JP2013182058A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner having both excellent developability and high color gamut and high coloring power.SOLUTION: The toner contains a binder resin, a pigment, and an azo compound. The azo compound is a specific azo compound, and in an inclined charge measurement using an aluminum inclined plate applied with the azo compound, the charged amount is 5 μC/g or less.

Description

  The present invention relates to a toner for developing an electrostatic image used in an image forming method such as electrophotography and electrostatic printing.

The electrophotographic technology used for copiers, printers, facsimiles and the like continues to develop, and toner having higher coloring power than before has been attracting attention. It has been proposed that an image is formed with a small amount of toner by using a toner with high coloring power, thereby achieving a long life and size reduction of the toner container and further energy saving. However, even if the amount of pigment was simply increased, the pigment dispersion in the toner deteriorated, and both the high color gamut and the high coloring power could not be satisfied. Furthermore, a large amount of pigment has had an adverse effect on the charging property. Therefore, for the purpose of improving the pigment dispersion in the toner, a polymer dispersant having a portion having a high affinity for the pigment and a polymer component imparting the dispersibility in the medium has been used.
For example, as an inkjet application, an example using a polymer dispersant in which a portion having affinity for a pigment composed of a pigment derivative having a bisazo structure is suspended in a polymer is disclosed (Patent Document 1). On the other hand, as a polymer pigment dispersant for toner, an example using a dispersant in which an azo or bisazo chromophore bonded to a polymer containing an acetoacetanilide substitution product is used is disclosed (Patent Document 2). Recently, there has been proposed a dispersant having a site having an affinity for a polymer having a high compatibility with the toner binder resin and a pigment having an aromatic skeleton (Patent Document 3).

Special table 2009-501251 Japanese Patent No. 3984840 JP 2010-152208 A

However, when toners are produced using these pigment dispersants, it has been difficult to obtain a toner having both the required developability, high color gamut and high coloring power. In Patent Document 1, it was found that excellent dispersibility cannot be obtained unless a pigment derivative similar to the pigment used in the toner. In Patent Document 2, sufficient pigment dispersibility cannot be obtained with a toner produced in an aqueous medium. In Patent Document 3, it has been found that, depending on the pigment type, a sufficient pigment dispersion effect cannot be obtained unless a large amount of dispersant is added, and the dispersant has an adverse effect on the toner chargeability.
The present invention aims to solve the above problems. In other words, it is possible to exhibit an excellent dispersion effect regardless of various pigments and production methods, and by using a pigment dispersant that does not affect the toner chargeability even when the amount added is increased, excellent developability and high color gamut / An object of the present invention is to provide a toner having both high coloring power.

［前記一般式（１）中、Ｒ_１、Ｒ_２、及びＡｒのいずれかは、単結合又は連結基を介してポリマー成分が結合する構造を有し、
Ｒ_１は、アルキル基、フェニル基、ＯＲ_４基又はＮＲ_５Ｒ_６基を表し、Ｒ_４乃至Ｒ_６は、それぞれ独立して、水素原子、アルキル基、フェニル基又はアラルキル基を表す。Ｒ_１がポリマー成分と結合する場合、単結合又は連結基を介して結合し、Ｒ_１に結合する連結基は、アミド基、エステル基、ウレタン基、ウレア基、アルキレン基、フェニレン基、−Ｏ−、−ＮＲ_３−及び−ＮＨＣＨ（ＣＨ_２ＯＨ）−からなる群より選ばれる二価の連結基であり、Ｒ_３は、水素原子、アルキル基、フェニル基又はアラルキル基を表す。
Ｒ_２は、アルキル基、フェニル基、ＯＲ_８基又はＮＲ_９Ｒ_１０基を表し、Ｒ_８乃至Ｒ_１０は、それぞれ独立して、水素原子、アルキル基、フェニル基又はアラルキル基を表す。Ｒ_２がポリマー成分と結合する場合、単結合又は連結基を介して結合し、Ｒ_２に結合する連結基は、アルキレン基、フェニレン基、−Ｏ−、−ＮＲ_７−及び−ＮＨＣＨ（ＣＨ_２ＯＨ）−からなる群より選ばれる二価の連結基であり、Ｒ_７は、水素原子、アルキル基、フェニル基又はアラルキル基を表す。
Ａｒは、アリール基を表し、Ａｒがポリマー成分と結合する場合、単結合又は連結基を介して結合し、Ａｒに結合する連結基は、アミド基、エステル基、ウレタン基、ウレア基、アルキレン基、フェニレン基、−Ｏ−、−ＮＲ_３−及び−ＮＨＣＨ（ＣＨ_２ＯＨ）−からなる群より選ばれる二価の連結基であり、Ｒ_３は、水素原子、アルキル基、フェニル基又はアラルキル基を表す。
前記単結合又は連結基が、Ｒ_１、Ｒ_２、又はＡｒに結合する場合は、Ｒ_１、Ｒ_２、又はＡｒの水素原子と置換して結合する。］
前記アゾ化合物を塗布したアルミ傾斜板を用いた傾斜帯電測定において、帯電量が５μＣ／ｇ以下であることを特徴とするトナーである。 The present invention is a toner containing a binder resin, a pigment and an azo compound, wherein the azo compound is an azo compound represented by the following general formula (1):

[In the general formula (1), any one of R ₁ , R ₂ , and Ar has a structure in which a polymer component is bonded through a single bond or a linking group,
R ₁ represents an alkyl group, a phenyl group, an OR ₄ group or an NR ₅ R ₆ group, and R _{4 to} R ₆ each independently represent a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. When R ₁ is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to R ₁ is an amide group, ester group, urethane group, urea group, alkylene group, phenylene group, -O A divalent linking group selected from the group consisting of —, —NR ₃ — and —NHCH (CH ₂ OH) —, and R ₃ represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group;
R ₂ represents an alkyl group, a phenyl group, an OR ₈ group or an NR ₉ R ₁₀ group, and R _{8 to} R ₁₀ each independently represent a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. When R ₂ is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to R ₂ is an alkylene group, a phenylene group, —O—, —NR ₇ — and —NHCH (CH ₂ OH)-is a divalent linking group selected from the group consisting of-, and R ₇ represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
Ar represents an aryl group, and when Ar is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to Ar is an amide group, an ester group, a urethane group, a urea group, or an alkylene group. , A phenylene group, —O—, —NR ₃ — and —NHCH (CH ₂ OH) —, a divalent linking group selected from the group consisting of R ₃ is a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. Represents.
When the single bond or linking group is bonded to R ₁ , R ₂ , or Ar, it is bonded to a hydrogen atom of R ₁ , R ₂ , or Ar. ]
The toner has a charge amount of 5 μC / g or less in gradient charge measurement using an aluminum inclined plate coated with the azo compound.

  According to the present invention, a toner having both excellent developability, high color gamut and high coloring power can be obtained.

The figure which shows the situation at the time of measuring the charge quantity of the azo compound with the cascade type surface charge quantity measuring device Schematic diagram of an apparatus for measuring the triboelectric charge of toner

［前記一般式（１）中、Ｒ_１、Ｒ_２、及びＡｒのいずれかは、単結合又は連結基を介してポリマー成分が結合する構造を有し、
Ｒ_１は、アルキル基、フェニル基、ＯＲ_４基又はＮＲ_５Ｒ_６基を表し、Ｒ_４乃至Ｒ_６は、それぞれ独立して、水素原子、アルキル基、フェニル基又はアラルキル基を表す。Ｒ_１がポリマー成分と結合する場合、単結合又は連結基を介して結合し、Ｒ_１に結合する連結基は、アミド基、エステル基、ウレタン基、ウレア基、アルキレン基、フェニレン基、−Ｏ−、−ＮＲ_３−及び−ＮＨＣＨ（ＣＨ_２ＯＨ）−からなる群より選ばれる二価の連結基であり、Ｒ_３は、水素原子、アルキル基、フェニル基又はアラルキル基を表す。
Ｒ_２は、アルキル基、フェニル基、ＯＲ_８基又はＮＲ_９Ｒ_１０基を表し、Ｒ_８乃至Ｒ_１０は、それぞれ独立して、水素原子、アルキル基、フェニル基又はアラルキル基を表す。Ｒ_２がポリマー成分と結合する場合、単結合又は連結基を介して結合し、Ｒ_２に結合する連結基は、アルキレン基、フェニレン基、−Ｏ−、−ＮＲ_７−及び−ＮＨＣＨ（ＣＨ_２ＯＨ）−からなる群より選ばれる二価の連結基であり、Ｒ_７は、水素原子、アルキル基、フェニル基又はアラルキル基を表す。
Ａｒは、アリール基を表し、Ａｒがポリマー成分と結合する場合、単結合又は連結基を介して結合し、Ａｒに結合する連結基は、アミド基、エステル基、ウレタン基、ウレア基、アルキレン基、フェニレン基、−Ｏ−、−ＮＲ_３−及び−ＮＨＣＨ（ＣＨ_２ＯＨ）−からなる群より選ばれる二価の連結基であり、Ｒ_３は、水素原子、アルキル基、フェニル基又はアラルキル基を表す。
前記単結合又は連結基が、Ｒ_１、Ｒ_２、又はＡｒに結合する場合は、Ｒ_１、Ｒ_２、又はＡｒの水素原子と置換して結合する。］
前記アゾ化合物を塗布したアルミ傾斜板を用いた傾斜帯電測定において、帯電量が５μＣ／ｇ以下であることを特徴とする。 The toner of the present invention is a toner containing a binder resin, a pigment and an azo compound, wherein the azo compound is an azo compound represented by the following general formula (1):

