amplitude temperature range ± 0.318 ° C./min In this temperature rising process, a specific heat change is obtained in the temperature range of 20 ° C. to 140 ° C. The glass transition temperature Tg of the toner is defined as an intersection point between the baseline intermediate line and the differential heat curve before and after the specific heat change of the reversible specific heat change curve. The melting point Tm (C) of the crystalline polyester is the maximum endothermic peak temperature in the specific heat change curve.

(wax)
The toner of the present invention may contain a wax. In that case, at least one of the waxes preferably has a melting point (temperature corresponding to the maximum endothermic peak of the DSC endothermic curve in the temperature range of 20 to 200 ° C.) of 30 ° C. or more and 120 ° C. or less, and 50 ° C. or more and 100 ° C. The following is more preferable. Further, it is preferably a wax that is solid at room temperature, and in particular, a solid wax having a melting point of 50 ° C. or higher and 100 ° C. or lower is preferable from the viewpoint of toner blocking resistance, multi-sheet durability, low-temperature fixability, and offset resistance.

  Examples of the wax include paraffin wax, polyolefin wax, polymethylene wax such as microcrystalline wax and Fischer-Tropsch wax, petroleum wax such as amide wax and petrolatum and derivatives thereof, montan wax and derivatives thereof, carnauba wax and candelilla wax. Use of known waxes such as natural waxes and derivatives thereof, hydrogenated castor oil and derivatives thereof, vegetable waxes, animal waxes, higher fatty acids, long chain alcohols, ester waxes, ketone waxes and derivatives thereof such as graft compounds and block compounds Is possible. These can be used alone or in combination.

The content of the wax in the toner of the present invention is preferably 3 parts by weight or more and 30 parts by weight or less, more preferably 3 parts by weight or more and 20 parts by weight or less, with respect to 100 parts by weight of the binder resin. More preferred is less than or equal to parts by weight. If the amount of wax added is not less than the lower limit value, the effect of preventing offset is unlikely to be lowered, and if it is not more than the upper limit value, the anti-blocking effect is less likely to be reduced, and toner drum fusion or toner development sleeve fusion is less likely to occur. .
When obtaining the above physical properties, when it is necessary to extract the wax from the toner, the extraction method is not particularly limited, and any method can be used. For example, a predetermined amount of toner is Soxhlet extracted with toluene, and after removing the solvent from the obtained toluene-soluble component, a chloroform-insoluble component is obtained. Thereafter, identification analysis is performed by IR method or the like.
In addition, quantitative analysis is performed by DSC or the like. In the present invention, the measurement is performed using DSC-2920 manufactured by TA Instruments Japan.
The measuring method is the same as the calculation of the glass transition temperature (Tg) of the pigment dispersant. The glass transition point is defined as the point of intersection between the baseline line before and after the specific heat change during measurement and the differential heat curve. Further, the maximum endothermic peak temperature of the wax component is obtained from the obtained DSC curve at the time of temperature increase.

(Charge control agent)
A known charge control agent can be used in the toner of the present invention.
The content of the charge control agent is preferably 0.01 parts by mass or more and 20 parts by mass or less, and 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin in the toner. Is more preferable.

(Pigment)
The toner of the present invention contains a pigment as a colorant. The pigment is carbon black, C.I. I. Pigment red 122, C.I. I. Pigment red 150, and C.I. I. Selected from the group consisting of CI Pigment Yellow 185.
The addition amount of these pigments is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.

(Other additives)
In the toner of the present invention, various known inorganic and organic additives can be used for the purpose of imparting various characteristics within a range that does not impair the effects of the present invention. The additive to be used preferably has a particle size of 3/10 or less of the weight average particle size of the toner particles from the viewpoint of durability when added to the toner. The particle size of the additive means the average particle size obtained by observing the surface of the toner particles with a scanning electron microscope.
The content of these additives is preferably 0.01 parts by mass or more and 5 parts by mass or less, and more preferably 0.02 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the toner.
These additives may be used alone or in combination.
Moreover, these additives may be hydrophobized. As a method for the hydrophobization treatment, various coupling agents such as a silane coupling agent or a titanium coupling agent can be used, but it is preferable to increase the degree of hydrophobicity with silicone oil. This is because moisture adsorption of inorganic fine particles under high humidity can be suppressed, and furthermore, contamination of the regulating member and charging member can be suppressed, so that a high-quality image can be obtained.

(Toner production method)
Next, a method for producing the toner of the present invention will be described.
As a method for producing the toner of the present invention, a pulverization method, a dispersion polymerization method, a solution suspension method (suspension production method) in which a raw material dissolved and dispersed in an organic solvent is granulated in an aqueous medium to form a toner. And a method of obtaining a toner such as a particle method.
Toner is produced by granulating a mixed solution in which a toner composition containing a binder resin is dissolved or dispersed in an organic solvent in an aqueous medium and removing the organic solvent contained in the granulated particles. Also in this case, it is preferable to produce the toner by the following method in order to exert the effects of the present invention.
1) A mixed solution in which a toner composition containing a pigment, the pigment dispersant, and a binder resin is dissolved or dispersed in an organic solvent is prepared in advance.
2) After forming the state in which the pigment dispersant is adsorbed to the pigment, a wax is added and dissolved as necessary,
3) A toner is manufactured by granulating the mixed solution in an aqueous medium.

The toner production method of the present invention will be described in more detail.
As a method for producing the toner of the present invention, a binder resin and a pigment constituting the toner are dissolved or dispersed in an organic solvent, and a mixed solution thereof is granulated in an aqueous medium and contained in the granulated particles. A solution suspension method (suspension granulation method) in which a toner is produced by removing the organic solvent is preferable.
This is because by selecting an organic solvent as appropriate, it is difficult to dissolve in vinyl-based polymerizable monomers usually used in suspension polymerization methods, but a polyester resin having a low melt viscosity is used as a toner. This is because it can be used as a binder resin. Further, since a large amount of crystalline polyester resin can be added, it is a method that can achieve further low-temperature fixability of the toner.
However, in the toner manufacturing process, the organic solvent is finally removed to obtain toner particles, and the dispersion state of the pigment dispersed in the organic solvent changes depending on the surrounding environment of the pigment. .