[In the general formula (1), any one of R ₁ , R ₂ , and Ar has a structure in which a polymer component is bonded through a single bond or a linking group,
R ₁ represents an alkyl group, a phenyl group, an OR ₄ group or an NR ₅ R ₆ group, and R _{4 to} R ₆ each independently represent a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. When R ₁ is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to R ₁ is an amide group, ester group, urethane group, urea group, alkylene group, phenylene group, -O A divalent linking group selected from the group consisting of —, —NR ₃ — and —NHCH (CH ₂ OH) —, and R ₃ represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group;
R ₂ represents an alkyl group, a phenyl group, an OR ₈ group or an NR ₉ R ₁₀ group, and R _{8 to} R ₁₀ each independently represent a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. When R ₂ is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to R ₂ is an alkylene group, a phenylene group, —O—, —NR ₇ — and —NHCH (CH ₂ OH)-is a divalent linking group selected from the group consisting of-, and R ₇ represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
Ar represents an aryl group, and when Ar is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to Ar is an amide group, an ester group, a urethane group, a urea group, or an alkylene group. , A phenylene group, —O—, —NR ₃ — and —NHCH (CH ₂ OH) —, a divalent linking group selected from the group consisting of R ₃ is a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. Represents.
When the single bond or linking group is bonded to R ₁ , R ₂ , or Ar, it is bonded to a hydrogen atom of R ₁ , R ₂ , or Ar. ]
In the gradient charging measurement using the aluminum inclined plate coated with the azo compound, the charge amount is 5 μC / g or less.

By using the above azo compound, an excellent dispersion effect can be exhibited regardless of various pigments and production methods, and there is no influence on the toner charging property even if the addition amount is increased, and excellent developability, high color gamut, and high coloration. The inventors have found that a toner having both strengths can be obtained and led to the invention.
The structure of the formula (1) provided by the present invention will be described in detail.
The structure represented by the above formula (1) has tautomers represented by the following formulas (T1) and (T2) as shown in the following figure. Is also within the scope of the present invention.

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

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

  In the above formula (1), π-π bondability is strong, and in the formulas (T1) and (T2), hydrogen bondability is strong. On the other hand, as a result of repeated studies by the present inventors, it was found that there are roughly classified pigments having a strong π-π interaction and pigments having a strong hydrogen bonding interaction. That is, according to the present invention, by adopting the above resonance structure by the structure of the formula (1), an optimum structure having strong affinity for various pigments can be obtained, so that high affinity can be obtained regardless of the pigment. I think that is possible. As described above, the azo compound of the present invention is a polymer component that promotes dispersion into a binder resin, a portion having a high affinity for various pigments (hereinafter also referred to as an azo skeleton unit) due to the structure of the above formula (1). , And a connecting portion that binds the azo skeleton unit and the polymer component to obtain high pigment dispersibility in the toner binder resin.

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

R ₂ in the formula (1) can be arbitrarily selected from the substituents listed above and a hydrogen atom.
Among them, in order for the azo skeleton unit to improve the affinity due to the π-π interaction to a pigment having a large π conjugate plane such as carbon black, copper phthalocyanine, quinacridone, and carmine, R ₂ is an NR ₉ R ₁₀ group. And R ₉ is preferably a hydrogen atom, and R ₁₀ is an alkyl group having 1 to 6 carbon atoms or a phenyl group.
Moreover, when R2 _couple | bonds with a polymer component, it couple | bonds through a single bond or a coupling group. The linking group bonded to R ₂ is preferably a divalent linking group selected from the group consisting of an alkylene group, a phenylene group, —O—, —NH—, and —NHCH (CH ₂ OH) —.
Further, in the case _{where R 2} is bound to the polymer component, _{R 2} is _NR 9 _{R 10} group, and _{R 9} is a hydrogen _atom, and _{R 10} is a phenyl group, the phenyl group is a divalent linking group Thus, the mode of binding to the polymer component can be suitably exemplified. Furthermore, the aspect whose said coupling group is -NH- or -O- can be illustrated suitably.
The above linking group, when bound to R ₂ is bonded through substitution of the hydrogen atom of R _2.

Ar in the above formula (1) represents an aryl group, and examples thereof include a phenyl group and a naphthyl group.
In the azo compound of the present invention, the affinity for pigments having a large π-conjugated plane can be improved by having the Ar structure in the above formula (1).
Ar in the above formula (1) does not significantly inhibit the affinity of the azo skeleton unit due to the π-π interaction to the pigment having a large π conjugate plane, and also improves the affinity due to hydrogen bonding to the pigment. Therefore, it may be further substituted with a substituent.
Examples of the substituent that may be substituted with Ar 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. . These substituents are preferably selected as appropriate so that they form a hydrogen bond to the functional group of the pigment and become strong.
Further, when Ar is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to Ar is an amide group, ester group, urethane group, urea group, alkylene group, phenylene group, -O. A divalent linking group selected from the group consisting of —, —NH— and —NHCH (CH ₂ OH) — can be preferably exemplified.
In addition, when the said single bond or a coupling group couple | bonds with Ar, it substitutes and combines with the hydrogen atom of Ar, or the hydrogen atom of the substituent of Ar.

In the present invention, the azo compound represented by the above formula (1) is an azo compound represented by the following formula (2) from the viewpoint of enhancing the π-π interaction and the hydrogen bonding interaction. preferable.

In the present invention, in the above formula (2), any one of R ₁ , R ₂ , R _{11 to} R ₁₅ has a structure in which a polymer component is bonded via a single bond or a linking group.
In addition, R ₁ and R ₂ , and the linking group bonded to R ₁ and R ₂ are the same as those represented by the above formula (1).
R _{11 to} R ₁₅ are each independently a hydrogen atom, COOR ₁₆ group, CONR ₁₇ R _1
Eight groups are represented. R _{16 to} R ₁₈ each independently represents a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group.
The alkyl group in R _{16 to} R ₁₈ is preferably an alkyl group having 1 to 6 carbon atoms. For example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, n -Linear, branched or cyclic alkyl groups such as hexyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclohexyl group and the like. Among these, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are preferable from the viewpoint of preventing a decrease in affinity with the colorant due to steric hindrance.
Examples of the aralkyl group in R _{16 to} R ₁₈ include a benzyl group and a phenethyl group.
In the present invention, in formula (2), at least one of R _{11 to} R ₁₅ is preferably a COOR ₁₆ group or a CONR ₁₇ R ₁₈ group. The COOR ₁₆ group is preferably substituted at the substitution position located in the β-position from the azo bond position, and the CONR ₁₇ R ₁₈ group is preferably substituted at the substitution position located in the β-position or the γ-position. The COOR ₁₆ group and the CONR ₁₇ R ₁₈ group substituted at the β-position have a stronger π-π interaction and can improve the affinity with the pigment. Furthermore, the CONR ₁₇ R ₁₈ group substituted at the γ-position exhibits more hydrogen bonding interaction and can improve the affinity with the pigment.
R _{16 to} R ₁₈ can be arbitrarily selected from the substituents listed above and a hydrogen atom, but from the viewpoint of affinity for the pigment, R ₁₆ is a methyl group, and R ₁₇ and R ₁₈ are hydrogen. The case where it is an atom or a methyl group is preferable. At this time, not only steric hindrance does not occur, but also the presence of an ester bond or an amide bond increases the affinity due to hydrogen bonding and polarity to the pigment.
As described above, the azo compound represented by the above formula (2) can enhance the desired interactivity by changing the type of substituents and the substitution positions of R _{11 to} R ₁₅ .
On the other hand, when R _{11 to} R ₁₅ are bonded to the polymer component, they are bonded through a single bond or a linking group, and the linking group bonded to R _{11 to} R ₁₅ is an amide group, an ester group, a urethane group, a urea group, A divalent linking group selected from the group consisting of an alkylene group, a phenylene group, —O—, —NH—, and —NHCH (CH ₂ OH) — is preferable. In addition, when a single bond or a linking group is bonded to R _{11 to} R ₁₅ , it is bonded to a hydrogen atom of R ₁ , R ₂ , R _{11 to} R ₁₅ .

Further, in the above formula (1), it is preferable that R ₂ is an NR ₉ R ₁₀ group, R ₉ is a hydrogen atom, and R ₁₀ is a phenyl group. When R ₂ is an amino group, the π-π interaction becomes stronger and the interaction with carbon black or the like becomes stronger and the dispersibility of the pigment is further improved.
In the above formula (1), R ₂ is an NR ₉ R ₁₀ group, R ₉ is a hydrogen atom, R ₁₀ is a phenyl group, and the phenyl group is bonded via a divalent linking group. The aspect couple | bonded with a component can illustrate suitably. When R ₁₀ is a phenyl group having a bonding site with a polymer component, the influence on the π-π interaction and the hydrogen bonding interaction due to the structure in the above formula (1) is small, and the affinity with the pigment Sexuality can be maintained at a higher level.

Examples of the combination of substituents in the above formula (1) will be described with reference to examples, but are not limited thereto. When the above formula (1) is represented by the following formula (3), the balance between the hydrogen bonding interaction with the pigment and the π-π interaction property is excellent.

In said formula (3), L represents the bivalent coupling group for couple | bonding with a polymer component. The linking group L is not particularly limited as long as it is a divalent linking group, but from the group consisting of an alkylene group, a phenylene group, —O—, —NH—, and —NHCH (CH ₂ OH) —. The bivalent coupling group chosen is illustrated suitably.
Since the structure represented by the above formula (3) is excellent in both hydrogen bonding interaction and π-π interaction, interaction with various pigments is possible regardless of a specific pigment. Excellent pigment dispersibility in the binder resin. In the above formula (3), the substitution position of L (the substitution position of the phenyl group with a hydrogen atom) may be any of the o-position, m-position, and p-position with respect to the amide group. . The affinity with the pigment due to the difference in these substitution positions is the same.

  Moreover, the said Formula (1) is suitable for improving (pi)-(pi) interaction property, when represented by following formula (4).

In said formula (4), L represents the bivalent coupling group for couple | bonding with a polymer component. The linking group L is not particularly limited as long as it is a divalent linking group, but from the group consisting of an alkylene group, a phenylene group, —O—, —NH—, and —NHCH (CH ₂ OH) —. The bivalent coupling group chosen is illustrated suitably.
The structure of the above formula (4) has a high affinity with a pigment having high planarity such as carbon black, and has a high affinity with a pigment that easily interacts with π-π, and is excellent in pigment dispersibility. In the above formula (4), the substitution position of L (substitution position of the phenyl group with a hydrogen atom) may be any position of the o-position, m-position, or p-position with respect to the amide group. . The affinity with the pigment due to the difference in these substitution positions is the same.

In the present invention, a conventionally known polymer or copolymer can be used as the polymer component. However, in the present invention, from the viewpoint of improving the compatibility between the azo compound and the binder resin, and from the viewpoint of controlling the chargeability of the azo compound, a vinyl monomer polymer or copolymer, or Polyester and the like are preferable.
From the viewpoint of improving the compatibility between the azo compound and the binder resin, it is preferable that the structures of the polymer components of the binder resin and the azo compound are similar. For example, when the binder resin contains a vinyl resin as a main component, the polymer component of the azo compound is preferably based on a vinyl resin. On the other hand, when the said binder resin contains a polyester resin as a main component, it is preferable that the polymer component of an azo compound has a polyester resin as a main component. By doing so, the compatibility between the polymer component of the azo compound and the toner binder resin is enhanced, and the pigment dispersion effect is more remarkably exhibited. In addition, the above-mentioned “containing as a main component” means containing 50% by mass or more.
On the other hand, from the viewpoint of controlling the chargeability of the azo compound, the polymer component is preferably a vinyl resin (for example, a styrene polymer or copolymer, an acrylic polymer or copolymer, or a polyester resin). .

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

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

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

R ₁₉ in the general formula (5) is preferably a hydrogen atom or a methyl group from the viewpoint of polymerizability of the monomer unit.
R ₂₀ in the general formula (5) is preferably a carboxylic acid ester group, a carboxylic acid amide group, a phenyl group, or a carboxyl group, but the dispersibility and compatibility of the azo compound in the binder resin constituting the toner. From the viewpoint, a phenyl group, a carboxylic acid ester group, or a carboxylic acid amide group is preferable.
Although it does not specifically limit as said carboxylic acid ester group or carboxylic acid aralkyl ester group, For example, methyl ester group, ethyl ester group, n-propyl ester group, isopropyl ester group, n-butyl ester group, isobutyl Examples include ester groups such as ester groups, sec-butyl ester groups, tert-butyl ester groups, dodecyl ester groups, 2-ethylhexyl ester groups, stearyl ester groups, phenyl ester groups, benzyl ester groups, and 2-hydroxyethyl ester groups. .
Examples of the carboxylic acid amide group include an N-methylamide group, an N, N-dimethylamide group,
Examples include amide groups such as N, N-diethylamide group, N-isopropylamide group, N-tert-butylamide group, and N-phenylamide group.
In addition, the substituent of R ₂₀ in the general formula (5) may be further substituted, thereby inhibiting the polymerizability of the monomer unit or significantly reducing the compatibility of the azo compound with the binder resin. If it does not do, it will not be restricted in particular. In this case, examples of the substituent that may be substituted include an alkoxy group, an amino group, and an acyl group.

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

［式（５−１）中、Ｒ_２１は、水素原子又は炭素原子数が１乃至２のアルキル基を表し、Ｒ_２２は、炭素原子数が１乃至２２のアルキル基又は炭素原子数が７乃至８のアラルキル基を表す。ｌは、０又は正の整数値を表す。］

[In Formula (5-1), R ₂₁ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R ₂₂ represents an alkyl group having 1 to 22 carbon atoms or 7 to 7 carbon atoms. 8 represents an aralkyl group. l represents 0 or a positive integer value. ]

R ₂₁ in the general formula (5-1) is preferably a hydrogen atom or a methyl group from the viewpoint of polymerizability of the monomer unit.
The alkyl group represented by R ₂₂ in the general formula (5-1) is an alkyl group having 1 to 22 carbon atoms, or the number of carbon atoms from the viewpoint of dispersibility and compatibility with the binder resin constituting the toner. Is preferably an aralkyl group having 7 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 7 to 8 carbon atoms. In addition, this alkyl group may take any structure of a linear structure, a branched structure, or a cyclic structure.
On the other hand, examples of the aralkyl group in R ₂₂ include a benzyl group, an α-methylbenzyl group, and a phenethyl group.

［式（５−２）中、Ｒ_３３は、水素原子、又は炭素原子数が１乃至２のアルキル基を表す
。ｍは、０又は正の整数値を表す。］

[In the formula (5-2), R ₃₃ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. m represents 0 or a positive integer value. ]

［式（５−３）中、Ｒ_３４は、水素原子、又は炭素原子数が１乃至２のアルキル基を表す。ｎは、０又は正の整数値を表す。］

[In Formula (5-3), R ₃₄ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. n represents 0 or a positive integer value. ]

［式（５−４）中、Ｒ_３５は、水素原子、又は炭素原子数が１乃至２のアルキル基を表し、Ｒ_３６及びＲ_３７は、それぞれ独立して、水素原子、炭素原子数１乃至４のアルキル基、又はフェニル基を表す。ｐは、０又は正の整数値を表す。］

[In Formula (5-4), R ₃₅ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R ₃₆ and R ₃₇ each independently represent a hydrogen atom, 1 to 4 represents an alkyl group or a phenyl group. p represents 0 or a positive integer value. ]

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

In the present invention, the case where the polymer component has a polyester skeleton will be described in detail below.
When the binder resin constituting the toner is a polyester resin, from the viewpoint of compatibility with the binder resin, the polymer component is represented by at least the following general formula (6-1) and the following general formula (6-2). It is preferable to contain a polycondensation polymer containing a monomer unit as a constituent component. Or it is preferable to contain the polycondensation polymer which contains the monomer unit represented by the following general formula (6-3) as a structural component.

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

L ₃ in the above general formula (6-2) represents a divalent linking group. From the viewpoint of affinity for the binder resin, L ₃ is an alkylene group or a phenylene group, or the above general formula This is a case where (6-2) is represented by the following general formula (6-4).