  When a toner is produced by the dissolution suspension method, a three-dimensional solid is not necessary unless the molecular chain of the polymer component, which is the dispersing group of the pigment dispersant, is sufficiently expanded in the organic solvent in which the binder resin and the crystalline polyester resin are dissolved. The dispersibility of the pigment cannot be maintained well due to the repulsive effect. In particular, in the step of removing the organic solvent, which is a good solvent, if the polymer component of the pigment dispersant does not have good affinity for both the toner binder resin and the crystalline polyester resin, It contracts and the dispersibility of the pigment cannot be maintained well. Since a large physical force as in the pulverization method is not applied, the influence of the affinity of each material becomes significant.

Therefore, the following two conditions are indispensable as in the present invention, and the polymer component of the pigment dispersant must have a monomer composition suitable for it.
(I) The difference (A−B) between the SP value (A) of the pigment dispersant and the SP value (B) of the crystalline polyester resin is −0.90 or more and +1.00 or less.
(Ii) The difference (A−C) between the SP value (A) of the pigment dispersant and the SP value (C) of the binder resin is −2.00 or more and +2.00 or less.

In order to obtain a sufficient steric repulsion effect without any harmful effects, the following conditions are also essential.
(Iv) The number average molecular weight (Mn) of the polymer component of the pigment dispersant is 3000 to 20000.
At that time, of course, unless the adsorbing group component of the pigment dispersant is firmly adsorbed to the pigment, the pigment dispersant is removed from the pigment, particularly during the organic solvent removing step. Since the effect is lost, the following conditions are also essential.
(Iii) The pigment dispersant has a polymer component and an adsorption component having an adsorption rate of 30% or more to the pigment, and the polymer component has a partial structure represented by a vinyl polymer.
Hereinafter, the measurement method used in the present invention will be described.

<Method for Measuring Glass Transition Temperature of Pigment Dispersant and Amorphous Polyester Resin>
The glass transition temperature (Tg) of the pigment dispersant or amorphous polyester resin in the present invention can be determined by differential scanning calorimetry (DSC) measurement.
In DSC measurement, from the measurement principle, it is preferable to measure with a differential scanning calorimeter of high accuracy internal heat type input compensation type. For example, DSC-7 manufactured by Perkin Elmer and DSC-2920 manufactured by TA Instruments Japan can be used. In the present invention, the measurement is performed using DSC-2920 manufactured by TA Instruments Japan.
The measurement is performed according to ASTM D3418-82. 10 mg of a measurement sample is precisely weighed and placed in an aluminum pan, and measurement is performed at a temperature increase rate of 10 ° C./min in a measurement range of 30 to 200 ° C. using an aluminum pan as a reference. A specific heat change is obtained in the temperature range of 40 ° C. to 100 ° C. during the temperature raising process. At this time, the temperature at the point of intersection between the line of the midpoint of the baseline before and after the change in specific heat and the differential heat curve is defined as the glass transition temperature.

<Method for measuring adsorption rate of pigment dispersant to pigment>
The adsorption rate of the pigment dispersant to the pigment was measured as follows.
[Create calibration curve]
(A) 5 mL of “the styrene solution of the pigment dispersant” containing the above pigment dispersant in a mass ratio of styrene / the pigment dispersant = 5.0 / 0.1 with respect to styrene is prepared (“solution 1”). "). Further, styrene is added to the solution 1 to prepare solutions diluted so that the content ratio of the pigment dispersant is 1/2, 1/4, 1/5, or 1/10 (hereinafter referred to as “respectively”). , “Solution 2”, “Solution 3”, “Solution 4” and “Solution 5”).
(B) Solutions 1, 2, 3, 4 and 5 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. And the said pigment dispersant was measured using GPC on the following conditions, and the calibration curve of the azo compound density | concentration (g / mL) in a liquid medium was created. The same operation was carried out for each of the pigment dispersants used in the present invention, and a calibration curve for each of the pigment dispersants 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 ° C.
・ Sample injection amount: 0.025 mL

[Measurement of adsorption rate]
(A) The same pigment as the toner to be actually produced, and the same pigment dispersant as that of the toner to be actually produced with styrene, and a dispersion having a mass ratio of pigment / styrene / azo compound = 1.0 / 5.0 / 0.1 After preparation, the mixture 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: About 80% of the composition was added to the volume of the centrifuge tube. ・ Centrifuge condition: 10000 rpm for 3 minutes (25 ° C.)
(B) The supernatant of the centrifuged composition is collected, filtered with a filter (Nippon Millipore, Mirex LH, pore size 0.45 μm, diameter 13 mm), and supernatant using the above 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) −The pigment dispersant concentration in the supernatant of the composition (g / mL)} / {Azo compound concentration in solution 1 (g / mL)} × 100

<Method for Measuring Acid Value of Pigment Dispersant, Crystalline Polyester Resin, and Amorphous Polyester Resin>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. That is, the number of mg of potassium hydroxide required to neutralize free fatty acids and resin acids contained in 1 g of a sample is referred to as an acid value.
In the present invention, the acid value is measured according to JIS K 0070-1992. Specifically, the measurement is performed according to the following procedure.

(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 to avoid contact with carbon dioxide, etc., it is placed in an alkali-resistant container and left for 3 days, followed by filtration to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. As the factor of the potassium hydroxide solution, take 25 mL of 0.1 mol / L hydrochloric acid in an Erlenmeyer flask, add a few drops of the phenolphthalein solution, titrate with the potassium hydroxide solution, and the hydroxylation 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 the sample is precisely weighed into a 200 mL Erlenmeyer flask, and 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 added (that is, only a mixed solution of toluene / ethanol (2: 1) is used).

(3) Calculation of acid value The obtained result is substituted into the following formula to calculate the acid value.
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 pigment dispersant>
The amine value in the present invention is measured according to JIS K 7237-1995. Specifically, the measurement is performed according to the following procedure.
(1) Preparation of reagent 0.1 g of crystal violet is dissolved in 100 mL of acetic acid to obtain a crystal violet solution. 8.5 mL of perchloric acid is slowly added and mixed into a mixed solution of 500 mL of acetic acid and 200 mL of acetic anhydride. 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 above perchloric acid acetic acid solution is that 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 a few drops of the crystal violet solution are added. Titrate with chloracetic acid solution. Obtained from the amount of perchloric acid acetic acid solution required for neutralization.