［式（６−４）中、Ｒ_２４はエチレン基、又はプロピレン基を表す。ｘ及びｙは、それぞれ０以上の整数であり、且つｘ＋ｙの平均値は２乃至１０である。］

[In the formula (6-4), R ₂₄ represents an ethylene group or a propylene group. x and y are each an integer of 0 or more, and the average value of x + y is 2 to 10. ]

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

L ₄ in the general formula (6-3) represents a divalent linking group, and preferably L ₄ is an alkylene group or an alkenylene group.
Examples of the alkylene group in L ₄ include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a hexamethylene group, a neopentylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, and an undecamethylene group. , A linear, branched or cyclic alkylene group such as a dodecamethylene group or a 1,4-cyclohexylene group.
Examples of the alkenylene group in L ₄ include a vinylene group, a propenylene group, a butenylene group, a butadienylene group, a pentenylene group, a hexenylene group, a hexadienylene group, a heptenylene group, an octanylene group, a decenylene group, an octadecenylene group, an eicosenylene group, or a triacontenylene group. Is mentioned. These alkenylene groups may have any of linear, branched, and cyclic structures. In addition, the position of the double bond may be any location as long as it has at least one double bond.
The substituent for L ₄ may be further substituted with a substituent as long as the affinity for the binder resin is not significantly impaired. In this case, examples of the substituent that may be substituted include an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, and combinations thereof.
The L ₄ can be arbitrarily selected from the substituents listed above, but from the viewpoint of affinity for the binder resin, an alkylene group having 6 or more carbon atoms or an alkenylene group is preferable, and a combination thereof. There may be.

From the viewpoint of improving the compatibility with the binder resin, the molecular weight of the azo compound is preferably a number average molecular weight (Mn) measured using a size exclusion chromatograph (SEC) of 3000 or more and 30000 or less. It is preferable that they are 5000 or more and 25000 or less.
As the number average molecular weight increases, the charging stability of the polymer component increases, but the compatibility between the binder resin and the azo compound tends to decrease and the dispersibility tends to decrease. On the other hand, when the number average molecular weight is small, the compatibility between the binder resin and the azo compound is increased and the dispersibility is improved, but the charging stability tends to be lowered.
The positions of the azo skeleton units in the azo compound of the present invention may be randomly scattered or may be unevenly distributed by forming one or a plurality of blocks at one end.
The greater the number of azo skeleton units in the azo compound, the better the affinity for the pigment, but if too much, the affinity for the water-insoluble solvent used in the production of the binder resin will decrease, The ease of manufacturing tends to decrease. Therefore, the number of azo skeleton units is preferably in the range of 0.1 to 30 and more preferably in the range of 0.5 to 15 with respect to the number of monomers 100 forming the polymer component. preferable.

The charge amount of the azo compound of the present invention will be described. Even in the case of the azo compound represented by the above formula (1), if the charge amount is not less than 5 μC / g in the inclined charge measurement using the aluminum inclined plate coated with the azo compound, good toner charging characteristics are obtained. Can't get. That is, when the charge amount of the azo compound is larger than 5 μC / g, it is difficult for the toner to be negatively charged, and a charge amount suitable for image formation cannot be obtained. Further, the preferable range of the charge amount is 3 μC / g or less, more preferably 1 μC / g or less. Within this range, a more appropriate charge amount can be imparted to the toner. The charge amount is -1.5 C / g.
The above is preferable.
The charge amount of the azo compound varies depending on the amount of the azo skeleton unit introduced into the azo compound, but is greatly influenced by the charge characteristics of the polymer component. Therefore, the charge amount of the azo compound can be controlled by changing the composition of the polymer component.

In the azo compound of the present invention, when the acid value of the azo compound is AV (mg KOH / g) and the amine value of the azo compound is AmV (mg KOH / g), the ratio [AmV / AV] of AmV to AV is 0. It is preferably 0.50 or more and more preferably 0 or more and 0.30 or less. This is because an azo compound having a high acid value has a strong negative chargeability tendency, and an azo compound having a high amine value has a strong positive chargeability tendency. That is, if AmV / AV is 0.50 or less, it becomes easy to control the chargeability of the azo compound to negative chargeability, which is preferable for controlling the charge amount of the azo compound. The adjustment of AV and AmV can be controlled by changing the composition of the polymer component.
Also, the higher the acid value, the more negatively charged the azo compound because it is more negatively charged. However, when a toner is produced using a compound having an acid value that is too high, the toner tends to retain moisture. . Therefore, it shows a tendency to lower the charging stability of the toner. Therefore, the acid value AV (mgKOH / g) of the azo compound is preferably 30 mgKOH / g or less, and more preferably 0 mgKOH / g or more and 15 mgKOH / g or less.
On the other hand, since a compound having a high amine value becomes positively chargeable, it is preferable to make it low in order to make the azo compound negatively chargeable. In order to eliminate the influence on the toner chargeability, AmV (mgKOH / g) is preferably 5 mgKOH / g or less, and more preferably 0 mgKOH / g or more and 3 mgKOH / g or less.
In the present invention, as a method for adjusting the acid value of the azo compound, R ₂₀ in the above formula (5) adjusts the composition ratio of the monomer unit in which the carboxyl group is a carboxyl group, or the carboxyl group is a methyl group or the like. It can be suitably exemplified by adjusting by esterification with. On the other hand, as a method for adjusting the acid value of the azo compound, it is preferable to adjust the composition ratio of the monomer unit in which R ₂₀ in the above formula (5) is a carboxylic acid amide group.

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

_[R 1, _{R 2} in the formula (8) and (9) are each synonymous with _R 1, _{R 2} in the formula (1). Ar ₁ in the formulas (7) and (9) represents an arylene group. P ₁ is a polymer or copolymer containing the monomer unit represented by the above formula (5) or (6) as a constituent component. Q ₁ in the formulas (7) and (9) represents a substituent that reacts with P ₁ to form a single bond or a divalent linking group. ]

In the scheme of the method (i) exemplified above, Step 1 of synthesizing the azo skeleton unit (9) by diazo coupling the compound (8) with the aniline derivative represented by the formula (7), the azo skeleton unit ( The above azo compound can be synthesized by Step 2 in which 9) and the polymer component P ₁ are combined by a condensation reaction or the like.
The polymer component represented by P ₁ can control the molecular weight distribution and the molecular structure using a known method. For example, a polymer component with a controlled molecular weight distribution or molecular structure can be produced by using a method using an addition-cleavage type chain transfer agent, NMP method, ATRP method, RAFT method, MAGIX method, DT method, etc. it can.
Next, step 2 will be described. In step 2, a known method can be used. Specifically, for example, by using a polymer component P ₁ having a carboxyl group and an azo skeleton unit (9) in which Q ₁ is a substituent having an amino group, P ₁ and Q ₁ are carboxylic acid amides. The above azo compound linked by a bond can be synthesized. Specific examples include a method using a dehydrating condensing agent, such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, the Schotten-Baumann method, and the like.

［式（９）中のＲ_１、Ｒ_２、Ａｒ_１、及びＱ_１は、上記方法（ｉ）のスキーム中の式（９）中のＲ_１、Ｒ_２、Ａｒ_１、及びＱ_１と各々同義である。式（１０）中のＱ_２は、式（９）中のＱ_１と反応して、式（１１）中のＱ_３を形成する置換基を表す。式（１０）及び（１１）中のＲ_１９は、水素原子、アルキル基を表し、Ｑ３は式（９）中のＱ１及び式（１０）中のＱ_２が反応し、形成する二価の連結基を構成する置換基を表す。］ Next, the method (ii) will be described in detail by showing an example of the scheme.

[R ₁ , R ₂ , Ar ₁ , and Q ₁ in Formula (9) are the same as R ₁ , R ₂ , Ar ₁ , and Q _{1 in} Formula (9) in the scheme of the method (i), respectively. It is synonymous. Q ₂ in formula (10) represents a substituent that reacts with Q ₁ in formula (9) to form Q ₃ in formula (11). _{R 19} in the formula (10) and (11) represents a hydrogen atom, an alkyl group, Q3 is connected _a divalent _{Q 2} of Q1 and the formula (10) in the equation (9) is reacted to form The substituent which comprises group is represented. ]

In the scheme of the method (ii) exemplified above, the azo skeleton unit having a polymerizable functional group is obtained by reacting the azo skeleton unit represented by the formula (9) with the vinyl group-containing compound represented by the formula (10). The above azo compound is synthesized by the step 3 of synthesizing (11) and the step 4 of copolymerizing the azo skeleton unit (11) having a polymerizable functional group with the monomer unit represented by the above formula (5) or the like. can do.
For example, an isocyanate group-containing vinyl group-containing compound (10) (for example, 2-isocyanatoethyl methacrylate (manufactured by Showa Denko KK, trade name: Karenz MOI)) and an azo compound in which Q ₁ is a substituent having a hydroxyl group By using the skeleton unit (9), it is possible to synthesize the azo skeleton unit (11) having the polymerizable functional group, in which the linking group is a urethane bond.

［式（９）中のＲ_１、Ｒ_２、Ａｒ_１、及びＱ_１は上記方法（ｉ）のスキーム中の式（９）中のＲ_１、Ｒ_２、Ａｒ_１、及びＱ_１と各々同義である。式（１２）中のＱ_４は、式（９）中のＱ_１と反応して、式（１３）中のＱ_５を形成する置換基を表す。Ａは塩素原子、臭素原子、ヨウ素原子を表す。式（１３）中のＲ_１、Ｒ_２、及びＡｒ_１は、上記式（９）中のＲ_１、Ｒ_２、及びＡｒ_１と同意義を表し、Ｑ_５は式（９）中のＱ１及び式（１２）中のＱ_４が反応し、形成する連結基を表す。］ Next, method (iii) will be described in detail with reference to an example of a scheme.