(2) Operation (A) Main test 2.0 g of the sample is precisely weighed in a 200 mL beaker, and 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 as an indicator 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 added (that is, only a mixed solution of o-nitrotoluene / acetic acid (9: 2) is used).

(3) Calculation of amine value The obtained result is substituted into the following formula to calculate the amine value.
AmV = [(D−C) × f × 5.61] / S
Here, AmV: amine value (mgKOH / g), C: addition amount of perchlorate acetic acid solution in blank test (mL), D: addition amount of perchlorate acetic acid solution in this test (mL), f: excess Factor of chloracetic acid solution, S: sample (g).

<Composition analysis of pigment dispersant>
The structure of the pigment dispersant having the polymer part and the adsorption unit of the present invention was determined using the following apparatus.
¹ H NMR and ¹³ C NMR
ECA-400 manufactured by JEOL Ltd. (solvent heavy chloroform)
FT-NMR AVANCE-600 manufactured by Bruker (solvent heavy chloroform)

<Measurement of molecular weight of the above pigment dispersant and amorphous polyester resin by GPC>
The number average molecular weight (Mn) of the pigment dispersant in the present invention, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the amorphous polyester resin are determined by gel permeation chromatography (GPC) according to the following procedure. Use to measure.
Dissolve the sample in tetrahydrofuran (THF) over 24 hours at room temperature. The obtained solution is filtered through a solvent-resistant membrane filter “Mysholy disk” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is prepared so that the concentration of the component soluble in THF is about 0.8% by mass. Measurement is performed under the following conditions using this sample solution.

Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Shodex KF-801, 802, 803, 804, 805, 806,
7 series of 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Oven temperature: 40.0 ° C
Sample injection volume: 0.10 mL
In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

<Measurement of SP value of binder resin, crystalline polyester, pigment dispersant>
The SP values of the binder resin, crystalline polyester, and pigment dispersant were measured as follows by a cloud point titration measurement method.
In a 50 mL sample tube bottle, about 1.48 g of precisely weighed binder resin, crystalline polyester or pigment dispersant is dissolved in about 10.00 g of precisely weighed chloroform. Next, one drop (about 200 mg) of methanol is added with a Pasteur pipette, the lid is closed, the weight is measured, and the mixture is stirred for 1 minute with a microrotor for magnetic stirrer (full length 3 mm × diameter Φ3 mm). After stirring, visually stir the solution to see if it is cloudy. If not cloudy, repeat the above procedure until cloudy.
Similarly, heptane is used instead of methanol.
The SP values of the binder resin, crystalline polyester, and pigment dispersant were calculated from the following formulas based on the respective weights of chloroform and methanol or heptane at the time of cloudiness.

SP value of binder resin, crystalline polyester, pigment dispersant = (SP _α + SP _β ) / 2
^{_{SP α = (Vm 1/2 × SPm}} + Vc · mL 1/2 × SPc) / (Vm 1/2 + Vc 1/2)
SP _β (Vc ^1/2 × SPc + Vh ^1/2 × SPh) / (Vc ^1/2 + Vh ^1/2 )
Vm (cm ³ ): volume of methanol at the time of cloudiness (specific gravity of methanol: 0.792)
Vc (cm ³ ): volume of chloroform at the time of cloudiness (specific gravity of chloroform: 1.490)
Vh (cm ³ ): volume of heptane at the time of cloudiness (specific gravity of heptane: 0.684)
SPm: SP value of methanol (14.5 cal / cm ³ )
SPc: SP value of chloroform (9.3 cal / cm ³ )
SPh: SP value of heptane (7.4 cal / cm ³ )
SPm, SPc, and SPh are cited from Non-Patent Document 1.

  The binder resin is a bulk polymerization under the same reaction conditions (temperature and time) as the toner particles in the toner particles of each of Examples and Comparative Examples described later, using only the vinyl polymerizable monomer and the initiator in each formulation. The SP value of the resin produced by performing the above was defined as the SP of the binder resin.

<Measurement of average particle size and particle size distribution of toner>
The average particle size and particle size distribution of the toner can be measured by various methods such as Coulter Counter TA-III type or Coulter Multisizer (manufactured by 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 attached dedicated software “Beckman Coulter Multisizer 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 was 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 dedicated to 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 solution is placed in 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 the solution with ion exchange water about 3 times by mass 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 Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) 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 contaminant 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 the state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 toners are used.
Add mg in small amounts to the electrolytic aqueous solution and disperse. Further, when confirming the granulation property of the toner particles, the toner particle suspension after completion of the polymerization reaction is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In 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 of (1) installed in the sample stand, the electrolyte solution of (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. The “average diameter” on the “analysis / weight statistical value (arithmetic average)” screen when the graph / volume% is set in the dedicated software is the weight average particle diameter (D4). When the graph / number% is set in the dedicated software, the “average diameter” on the “analysis / number statistics (arithmetic average)” 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 volume% / D50 number% is 50% particle diameter based on weight distribution / 50% particle diameter based on number distribution.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, a following example does not limit this invention at all. In the following examples and comparative examples, “part” and “%” are based on mass.
<Production Example of Polymer Component (A-1) of Pigment Dispersant>
100 parts of propylene glycol monomethyl ether was heated while being purged with nitrogen, refluxed at a liquid temperature of 120 ° C. or higher, and a mixture of the following materials was added dropwise over 3 hours.

滴下終了後、溶液を３時間撹拌した後、液温１７０℃まで昇温しながら常圧蒸留し、液温１７０℃到達後は１ｈＰａで減圧下１時間蒸留して脱溶剤し、樹脂固形物を得た。上記固形物をテトラヒドロフランに溶解し、ｎ−ヘキサンで再沈殿、析出した固体を濾別することでポリマー成分（Ａ−１）を得た。得られたポリマー成分（Ａ−１）の組成を表４に示す。

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 matter was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was separated by filtration to obtain a polymer component (A-1). Table 4 shows the composition of the obtained polymer component (A-1).