[R ₁ , R ₂ , Ar ₁ , and Q ₁ in Formula (9) are the same as R ₁ , R ₂ , Ar ₁ , and Q ₁ in Formula (9) in the scheme of the method (i), respectively. It is. Q ₄ in formula (12) represents a substituent that reacts with Q ₁ in formula (9) to form Q ₅ in formula (13). A represents a chlorine atom, a bromine atom, or an iodine atom. R ₁ , R ₂ , and Ar _{1 in} formula (13) represent the same meaning as R ₁ , R ₂ , and Ar ₁ in formula (9), and Q ₅ represents Q1 in formula (9) and Q ₄ in formula (12) represents a linking group formed by reaction. ]

In the scheme of the method (iii) exemplified above, the azo skeleton unit represented by the formula (9) is reacted with the halogen atom-containing compound represented by the formula (12) to obtain an azo skeleton unit having a halogen atom (13 ) Is synthesized, and the azo compound is synthesized by the step 6 of polymerizing with a monomer unit represented by the above formula (5) using the halogen atom-containing azo skeleton unit (13) as a polymerization initiator. be able to.
As the halogen atom-containing compound (12) having a carboxyl group, acid halides and acid anhydrides thereof can be used in the same manner.
In Step 6, the ATRP method in the method (i) is used, and the azo skeleton unit (13) 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 polymerization.

［式（１４）、（１６）、（１８）及び（１９）中のＡｒ_２はアリーレン基を表す。式（１５）、（１６）、（１８）及び（１９）中のＲ_１は上記式（１）中のＲ１と同義である。式（１５）中のＱ_６は、式（１４）のアミノ基と反応して、式（１６）中のアミド基を形成する際に脱離する置換基を表す。Ｐ_１は上記方法（ｉ）のスキーム中のＰ_１と同義である。］ When R ₂ in the above formula (1) is an NR ₉ R ₁₀ group, R ₉ is a hydrogen atom, and R ₁₀ is a phenyl group, the azo compound is synthesized, for example, by the following method (iv). be able to.

[Ar ₂ in formulas (14), (16), (18) and (19) represents an arylene group. R ₁ in the formulas (15), (16), (18) and (19) has the same meaning as R ₁ in the above formula (1). Q ₆ in the formula (15) represents a substituent that is eliminated when reacting with the amino group in the formula (14) to form an amide group in the formula (16). P ₁ has the same meaning as P _{1 in} the scheme of the method (i). ]

In the scheme of the method (iv) exemplified above, an aniline derivative represented by the formula (14) and the compound (15) are amidated to obtain a compound represented by the compound (16) Step 7, the compound (16) and Step 8 of coupling the diazo component of the aniline analog represented by formula (17) to obtain an azo skeleton unit represented by formula (18), nitro group of the azo skeleton unit represented by formula (18) Is reduced to an amino group with a reducing agent to obtain an azo skeleton unit represented by the formula (19), an amino group of the azo skeleton unit represented by the formula (19), and a separately synthesized P ₁ The azo compound can be synthesized by the step 10 in which the carboxyl group of the polymer component is bonded by amidation.
In addition, when R ₁ in the compound (15) is a methyl group, it can be synthesized by a method using diketene instead of the compound (15).
In Step 10, the amino group of the azo skeleton unit represented by Formula (19) and the carboxyl group of the polymer component represented by P ₁ are converted using the same method as in Step 2 in Method (i). The azo compound can be synthesized by bonding by amidation or the like. In addition, even if the polymer component represented by P ₁ has an epoxy group (for example, a copolymer of 2,3-epoxypropyl methacrylate), amino in the azo skeleton unit represented by the formula (19) It is possible to react and bond with a group.
The compound obtained in each step of the exemplified synthesis method can be purified by using a normal organic compound isolation and purification method. Examples of isolation and purification methods include recrystallization methods and reprecipitation methods using organic solvents, column chromatography using silica gel, and the like. By purifying these methods singly or in combination of two or more, it is possible to obtain a highly pure compound.

  Next, the toner binder resin of the present invention will be described. The binder resin of the toner of the present invention is not particularly limited, and styrene-methacrylic acid copolymer, styrene-acrylic acid copolymer, polyester resin, epoxy resin, styrene-butadiene, which are generally used for toners. A copolymer is mentioned. In a method for directly obtaining toner particles by a polymerization method, a monomer for forming them is used. These are used singly or by appropriately mixing monomers so that the theoretical glass transition temperature (Tg) is in the range of 40 to 75 ° C. When the theoretical glass transition temperature is less than 40 ° C., problems are likely to occur in terms of storage stability and durability stability of the toner. On the other hand, when it exceeds 75 ° C., transparency tends to decrease in the case of full-color image formation of the toner. It is in. The binder resin in the toner of the present invention uses a non-polar resin such as polystyrene in combination with a polar resin such as a polyester resin or polycarbonate resin, so that the distribution of additives such as colorants, charge control agents, and waxes in the toner is distributed. Can be controlled. For example, when the toner particles are directly produced by suspension polymerization or the like, the polar resin may be added during the polymerization reaction from the dispersion step to the polymerization step. The polar resin is added according to the balance of the polarities of the monomer unit composition serving as toner particles and the aqueous medium. As a result, the resin concentration can be controlled to continuously change from the toner particle surface toward the center, for example, the polar resin forms a thin layer on the surface of the toner particle. At this time, by using a polar resin that interacts with the azo compound, the pigment, and the charge control agent, the state of the pigment in the toner particles can be changed to a desired form.

The toner of the present invention contains a pigment as a colorant. As the pigment used in the cyan colorant, a copper phthalocyanine compound and a derivative thereof, an anthraquinone compound, and a basic dye lake compound can be used. Specific examples include the following. C. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment Blue 15: 4.
Examples of the pigment used for the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples include the following. C. I. Pigment violet 19, C.I. I. Pigment red 31, C.I. I. Pigment red 122, C.I. I. Pigment red 150, C.I. I. Pigment Red 269.
Examples of the pigment used for the yellow colorant include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples include the following. C. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 155, C.I. I. Pigment Yellow 180
, C.I. I. Pigment Yellow 185.
Examples of the black colorant include carbon black, a magnetic material, and those that are toned to black using the yellow, magenta, and cyan colorants.
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 polymerizable monomer or the binder resin.

  In the toner of the present invention, the use ratio (mass basis) of the azo compound and the pigment is preferably 0.1: 100 to 30: 100, more preferably 0.5: 100 to 15: 100. .

  The method for producing the toner of the present invention will be specifically described. The toner of the present invention contains at least a binder resin, a pigment, and an azo compound. The toner production method of the present invention preferably has a step of dispersing a pigment in an organic medium. Specific examples include known melt kneading and pulverizing methods, dissolution suspension methods, and suspension polymerization methods.

Hereinafter, the measurement method used in the present invention will be described.
<Measurement method of charge amount of azo compound>
The charge amount of the azo compound was measured using a cascade type surface charge amount measuring apparatus (manufactured by Toshiba Chemical Co., Ltd.). FIG. 1 shows the situation when the charge amount of the azo compound is measured by the measuring device. The specific measurement method is as follows.
Add 0.5 g of azo compound and 1.5 g of methyl ethyl ketone (MEK) to the sample bottle and place in a warm bath with a shaker at 80 ° C. The sample solution was prepared by shaking for 15 min at a speed of 150 rpm. The sample solution was placed on a SUS plate for measuring the inclined charge amount No. 10 (thickness 22.86 μm: manufactured by Yasuda Seiki Seisakusho Co., Ltd.) is applied uniformly and dried in a vacuum dryer at 40 ° C. for 24 hours to prepare a measurement sample plate.
The measurement sample plate is fixed to a fluororesin table with a gradient of 60 degrees in the cascade surface charge measuring device in an N / N (22 ° C., 55% RH) environment. Then, the reference powder was allowed to flow from the inlet for 20 seconds, and the charge amount of the measurement sample plate was measured (three points were taken for each measurement point sample, and the average value was taken as the charge amount). In FIG. 1, 1 is a reference powder inlet, 2 is an inclined plate (sample stage), 3 is a reference powder, 4 is a tray, 5 is an insulating plate, 6 is an electrometer, and 7 is a meter connection terminal. .
First, the mass of the saucer 4 is weighed to obtain W1 [g]. A measurement sample plate is fixed to the inclined plate 2 having an inclination of 60 degrees, and the reference powder 3 is dropped from the reference powder inlet 1 for 20 seconds. After dropping the reference powder, the electric charge of the measurement sample plate is measured with the electrometer 6 and is defined as Q [nC]. In addition, the mass of the entire tray 4 after the reference powder is dropped is weighed to be W2 [g]. The inclined charge amount is calculated by the following equation. As a reference powder, the Japan Imaging Society standard carrier (N-02) is used.
Charge amount of azo compound [nC / g] = Q / (W2-W1)

<Method for measuring acid value of azo compound>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample.
The acid value AV of the azo compound is measured according to JIS K 0070-1992. Specifically, it is measured 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 not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution is that 25 ml of 0.1M hydrochloric acid is placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution is added, titrated with the potassium hydroxide solution, and the potassium hydroxide solution required for neutralization is added. Get from quantity. As the 0.1M hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
(2) Operation (A) Main test 2.0 g of a sample is precisely weighed into a 200 ml Erlenmeyer flask, 100 ml of a mixed solution of toluene / ethanol (2: 1) is added and dissolved over 5 hours. Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) Calculation of acid value AV = [(B−AB) × f × 5.61] / S
Here, AV: acid value (mgKOH / g), A: addition amount (ml) of potassium hydroxide solution in blank test, B: addition amount (ml) of potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

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

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

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

First, production examples of the azo skeleton unit used in the present invention will be described.
<Production example of azo skeleton unit 1 (compound (20))>
An azo skeleton unit 1 (20) having a compound represented by the following structure was produced according to the following scheme.

  First, 30.0 parts of water and 11.0 parts of concentrated hydrochloric acid were added to 5.00 parts of 4-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.), and the mixture was ice-cooled to 10 ° C or lower. To this solution, 3.46 parts of sodium nitrite dissolved in 8.10 parts of water was added and reacted at the same temperature for 1 hour. Next, 0.657 part of sulfamic acid was added and the mixture was further stirred for 20 minutes (diazonium salt solution). To 48.0 parts of water, 8.13 parts of acetoacetanilide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was ice-cooled to 10 ° C. or less, and the diazonium salt solution was added. Thereafter, 14.3 parts of sodium carbonate dissolved in 80.0 parts of water was added and reacted at 10 ° C. or lower for 2 hours. After completion of the reaction, 50 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 azo skeleton unit 1 (20). The azo skeleton unit 1 is shown in Table 1.

クロロホルム３０．０部に化合物（２０）３．００部、トリエチルアミン１．２０部を加えて１０℃以下に氷冷した。この溶液に、アクリロイルクロリド（東京化成工業株式会社製）１．０３部を加えて同温度で２０分反応させた。これをクロロホルムで抽出し、濃縮、精製することで、アゾ骨格ユニット２（２１）を得た。アゾ骨格ユニット２について表１に示す。 <Production example of azo skeleton unit 2 (compound (21))>
An azo skeleton unit 2 (21) represented by the following structure was produced according to the following scheme.

To 30.0 parts of chloroform were added 3.00 parts of compound (20) and 1.20 parts of triethylamine, and the mixture was ice-cooled to 10 ° C or lower. To this solution, 1.03 part of acryloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and reacted at the same temperature for 20 minutes. This was extracted with chloroform, concentrated and purified to obtain azo skeleton unit 2 (21). The azo skeleton unit 2 is shown in Table 1.

<Production example of azo skeleton unit 3 (compound (23))>
In the production example of the azo skeleton unit 2 (compound (21)), 1.03 part of acryloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to obtain 1.50 parts of 2-isocyanatoethyl methacrylate, 3 at 70 degrees. Reacted for hours. This was extracted with chloroform, concentrated and purified to obtain an azo skeleton unit (23). The azo skeleton unit 3 is shown in Table 1.

アゾ骨格ユニット１の製造例で、４−アミノフェノール５．００部であったところを、４−ニトロアニリン（東京化成工業株式会社製）６．３３部にして化合物（２４）を得た。
次に、Ｎ，Ｎ−ジメチルホルムアミド１５０部に化合物（２４）６．７５部及びパラジウム−活性炭素（パラジウム５％）０．４部を加えて、水素ガス雰囲気下（反応圧力０．１乃至０．４ＭＰａ）、４０℃で３時間撹拌した。反応終了後、溶液を濾別し、濃縮してアゾ骨格ユニット４（２５）を得た。アゾ骨格ユニット４について表１に示す。 <Production example of azo skeleton unit 4 (compound (25))>
An azo skeleton unit (25) having a compound represented by the following structure was produced according to the following scheme.

In the production example of the azo skeleton unit 1, the compound (24) was obtained by replacing 5.00 parts of 4-aminophenol with 6.33 parts of 4-nitroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.).
Next, 6.75 parts of the compound (24) and 0.4 parts of palladium-activated carbon (palladium 5%) are added to 150 parts of N, N-dimethylformamide, and a hydrogen gas atmosphere (reaction pressure 0.1 to 0) is added. And 4 MPa) at 40 ° C. for 3 hours. After completion of the reaction, the solution was filtered and concentrated to obtain azo skeleton unit 4 (25). The azo skeleton unit 4 is shown in Table 1.

<Production example of azo skeleton unit 5 (compound (26))>
In the production example of the azo skeleton unit 2, the azo skeleton unit 5 (26) was obtained by the same operation except that the compound (20) was changed to the compound (25). The azo skeleton unit 5 is shown in Table 1.

<Production example of azo skeleton unit 6 (compound (29))>
An azo skeleton unit 6 (29) represented by the following structure was produced according to the following scheme.

First, 3.11 parts of 4-nitroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 30 parts of chloroform, and ice-cooled to 10 ° C. or less, and 1.89 parts of diketene (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. Then, it stirred at 65 degreeC for 2 hours. After completion of the reaction, the mixture was extracted with chloroform and concentrated to obtain compound (27).
Next, 40.0 parts of methanol and 5.29 parts of concentrated hydrochloric acid were added to 4.25 parts of dimethyl 2-aminoterephthalate (manufactured by Merck & Co., Inc.), and the mixture was ice-cooled to 10 ° C. or lower. To this solution, 2.10 parts of sodium nitrite dissolved in 6.00 parts of water was added and reacted at the same temperature for 1 hour. Next, 0.990 parts of sulfamic acid was added and the mixture was further stirred for 20 minutes (diazonium salt solution). 4.51 parts of the compound (27) was added to 70.0 parts of methanol, and the mixture was cooled to 10 ° C. or less with ice 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 (28).
Next, 8.58 parts of Compound (28) and 0.4 part of palladium-activated carbon (palladium 5%) are added to 150 parts of N, N-dimethylformamide, and the reaction is carried out under a hydrogen gas atmosphere (reaction pressure 0.1 to 0). And 4 MPa) at 40 ° C. for 3 hours. After completion of the reaction, the solution was filtered and concentrated to obtain azo skeleton unit 6 (29). The azo skeleton unit 6 is shown in Table 1.

<Production example of azo skeleton unit 7 (compound (30)) to 10 (compound (33))>
According to the production example of the azo skeleton unit 6, azo skeleton units 7 to 10 were obtained. The azo skeleton units 7 to 10 are shown in Table 1.
<Production example of azo skeleton unit 11 (compound (34)) and azo skeleton unit 12 (compound (35))>
In the production example of the azo skeleton unit 6, production of the azo skeleton unit 6 was performed except that 4.00 parts of N, N-dimethylacetoacetamide (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the obtained compound (27). According to the examples, azo skeleton units 11 to 12 were obtained. The azo skeleton units 11 and 12 are shown in Table 1.

<Azo skeleton unit 13 (compound (36))>
As the azo skeleton unit 13 (compound (36)), 4-phenylazo-1-naphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following formula (36) was used.

Next, production examples of the polymer component of the azo compound used in the present invention will be described.
<Production Example of Polymer Component (A-1) of Azo Compound>
Heat 100 parts of propylene glycol monomethyl ether while purging with nitrogen and reflux at a liquid temperature of 120 ° C. or higher. To this, 152 parts of styrene, 36 parts of butyl acrylate, 9.4 parts of acrylic acid (styrene / acrylic acid / butyl acrylate) = 78.0 / 7.0 / 15.0 [m
ol%]), and tert-butyl peroxybenzoate [organic peroxide polymerization initiator, manufactured by NOF Corporation, trade name: perbutyl Z] was added dropwise over 3 hours. . After completion of the dropwise addition, the solution was stirred for 3 hours and then distilled at atmospheric pressure while raising the liquid temperature to 170 ° C. After reaching the liquid temperature of 170 ° C., it was distilled for 1 hour under reduced pressure at 1 hPa to remove the solvent. Obtained. The solid was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was filtered off to obtain a polymer component (A-1) of an azo compound. Table 2 shows the physical properties of the polymer component (A-1) of the obtained azo compound.

<Production Examples of Polymer Components (A-2) to (A-6) of Azo Compound>
The polymer components (A-2) to (A-6) of the azo compound are the same as the polymer component (A-1) of the azo compound except that the type and composition ratio of the polymerizable monomer are changed as shown in Table 2. Manufactured. Table 2 shows the physical properties of the polymer components (A-2) to (A-6) of the obtained azo compound.