<Production Examples of Polymer Components (A-2) to (A-13) and (A-20) to (A-22) of Pigment Dispersant>
As shown in Table 4, the polymer components (A-2) to (A-13) and (A-20) to (A-22) changed the types and composition ratios of the polymerizable monomers. The polymer components (A-2) to (A-13) and (A-20) to (A-22) of the azo compound were changed in the same manner as the polymer component (A-1) except that the type and composition ratio were changed. Manufactured. The total mass of the polymerizable monomers was the same as that of the polymer component (A-1).
Table 4 shows the compositions of the obtained polymer components (A-2) to (A-13) and (A-20) to (A-22).

<Production Example of Polymer Component (A-14) of Pigment Dispersant>
Trimethylolpropane tris (3-mercaptopropionate) [manufactured by Sakai Chemical Co., Ltd.] (β-mercaptopropionic acid) 0.15 parts by mass is additionally added together with a polymerizable monomer, and 1.25 parts by weight of perbutyl Z is perbutyl. D [manufactured by NOF Corporation] was changed to 20.0 parts by mass. Thus, the polymer component (A-14) of the azo compound was produced in the same manner as the polymer component (A-1) except that the composition ratio of the polymerizable monomer was changed as shown in Table 4. Table 4 shows the composition of the obtained polymer component (A-14).

<Production Example of Polymer Component (A-15) of Pigment Dispersant>
Trimethylolpropane tris (3-mercaptopropionate) [manufactured by Sakai Chemical Co., Ltd.] (β-mercaptopropionic acids) was changed to 0.10 parts by mass, respectively, and the same pigment as in the polymer component (A-14) A polymer component (A-15) of a dispersant was produced. Table 4 shows the composition of the obtained polymer component (A-15).

<Production Examples of Polymer Components (A-16) to (A-19) of Pigment Dispersant>
The polymer component of the azo compound (A-1) is the same as the polymer component (A-1) except that perbutyl Z is changed to 2.00 parts by weight, 1.50 parts by weight, 0.90 parts by weight, and 0.80 parts by weight, respectively. A-16) to (A-19) were produced. Table 4 shows the compositions of the obtained polymer components (A-16) to (A-19).

<Production Example of Polymer Component (A-23) of Pigment Dispersant>
The following materials were mixed in an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, and reacted at 220 ° C. under a nitrogen atmosphere and normal pressure for 15 hours. Furthermore, it was made to react under reduced pressure of 10-20 mmHg for 2.5 hours, and the polyester resin (a) was obtained.

The physical properties of the polyester resin (a) are as follows.
Mw = 12,000, Mw / Mn = 2.49, Tg = 74.9 (° C.), acid value = 12.1 (mgKOH / g)
The polyester resin (a) obtained, 100 parts by mass of 440.0 parts by mass of dehydrated chloroform was completely dissolved, and then cooled with ice while 2-isocyanatoethyl methacrylate [manufactured by Showa Denko Co., Ltd., 4 parts by mass of the trade name “Karenz MOI” was added. Thereafter, the mixture was stirred at room temperature (25 ° C.) for a whole day and night.
The resin solution was gradually dropped into a container containing 550.0 parts by mass of methanol to reprecipitate the resin component, followed by filtration, purification and drying to obtain a polyester resin (b).
Subsequently, the following materials were added to a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube, and the polymerization reaction was performed at a temperature of 110 ° C. while stirring.

ビニル変性ポリエステル樹脂（ポリマー成分（Ａ−２３））を得た。分子量Ｍｎは１８０００であった。

A vinyl-modified polyester resin (polymer component (A-23)) was obtained. The molecular weight Mn was 18000.

Ｓｔ：スチレン、ＡＡ：アクリル酸、ＡＡｍ：アクリルアミド、
ＭＡ：メチルアクリレート、ＢＡ：ｎ−ブチルアクリレート、
２−ＥＨＡ：２−エチルヘキシルアクリレート、ＳｔＭＡ：ステアリルメタクリレート
ＤｄＭＡ：ドデシルアクリレート、ＢｅＡ：ベヘニルアクリレート

St: styrene, AA: acrylic acid, AAm: acrylamide,
MA: methyl acrylate, BA: n-butyl acrylate,
2-EHA: 2-ethylhexyl acrylate, StMA: stearyl methacrylate DdMA: dodecyl acrylate, BeA: behenyl acrylate

<Production example of polyester resin for toner binder resin>
(Production Example of Amorphous Polyester Resin 1)
The following materials were mixed in an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, and reacted at 220 ° C. under a nitrogen atmosphere and normal pressure for 22 hours.

さらに１０〜２０ｍｍＨｇの減圧下で１．５時間反応させ、非晶性ポリエステル樹脂１を得た。

Furthermore, it was made to react under reduced pressure of 10-20 mmHg for 1.5 hours, and the amorphous polyester resin 1 was obtained.

The physical properties of the obtained amorphous polyester resin 1 are shown below.
Mw = 9750, Mw / Mn = 2.55, Tg = 71.2 (° C.), acid value = 6.1 (mgKOH / g), SP value = 10.37 (cal / cm ³ )

(Production Example of Amorphous Polyester Resin 2)
The following materials were mixed in an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, and reacted at 220 ° C. under a nitrogen atmosphere and normal pressure for 22 hours.

さらに１０〜２０ｍｍＨｇの減圧下で１．５時間反応させ、非晶性ポリエステル樹脂２を得た。

Furthermore, it was made to react under reduced pressure of 10-20 mmHg for 1.5 hours, and the amorphous polyester resin 2 was obtained.

The physical properties of the obtained amorphous polyester resin 2 are shown below.
Mw = 15750, Mw / Mn = 2.55, Tg = 67.2 (° C.), acid value = 3.1 (mgKOH / g), SP value = 10.29 (cal / cm ³ )

(Production Example of Amorphous Polyester Resin 3)
The following materials were mixed in an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, and reacted at 220 ° C. under a nitrogen atmosphere and normal pressure for 22 hours.

さらに１０〜２０ｍｍＨｇの減圧下で１．５時間反応させ、非晶性ポリエステル樹脂３を得た。

Furthermore, it was made to react under reduced pressure of 10-20 mmHg for 1.5 hours, and the amorphous polyester resin 3 was obtained.

The physical properties of the obtained amorphous polyester resin 3 are shown below.
Mw = 12750, Mw / Mn = 2.85, Tg = 64.2 (° C.), acid value = 8.1 (mgKOH / g), SP value = 10.77 (cal / cm ³ )

(Production Example of Amorphous Polyester Resin 4)
The following materials were mixed in an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, and reacted at 220 ° C. under a nitrogen atmosphere and normal pressure for 22 hours.

さらに１０〜２０ｍｍＨｇの減圧下で１．５時間反応させ、非晶性ポリエステル樹脂４を得た。

Furthermore, it was made to react under reduced pressure of 10-20 mmHg for 1.5 hours, and the amorphous polyester resin 4 was obtained.

The physical properties of the obtained amorphous polyester resin 4 are shown below.
Mw = 15750, Mw / Mn = 2.95, Tg = 61.2 (° C.), acid value = 8.1 (mgKOH / g), SP value = 11.07 (cal / cm ³ )

(Example of production of crystalline polyester 1)
A reactor equipped with a stirrer, a thermometer, and an outflow cooler was charged with 175.0 parts by mass of sebacic acid, 166.5 parts by mass of 1,9-nonanediol, and 0.3 parts of tetrabutyl titanate. Time reaction was performed. Thereafter, the temperature was raised to 200 ° C., the pressure inside the system was gradually reduced, and the reaction was performed under reduced pressure for 5 hours to obtain crystalline polyester 1. Table 11 shows the physical properties of the obtained crystalline polyester 1.

(Example of production of crystalline polyester 2)
A reactor equipped with a stirrer, a thermometer and an outflow cooler was charged with 175.0 parts by mass of sebacic acid, 210.1 parts by mass of 1,12-dodecanediol, and 0.2 parts of tetrabutyl titanate. Time reaction was performed. Thereafter, the temperature was raised to 200 ° C., the pressure inside the system was gradually reduced, and the reaction was performed under reduced pressure for 5 hours to obtain crystalline polyester 2. Table 11 shows the physical properties of the obtained crystalline polyester 2.

(Example of production of crystalline polyester 3)
Under a nitrogen atmosphere, add 50 parts of xylene, 175.0 parts by weight of sebacic acid, and 210.1 parts of 1,12-dodecanediol to a pressure resistant reactor equipped with a dropping funnel, a Liebig condenser and a stirrer at 210 ° C. The temperature was raised to. The pressure at this time was 0.32 MPa. A mixture prepared by dissolving the following materials in 10 parts of xylene in a dropping funnel was added dropwise under pressure (0.31 MPa) over 2 hours.

滴下後、さらに２１０℃で３時間反応を行い、溶液重合を完了した。その後、テトラブトキシチタネート０．８０部を混合し、窒素雰囲気下、常圧下２１０℃で３時間縮重合反応を行った。その後テトラブトキシチタネートを０．０１０部追加し、２１０℃で２時間反応させた。その後、常圧に戻し、安息香酸３７．０部とトリメリット酸４．００部を添加し、さらに２２０℃で５時間反応させて結晶性ポリエステル３を得た。得られた結晶性ポリエステル３の物性を表１１に示す。

After the dropping, the reaction was further performed at 210 ° C. for 3 hours to complete the solution polymerization. Thereafter, 0.80 part of tetrabutoxy titanate was mixed, and a polycondensation reaction was performed at 210 ° C. under a nitrogen atmosphere for 3 hours. Thereafter, 0.010 part of tetrabutoxy titanate was added and reacted at 210 ° C. for 2 hours. Thereafter, the pressure was returned to normal pressure, 37.0 parts of benzoic acid and 4.00 parts of trimellitic acid were added, and the mixture was further reacted at 220 ° C. for 5 hours to obtain crystalline polyester 3. Table 11 shows the physical properties of the obtained crystalline polyester 3.

(Example of production of crystalline polyester 4)
Crystalline polyester 4 was obtained in the same manner as crystalline polyester 3, except that 29.7 parts of styrene were changed to 60.0 parts by weight of styrene. Table 11 shows the physical properties of the obtained crystalline polyester 4.

(Example of production of crystalline polyester 5)
Add 100.0 parts by mass of sebacic acid and 93.5 parts by mass of 1,10-decanediol to a reaction vessel equipped with a stirrer, thermometer, nitrogen introduction tube, dehydration tube, and decompression device and stir. While heating to 130 ° C. After adding 0.7 parts by mass of titanium (IV) isopropoxide as an esterification catalyst, the temperature was raised to 160 ° C. and polycondensation was performed over 5 hours. Then, it heated up at the temperature of 180 degreeC, it was made to react until it became a desired molecular weight, making it reduce pressure, and polyester (A) was obtained. The weight average molecular weight (Mw) of polyester (A) was 19000, and melting | fusing point (Tm) was 83 degreeC.
Subsequently, 100.0 parts by mass of polyester (A) and 440.0 parts by mass of dehydrated chloroform were added to a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube and completely dissolved. Thereafter, 5.0 parts by mass of triethylamine was added, and 15.0 parts by mass of 2-bromoisobutyryl bromide was gradually added while cooling with ice. Thereafter, the mixture was stirred at room temperature (25 ° C.) for a whole day and night.
The resin solution was gradually dropped into a container containing 550.0 parts by mass of methanol to reprecipitate the resin component, followed by filtration, purification and drying to obtain polyester (B).
Subsequently, the following materials were added to a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube, and the polymerization reaction was performed at a temperature of 110 ° C. while stirring.

所望の分子量となったところで反応を停止して、メタノール２５０．０質量部で再沈殿、濾過、精製し、未反応のスチレンおよび触媒を除去した。その後、５０℃に設定した真空乾燥機で乾燥してポリエステル部位とビニルポリマー部位を有する結晶性ポリエステル５を得た。得られた結晶性ポリエステル５の物性を表１１に示す。

When the desired molecular weight was reached, the reaction was stopped, and reprecipitation, filtration and purification were performed with 250.0 parts by mass of methanol to remove unreacted styrene and catalyst. Then, it dried with the vacuum dryer set to 50 degreeC, and obtained the crystalline polyester 5 which has a polyester site | part and a vinyl polymer site | part. Table 11 shows the physical properties of the obtained crystalline polyester 5.

(Production example of crystalline polyesters 6 and 7)
In the production example of crystalline polyester 5, 93.5 parts by mass of 1,10-decanediol was changed to 83 parts by mass of 1,9-nonanediol, and the addition amount of styrene was changed to 400.0 parts by mass and 450 parts by mass, respectively. Crystalline polyesters 6 and 7 were obtained in the same manner except that the changes were made. Table 11 shows the physical properties of the obtained crystalline polyesters 6 and 7.