<Production Example of Polymer Component (A-7) of Azo Compound>
The composition ratio of the polymerizable monomer is as shown in Table 2, and 0.20 part of trimethylolpropane tris (3-mercaptopropionate) [manufactured by Sakai Chemical Co., Ltd.] (β-mercaptopropionic acids) is additionally added as a polymerizable monomer. The same as the polymer component (A-1) of the azo compound except that it was added together with the polymer and the perbutyl Z content was 1.25 parts, but the perbutyl D (manufactured by NOF Corporation) was changed to 20.0 parts. Thus, an azo compound polymer component (A-7) was obtained. Table 2 shows the physical properties of the polymer component (A-7) of the obtained azo compound.

<Production Example of Polymer Component (A-8) of Azo Compound>
Polymer of azo compound in the same manner as polymer component (A-7) except that trimethylolpropane tris (3-mercaptopropionate) [manufactured by Sakai Chemical Co., Ltd.] (β-mercaptopropionic acids) was changed to 0.10 parts. Ingredient (A-8) was produced. Table 2 shows the physical properties of the polymer component (A-8) of the obtained azo compound.

<Production Example of Polymer Component (A-9) of Azo Compound>
The polymer component of the azo compound (A-9) was the same as the polymer component (A-1) of the azo compound except that the composition ratio of the polymerizable monomer was changed as shown in Table 2 and perbutyl Z was changed to 0.90 part. ) Was manufactured. Table 2 shows the physical properties of the polymer component (A-9) of the obtained azo compound.

<Production Example of Polymer Component (A-10) of Azo Compound>
The polymer component of the azo compound (A-10) was the same as the polymer component (A-1) of the azo compound except that the composition ratio of the polymerizable monomer was changed as shown in Table 2 and perbutyl Z was changed to 0.80 part. ) Was manufactured. Table 2 shows the physical properties of the polymer component (A-10) of the obtained azo compound.

<Production Example of Polymer Component (B-1) of Azo Compound>
In an autoclave equipped with a decompression device, water separation device, nitrogen gas introduction device, temperature measurement device, and stirring device, 15 parts of terephthalic acid, 36 parts of isophthalic acid, 126 parts of 2-mol adduct of bisphenol A-propylene oxide, 126 parts of dibutyltin oxide 0.030 parts The above polyester monomer was charged, reacted at 220 ° C. for 15 hours under a nitrogen atmosphere and normal pressure, and further reacted for 2.5 hours under reduced pressure of 10 to 20 mmHg to obtain a polymer component of an azo compound (B-1 ) The physical properties of the polymer component (B-1) of the azo compound are as follows: weight average molecular weight (Mw) = 12000, number average molecular weight (Mn) = 4800, Mw / Mn = 2.5, glass transition temperature (Tg) = 74.9. (° C.), acid value (AV) = 7.9 (mg KOH / g). Table 2 shows the physical properties of the polymer component (B-1) obtained.

<Production Example of Polymer Component (C-1) of Azo Compound>
In a four-necked 500 ml separable flask equipped with a stirrer, dropping funnel, reflux condenser, gas inlet tube, thermometer,
• 20 parts of dimethylol butanoic acid • 5 parts of N, N-bis (2-hydroxypropyl) aniline • 15 parts of polyethylene glycol • 70 parts of methyl ethyl ketone, the inside of the flask was replaced with dry nitrogen, and the temperature was raised to 80 ° C. with stirring. Warm up. Under stirring, 35 parts of isophorone diisocyanate was added dropwise over 10 minutes and allowed to react for 6 hours. The reaction product is cooled to 65 ° C., 300 parts of water and 11 parts of 25% ammonia water are added, and methyl ethyl ketone and alkaline water as a solvent are removed to obtain a polymer component (C-1) of an azo compound. It was. The physical properties of the polymer component (C-1) of the azo compound were Mw = 14000, Mn = 5200, Mn / Mw = 2.7, the acid value was 25.8 mgKOH / g, and the amine value was 4.3 mgKOH / g. . Table 2 shows the physical properties of the polymer component (C-1) obtained.

［スキーム中、「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表す記号である。］ Next, production examples of the azo compound used in the present invention will be described.
<Production Example of Azo Compound 1 (Compound (37))>
Azo compound 1 was obtained according to the following scheme.

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

To 500 parts of tetrahydrofuran, 2.00 parts of azo skeleton unit 6 (compound (29)) was added and heated to 65 ° C. to dissolve. After dissolution, the temperature is lowered to 50 ° C., and the polymer component (A-1
) 15.00 parts was dissolved, 2.0 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC.HCl) was added and stirred at 50 ° C. for 5 hours, and then 20 parts of methanol. Was added and reacted at 65 ° C. for 1 hour. 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 of methanol to obtain azo compound 1 (37). The structure of the obtained azo compound 1 is shown in Table 3, and the physical properties are shown in Table 4.

<Production Examples of Azo Compound 2 (Compound (38)) to 19 (Compound (55))>
Azo compounds 2 to 19 were obtained in the same manner except that the azo skeleton units and polymer components used in the production examples of azo compound 1 were as shown in Table 3. The structures of the obtained azo compounds 2 to 19 are shown in Table 3, and the physical properties are shown in Table 4.

［スキーム中、「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表す記号である。］ <Production Example of Azo Compound 20 (Compound (56))>
Azo compound 20 was obtained according to the following scheme.

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

  0.3 parts of acrylic acid, 10 parts of styrene, and 2.8 parts of butyl acrylate (styrene / acrylic acid / butyl acrylate = 79.0 / 3.0 / 18.0 [mol%]) and N, N- 9.44 parts of dimethylformamide, 1.06 parts of azo skeleton unit 2 (compound (21)) and 0.327 parts of azobisisobutyronitrile were added, and the mixture was stirred at 80 ° C. for 2 hours in a nitrogen atmosphere. Then, the azo compound 20 which is a compound (56) was obtained by refine | purifying with a recrystallization method from N, N- dimethylformamide. The structure of the obtained azo compound 20 is shown in Table 3, and the physical properties are shown in Table 4.

<Production Example of Azo Compound 21 (Compound (57)) and 22 (Compound 58))>
Azo compounds 21 and 22 were obtained in the same manner except that the azo skeleton units and polymer components used in the production examples of azo compound 20 were as shown in Table 3. The structures of the obtained azo compounds 21 and 22 are shown in Table 3, and the physical properties are shown in Table 4.

<Production Example of Azo Compound 23 (Compound (60))>
Azo compound 23 was obtained according to the following scheme.

First, 5.00 parts of azo skeleton unit 6 (compound (29)) and 1.48 parts of triethylamine are added to 25.0 parts of chloroform, and the mixture is cooled to 10 ° C. or lower with ice to give 2-bromoisobutyl bromide (manufactured by Tokyo Chemical Industry Co., Ltd.). ) 2.07 parts was added. Then, it stirred at room temperature for 6 hours. After completion of the reaction, extraction with chloroform and concentration gave compound (59).
Next, 50.0 parts of N, N-dimethylformamide, 2.50 parts of compound (59), 140 parts of styrene (33), N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine 77 parts and 0.64 parts of copper (I) bromide were added. Thereafter, the mixture was stirred at 120 ° C. for 45 minutes in a nitrogen atmosphere. After completion of the reaction, extraction with chloroform and purification by reprecipitation with methanol gave azo compound 23 (compound (60)). The structure of the azo compound 23 is shown in Table 3, and the physical properties are shown in Table 4.

<Production Example of Comparative Azo Compound 1 (Compound (61))>
A comparative azo compound 1 was obtained in the same manner except that the polymer component (A-1) of the azo compound in the production example of azo compound 1 was changed to (C-1). The structure of the comparative azo compound 1 is shown in Table 3, and the physical properties are shown in Table 4.

<Production Example of Comparative Azo Compound 2 (Compound (62))>
A comparative azo compound 2 was obtained in the same manner as in the production example of azo compound 1 except that the azo skeleton unit 6 was changed to the azo skeleton unit 13. The structure of the comparative azo compound 2 is shown in Table 3, and the physical properties are shown in Table 4.

<Structure of connecting part * 4>
In Table 3, (R ₂ -1), (Ar-1) to (Ar-6) represent the structure of the bonding portion between R ₂ and Ar of the above formula (1) and the polymer component.
“*” In the following formula represents a bonding site with the polymer component.