A production example of the pigment dispersant used in the present invention will be described.
<Production Example of Pigment Dispersant 1 [Compound (35)]>
Compound (34) having an azo skeleton partial structure represented by the following structure was produced according to the following scheme.

まず、クロロホルム３０部に４−ニトロアニリン（東京化成工業（株）製）３．１１部を加え、１０℃以下に氷冷し、ジケテン（東京化成工業（株）製）１．８９部を加えた。その後、６５℃で２時間撹拌した。反応終了後、クロロホルムで抽出し、濃縮して化合物（３２）を得た。

First, 3.11 parts of 4-nitroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) is added to 30 parts of chloroform, ice-cooled to 10 ° C. or less, and 1.89 parts of diketene (manufactured by Tokyo Chemical Industry Co., Ltd.) are added. It was. 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 (32).

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., Ltd.), 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 (the resulting solution is referred to as “diazonium salt solution”). 4.51 parts of the compound (32) was added to 70.0 parts of methanol, and the mixture was ice-cooled to 10 ° C. or less 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 (33).

Next, 8.58 parts of compound (33) and 0.4 part of palladium-activated carbon (palladium 5%) were added to 150 parts of N, N-dimethylformamide, and the reaction was performed under a hydrogen gas atmosphere (reaction pressure 0.1). And stirred at 40 ° C. for 3 hours. After completion of the reaction, the solution was filtered off and concentrated to obtain compound (34).
Next, the azo compound 8 [compound (35)] was produced according to the following scheme by combining the amino group of the compound (34) having an azo skeleton partial structure with 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, 3.20 parts of compound (34) was added to 500 parts of tetrahydrofuran, and heated to 80 ° C. to dissolve. 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) And stirred at 50 ° C. for 5 hours. Thereafter, 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 produce pigment dispersant 1 as compound (35).

<Production Example of Pigment Dispersant 2-31>
Pigment dispersants 2 to 31 were produced in the same manner as pigment dispersant 1 except that the azo skeleton partial structure and the polymer component were changed as shown in Table 12. Table 13 shows the physical properties of the obtained pigment dispersants 2-31.
<Production Example of Pigment Dispersant 32>
A pigment dispersant [Compound (37)] was produced according to the following scheme.

化合物（３４）１．９８部を４−フェニルアゾ−１−ナフチルアミン（東京化成工業（株）製）１．９８部に変えた以外は顔料分散剤１の製造例のポリマー結合工程と同様にして、顔料分散剤３２［化合物（３７）］を得た。得られた顔料分散剤３２［化合物（３７）］の物性は表１３に示す。

Except for changing 1.98 parts of compound (34) to 1.98 parts of 4-phenylazo-1-naphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), in the same manner as in the polymer binding step of the production example of pigment dispersant 1, Pigment dispersant 32 [Compound (37)] was obtained. Table 13 shows the physical properties of Pigment Dispersant 32 [Compound (37)].

  The azo skeleton partial structure shown in Table 12 will be described below.

［一般式（Ｗ１）および（Ｗ２）中、Ｒ_３、Ｒ_４およびＲ_５〜Ｒ_９はそれぞれ表１２中に示される置換基を示す。表１２中の（Ｒ_４−１）および（Ｒ_４−２）はそれぞれ下記構造を示す。］

[In General Formulas (W1) and (W2), R ₃ , R ₄ and R _{5 to} R ₉ each represent a substituent shown in Table 12. (R ₄ -1) and (R ₄ -2) in Table 12 each represent the following structure. ]

［上記（Ｒ_４−１）および（Ｒ_４−２）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示す。また、「＊＊＊」は下記一般式（Ｗ２−２）の「＊＊＊」と結合していることを示す。］

["*" In the above (R ₄ -1) and (R ₄ -2) is incorporated into the polymer component by a chemical bond and indicates that it is bonded to the polymer. Further, “***” indicates that it is combined with “***” in the following general formula (W2-2). ]

［一般式（Ｗ２−２）中、Ｒ_３、Ｒ_４およびＲ_５〜Ｒ_９はそれぞれ表１２中に示される置換基を表す。「＊＊＊」は、それぞれ上記（Ｒ_４−１）および（Ｒ_４−２）の「＊＊＊」と結合していることを示す。］

[In General Formula (W2-2), R ₃ , R ₄ and R _{5 to} R ₉ each represent a substituent shown in Table 12. “***” indicates that it is bonded to “***” in the above (R ₄ -1) and (R ₄ -2). ]

[Production of hydrophobic silica 1]
Hydrophobic silica 1 was obtained by treating 100 parts of silica (AEROSIL 200CF, manufactured by Nippon Aerosil Co., Ltd.) with 10 parts of hexamethyldisilazane and further with 20 parts of chlorophenyl silicone oil. The primary particle diameter of hydrophobic silica 1 was 12 nm, and the degree of hydrophobicity was 97.
[Production of hydrophobic titanium oxide 1]
100 parts of titanium oxide (P25, manufactured by Nippon Aerosil Co., Ltd.) was treated with 20 parts of γ-mercaptopropyltrimethoxysilane in toluene, filtered and dried to obtain hydrophobic titanium oxide 1. The primary particle diameter of hydrophobic titanium oxide 1 was 25 nm, and the degree of hydrophobicity was 60.

[Example 1]
(Synthesis of toner binder solution)
130 parts by mass of crystalline polyester resin 1 and 870 parts by mass of amorphous polyester resin 1 were dissolved and mixed in 2,000 parts by mass of an ethyl acetate solvent to obtain an ethyl acetate solution of toner binder (1).
(Create toner)
The following materials were placed in a beaker and stirred at 12,000 rpm with a TK homomixer at 55 ° C. to uniformly dissolve and disperse the toner material solution.

In a beaker, 706 parts of ion-exchanged water, 294 parts of hydroxyapatite 10% suspension [Superite 10 (manufactured by Nippon Chemical Industry Co., Ltd.)] and 0.17 parts of sodium dodecylbenzenesulfonate were uniformly dissolved. . Next, while stirring at 12,000 rpm with a TK homomixer at 55 ° C., the toner material solution was added and stirred for 3 hours.
Next, the mixed solution was transferred to a Kolben equipped with a stirring bar and a thermometer, and the temperature was raised to 98 ° C. to remove the solvent. The aqueous medium was cooled and washed with ion exchange water. Thereafter, drying and air classification were performed to obtain black colored particles.
0.3 parts by weight of hydrophobic titanium oxide 1 is added to 100 parts by weight of the obtained black colored particles, mixed with a Henschel mixer (manufactured by Mitsui Miike), 1.5 parts by weight of hydrophobic silica 1 is added, and the Henschel is further added. Toner 1 having an external additive was prepared by mixing with a mixer. Table 16 shows the physical properties of the obtained toner 1.

[Examples 2 to 58]
Toners 2 to 58 having external additives were produced in the same manner as in Example 1 except that the type and amount of pigment dispersant and the type of pigment were changed as shown in Table 15. Table 16 shows the physical properties of the obtained toners 2-58.
[Comparative Examples 1-6]
Toners 59 to 64 having external additives were prepared in the same manner as in Example 1 except that the type and amount of pigment dispersant and the type of pigment were changed as shown in Table 15. Table 16 shows the physical properties of the obtained toners 59 to 64.

[Examples 1 to 58]
Each of the toners 1 to 58 was subjected to various image evaluations using an evaluation machine.
Table 17 shows the results of various image evaluations.
[Comparative Examples 1-6]
Each of the toners 59 to 64 was subjected to various image evaluations using an evaluation machine.
Table 17 shows the results of various image evaluations.

（＊）アゾ化合物ではないが、アゾ化合物と同様に測定
Ｄ４：重量平均粒径、Ｄ１：数平均粒径

(*) Not an azo compound, but measured in the same manner as the azo compound D4: weight average particle diameter, D1: number average particle diameter

※１：現像剤担持体やトナー層規制部材へのトナーの融着や固着

* 1: Toner fusing or adhering to developer carrier or toner layer regulating member

Various image evaluations were performed as follows.
<Fog>
For the measurement of fog, an evaluation machine, which will be described later, is used as an image forming apparatus, and an endurance test is performed in a system that pauses for one minute every time two sheets are printed at a printing rate of 1% under the following environment. Later, it was left for 6 days in each environment.

その後の１枚目の画像サンプルのカブリ量を東京電色社製のＲＥＦＬＥＣＴ ＭＥＴＥＲ ＭＯＤＥＬＴＣ−６ＤＳを使用して測定し、下記式より算出した。耐久試験に用いた記録材としてはＡ４サイズの普通紙（キヤノンマーケティングジャパン社製、ＧＦ−Ｃ０８１Ａ４）を用いた。
カブリ量（％）＝（プリントアウト前の記録材の白色度）−（プリント後の記録材の非画像形成部（白地部）の白色度）

The fog amount of the first image sample after that was measured using REFECT METER MODELTC-6DS manufactured by Tokyo Denshoku Co., Ltd. and calculated from the following formula. A4 size plain paper (manufactured by Canon Marketing Japan Inc., GF-C081A4) was used as the recording material used in the durability test.
Fog amount (%) = (whiteness of recording material before printing out) − (whiteness of non-image forming portion (white background portion) of recording material after printing)

<Image density>
The initial image density is a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH), and the amount of toner on the paper is 0.38 (mg / cm ² ) using an evaluation machine described later. 1) was printed, and the image density of each image was measured. The density of the image sample was measured using REFECT METER MODELTC-6DS manufactured by Tokyo Denshoku Co., Ltd. A4 size plain paper (manufactured by Canon Marketing Japan Inc., GF-C081A4) was used as the recording material.

<Fixability>
Under a low-temperature and low-humidity environment (L / L: temperature 15 ° C., humidity 10% RH), using the evaluation machine described later, the machine and the cartridge filled with the toner are familiar with the environment (after leaving in the above environment for 24 hours) The power was turned on. Immediately after the weight-up, a 200 μm-wide horizontal line pattern (width 200 μm, interval 200 μm) was printed out, and the 50th printed image was used for evaluation of fixability. The fixing property was evaluated by rubbing the image with Sylbon paper at a load of 100 g for 5 reciprocations, and peeling of the image was evaluated by the average of the reduction rate (%) of the reflection density.
For the evaluation, bond paper having a surface smoothness of 10 [seconds] or less was used. The evaluation criteria are shown below.

<Offset resistance>
Offset resistance is normal temperature and humidity environment (N / N: temperature 23.5 ° C, humidity 60% RH), high temperature and humidity environment (H / H: temperature 32.5 ° C, humidity 80% RH). Evaluation was performed using an evaluation machine described later. The machine and the cartridge filled with toner were turned on after being in the environment (after being left in the above environment for 24 hours), and immediately after waiting for weight up, 100 solid images were printed out, and the image samples were evaluated. .
For the evaluation, an OHP film (CG3700, manufactured by Sumitomo 3M Limited) was used. The evaluation criteria are shown below.

<Fusion and adhesion of toner to toner layer regulating member>
The toner is fused and fixed to the toner layer regulating member in a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH), and in a high temperature and high humidity environment (H / H: temperature 32.5 ° C.). , Humidity 80% RH), and evaluated using an evaluation machine described later. An endurance test was performed by a method of pausing for 1 minute every time two sheets were printed at a printing rate of 1%, and an image sample of the endurance 8000th sheet from the beginning was visually evaluated. As the recording material, A4-sized plain paper (Canon Marketing Japan Co., Ltd., GF-C081A4) was used. The evaluation criteria are shown below.

<Filming to latent image carrier>
Filming on the latent image carrier is performed in a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and in a low temperature and low humidity environment (L / L: temperature 15 ° C., humidity 10% RH). Using an evaluation machine described later, a durability test was performed by continuous printing at a printing rate of 1%. The image sample of the 2000th durability from the beginning was evaluated visually. As the recording material, A4-sized plain paper (Canon Marketing Japan Co., Ltd., GF-C081A4) was used. The evaluation criteria are shown below.

<Evaluation of storage stability of toner>
The storage stability of the toner was evaluated by weighing 10 g of toner into a 100 mL polycup, leaving it in a constant temperature layer at 50 ° C. for 3 days, and then evaluating the screen with 200 mesh (opening). As a measuring device, a powder tester (manufactured by Hosokawa Micron Corporation) having a digital vibrometer (manufactured by DEGIBALBATIONIONERMODEL 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. The evaluation criteria are shown below.

(Evaluation machine)
The process speed of commercially available LBP-2710 (manufactured by Canon Inc.) was modified to 220 mm / s, the toner was removed from the commercially available magenta cartridge, and the inside was cleaned by air blow. Thereafter, 260 g of the toner of the present invention was filled, and other cyan, yellow and black cartridges were used after the toner was removed and inserted into each station.

Claims (10)

A toner having toner particles containing a binder resin, a pigment, a pigment dispersant and a crystalline polyester,
The binder resin is an amorphous polyester resin;
The pigment is carbon black, C.I. I. Pigment red 122, C.I. I. Pigment red 150, and C.I. I. A pigment selected from the group consisting of CI Pigment Yellow 185;
Toner, wherein the pigment dispersing agent, meet the following (i) ~ (iv), and having a partial structure represented by the following general formula (2):
(I) The difference (A−B) between the SP value (A) of the pigment dispersant and the SP value (B) of the crystalline polyester resin is −0.90 or more and +1.00 or less,
(Ii) The difference (A−C) between the SP value (A) of the pigment dispersant and the SP value (C) of the binder resin is −2.00 or more and +2.00 or less,
(Iii) The pigment dispersant has a polymer component and an adsorption component having an adsorption rate of 30% or more to the pigment, and the polymer component has a partial structure represented by a vinyl polymer,
(Iv) The number average molecular weight (Mn) of the polymer component of the pigment dispersant is 3000 to 20000.

[In the general formula (2), any one of R ₃ , R ₄ and Ar is bonded to the polymer component via a single bond or a linking group,
R ₃ represents an alkyl group, a phenyl group, an OR ₆ group or an NR ₇ R ₈ group.
R _{6 to} R ₈ each independently represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
When R ₃ is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to R ₃ 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 ₅ — and —NHCH (CH ₂ OH) —;
R ₅ represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
R ₄ represents an alkyl group, a phenyl group, an OR ₁₀ group or an NR ₁₁ R ₁₂ group.
R < ₁₀ > -R < ₁₂ > shows a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group each independently.
When R ₄ is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to R ₄ is an alkylene group, a phenylene group, a carboxylic acid ester group, a carboxylic acid amide group, or a sulfonic acid ester group. , A sulfonic acid amide group, —O—, —NR ₉ —, and —NHCH (CH ₂ OH) —.
R ₉ 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) —.
The single bond or a linking _group, when bound to R 3, _{R 4} or Ar _is bonded substituted with R 3, _{R 4} or Ar hydrogen atoms. ] The toner according to claim 1, wherein the polymer component of the pigment dispersant has a monomer unit represented by the following general formula (1).

[In General Formula (1), R ₁ represents an alkyl group, an aralkyl group, or a hydrogen atom, and R ₂ represents an alkyl group having 4 to 22 carbon atoms. ]   The toner according to claim 1, wherein the polymer component of the pigment dispersant has a partial structure represented by a vinyl polymer and a polyester resin. The toner according to claim 1, wherein the partial structure represented by the general formula (2) is a partial structure represented by the following general formula (3).

[In the general formula (3), any one of R ₃ , R ₄ , R _{13 to} R ₁₇ is bonded to the polymer component via a single bond or a linking group.
R ₃ represents an alkyl group, a phenyl group, an OR ₆ group or an NR ₇ R ₈ group.
R _{6 to} R ₈ each independently represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
When R ₃ is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to R ₃ 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 ₅ — and —NHCH (CH ₂ OH) —;
R ₅ represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
R ₄ represents an alkyl group, a phenyl group, an OR ₁₀ group or an NR ₁₁ R ₁₂ group.
R < ₁₀ > -R < ₁₂ > shows a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group each independently.
When R ₄ is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to R ₄ is an alkylene group, a phenylene group, a carboxylic acid ester group, a carboxylic acid amide group, or a sulfonic acid ester group. , A sulfonic acid amide group, —O—, —NR ₉ —, and —NHCH (CH ₂ OH) —.
R ₉ represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
R _{13 to} R ₁₇ each independently represent a hydrogen atom, a COOR ₁₈ group, or a CONR ₁₉ R ₂₀ group. When R _{13 to} R ₁₇ are bonded to a polymer component, they are bonded via a single bond or a linking group. , R _{13 to} R ₁₇ are each composed of an amide group, an ester group, a urethane group, a urea group, an alkylene group, a phenylene group, —O—, —NR ₃ —, and —NHCH (CH ₂ OH) —. A divalent linking group selected from the group;
R _{18 to} R ₂₀ each independently represent a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group.
The single bond or a linking _group, when bound to _{R 3, R 4, R 13} ~R 17 _is, R _{3, R 4,} and bind to replace the hydrogen atom of R 13 _{to R 17.} ] In the general formula (3),
R ₃ represents an alkyl group, a phenyl group, an OR ₆ group or an NR ₇ R ₈ group, and R _{6 to} R ₈ each independently represent a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group,
R ₄ represents —NH—, which is bonded to the polymer component via a linking group, and the linking group is a phenylene group;
R _{13 to} R ₁₇ each independently represent a hydrogen atom, a COOR ₁₈ group, or a CONR ₁₉ R ₂₀ group, and R _{18 to} R ₂₀ each independently represent a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group. The toner according to claim 4 , wherein The toner according to any one of claims 1 to 5 , wherein the number of adsorbing components per molecule of the pigment dispersant is 1.0 or more and 6.0 or less. The crystalline polyester, a dicarboxylic acid represented by the following general formula (4), according to any one of claims 1 to 6 having a component comprised of a diol represented by the following general formula (5) Toner.
HOOC- _(CH 2) m-COOH (4)
[In Formula (4), m shows the integer of 4-16. ]
HO— (CH ₂ ) n —OH Formula (5)
[In Formula (5), n shows the integer of 4-16. ] When the acid value of the pigment dispersant, the toner according to any one of claims 1 to 7 or less 10.0mgKOH / g. The amine value of the pigment dispersant, the toner according to any one of claims 1-8 or less 5.0 mgKOH / g.   The toner according to claim 1, wherein the pigment is carbon black.

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