上記Ｒ_２−１の「＊」は、ポリマー成分由来のカルボキシル基の炭素原子との結合部位を表す。Ａｒ−１、Ａｒ−２及びＡｒ−６の「＊」は、ポリマー成分由来のカルボキシル基の炭素原子との結合部位を表す。Ａｒ−３、Ａｒ−４及びＡｒ−５の「＊」は、はポリマー成分中に化学結合により組み込まれ、ポリマーと結合していることを表す。一方、上記「＊＊」、「＊＊＊」又は「＊＊＊＊」は下記一般式の「＊＊」、「＊＊＊」又は「＊＊＊＊」と結合していることを示す。

The “*” in R ₂ −1 represents a bonding site with a carbon atom of a carboxyl group derived from a polymer component. “*” In Ar-1, Ar-2 and Ar-6 represents a bonding site with a carbon atom of a carboxyl group derived from a polymer component. “*” In Ar-3, Ar-4, and Ar-5 is incorporated into the polymer component by a chemical bond and represents a bond to the polymer. On the other hand, the above “***”, “***” or “***” indicates that it is combined with “***”, “***” or “***” in the general formula below. .

［スキーム中、「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表す記号である。］ <* 5>
The structure of the comparative azo compound 2 is represented by the following formula (61).

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

Next, toner production examples will be described.
<Production Example of Black (hereinafter also referred to as Bk) Toner 1>
[Master batch adjustment process]
-Styrene (St) monomer 246 parts-Carbon black (CB1) 45 parts (Nipex 35 [made by Orion Engineered Carbon)]
・ 4.5 parts of aluminum compound of 3,5-di-tert-butylsalicylic acid [Bontron E88 (manufactured by Orient Chemical Co., Ltd.)]
-Azo compound 6 4.5 parts The above materials are introduced into an attritor (Mitsui Mining Co., Ltd.) and stirred with 200 mm, 25 ° C for 300 minutes using zirconia beads (350 parts) with a radius of 2.5 mm, and the black master. Batch dispersion 1 was prepared.
[Toner composition solution preparation step]
-Master batch dispersion 1 150 parts-Styrene (St) monomer 30 parts-N-butyl acrylate (BA) monomer 51 parts-Hydrocarbon wax 22.5 parts (Fischer-Tropsch wax; HNP-51, Maximum endothermic peak = 78 ° C)
45 parts of polar resin 1 (copolymer of styrene, methacrylic acid, methyl methacrylate and 2-hydroxyethyl methacrylate, Mw = 14800, Tg = 89 ° C., acid value AV = 22 mgKOH / g, hydroxyl value OHv = 8 mgKOH / g )
Polar resin 2 0.5 part (styrene-2-ethylhexyl acrylate copolymer containing 5% 2-acrylamido-2-methylpropanesulfonic acid, Tg = 81 ° C.)
The above materials were mixed and heated to 65 ° C., and uniformly dissolved and dispersed at 5,000 rpm for 60 minutes using a TK homomixer (manufactured by Tokushu Kika Kogyo) to obtain a toner composition solution. .
On the other hand, in a four-necked 2 liter flask equipped with a high speed stirrer TK- homomixer, after turning the _0.1M-Na 3 PO ₄ aqueous solution 175 parts to 300 parts of deionized water, the TK-12, The temperature was adjusted to 000 rpm and heated to 60 ° C. Thereafter, 9.3 parts of a 1.0 M CaCl ₂ aqueous solution was gradually added to obtain an aqueous medium containing a calcium phosphate compound.
Next, 8 parts of a 70% toluene solution of a polymerization initiator 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate is dissolved in the toner composition solution, and after sufficient mixing, the aqueous medium is mixed. It was thrown into. This was stirred at 12,000 rpm for 10 minutes with a TK homomixer at a temperature of 65 ° C. in an N ₂ atmosphere to granulate the polymerizable monomer composition. Thereafter, the temperature was raised to 75 ° C. while stirring with a paddle stirring blade, and polymerization was carried out for 5 hours. Thereafter, the heating rate was 1 ° C./min. The temperature was raised to 85 ° C. and reacted for 1 hour to complete the polymerization reaction. Next, the residual monomer of the toner particles was distilled off under reduced pressure, and the aqueous medium was cooled to obtain a toner particle dispersion.
Hydrochloric acid was added to the toner particle dispersion to adjust the pH to 1.4, and the mixture was stirred for 1 hour to dissolve the calcium phosphate salt. This was subjected to solid-liquid separation with a pressure filter under a pressure of 0.4 Mpa to obtain a toner cake. Next, ion-exchanged water was added to the pressure filter until the water became full, and washing was performed at a pressure of 0.4 Mpa. This washing operation was repeated three times and then dried to obtain toner particles.
1.5 parts by mass (number average primary particle size: 10 nm) of hydrophobic silica fine powder surface-treated with hexamethyldisilazane is added to 100 parts by mass of the obtained toner particles, and a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). Was mixed for 300 seconds to obtain Bk toner 1. Table 5 shows Bk toner 1.

<Production examples of Bk toners 2 to 12 and 19 to 27>
Bk toners 2 to 12 and 19 to 27 were obtained in the same manner as Bk toner 1 except that the types and addition amounts of the azo compound and carbon black were adjusted as shown in Table 4 in the production example of Bk toner 1. Table 5 shows Bk toners 2 to 12 and 19 to 27.

<Example of production of Bk toner 13>
[Method for Producing Toner Binder Resin A]
・ Toluene 300 parts ・ Styrene 200 parts ・ N-butyl acrylate 30 parts ・ Methacrylic acid 25 parts ・ Sodium styrene sulfonate 15 parts The above materials are put into a reaction vessel equipped with a stirrer, condenser, thermometer, and nitrogen introduction tube. Then, 25 parts of a 70% toluene solution of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate is dissolved. Next, 0.10 parts of trimethylolpropane tris (3-mercaptopropionate) [manufactured by Sakai Chemical Co., Ltd.] (β-mercaptopropionic acids) was added, the temperature was raised to 80 ° C. under a nitrogen atmosphere, and polymerization was performed for 4 hours. Went. Thereafter, the solvent was removed under reduced pressure, and then coarsely pulverized to 2 mm or less with a hammer mill to obtain toner binder resin A.
Toner binder resin A 154 parts Carbon black (CB2) 18 parts (MA-100 [Mitsubishi Chemical Corporation])
Hydrocarbon wax 24.7 parts (Fischer-Tropsch wax; HNP-51, maximum endothermic peak = 78 ° C.)
Polar resin 2 1.5 parts (styrene-2-ethylhexyl acrylate copolymer containing 5% 2-acrylamido-2-methylpropanesulfonic acid, Tg = 81 ° C.)
-Azo compound 23 1.8 parts The materials of the above formulation were mixed well with a Henschel mixer and then kneaded with a biaxial kneader set at a temperature of 130 ° C. The obtained kneaded product was cooled and coarsely pulverized to 2 mm or less with a hammer mill to obtain a coarsely pulverized product.
The obtained coarsely pulverized product was crushed to a weight average particle size of 100 μm using an ACM10 manufactured by Hosokawa Micron Co., Ltd. Used and pulverized. Thereafter, the resulting finely pulverized product was subjected to coarse particle classification using a turboplex 100ATP manufactured by Hosokawa Micron Corporation to obtain toner particles.
To 100 parts by mass of the toner particles, 1.5 parts by mass (number average primary particle size: 10 nm) of hydrophobic silica fine powder surface-treated with hexamethyldisilazane is added, and 300 by a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). A mixing step was performed for 2 seconds to obtain Bk toner 13. Table 5 shows the Bk toner 13.

<Example of production of Bk toner 14>
A Bk toner 14 was obtained in the same manner as the Bk toner 13 except that the azo compound 23 in the production example of the Bk toner 13 was changed to the azo compound 19. Table 5 shows the Bk toner 14.

<Example of production of Bk toner 15>
[Method for Producing Toner Binder Resin B1]
Propylene oxide modified bisphenol A (2 mol adduct) 20 parts Propylene oxide modified bisphenol A (3 mol adduct) 80 parts Terephthalic acid 20 parts Isophthalic acid 20 parts Trimellitic acid 1 part Tetrabutoxy titanium 30 parts The above materials were put into a reaction apparatus equipped with a stirrer, a thermometer, and an outflow cooler, and an esterification reaction was performed at 190 ° C. Thereafter, the system was gradually depressurized while being heated to 220 ° C., and a polycondensation reaction was performed at 150 Pa to obtain a toner binder resin B1.
[Method for Producing Toner Binder Resin B2]
-1,9-nonanediol 120 parts-Sebacic acid 130 parts-Trimellitic acid 1 part-Tetrabutoxytitanium 0.30 parts The esterification reaction was performed at 190 ° C. Thereafter, the system was gradually depressurized while being heated to 220 ° C., and a polycondensation reaction was performed at 150 Pa to obtain a toner binder resin B2.
Bk toner 15 was obtained in the same manner as Bk toner 13 except that the following materials were used in the production method of Bk toner 13.
-Toner binder resin B1 120 parts-Toner binder resin B2 34 parts-Carbon black (CB2) 18 parts (MA-100 [Mitsubishi Chemical Corporation])
Hydrocarbon wax 24.7 parts (Fischer-Tropsch wax; HNP-51, maximum endothermic peak = 78 ° C.)
Polar resin 2 1.5 parts (styrene-2-ethylhexyl acrylate copolymer containing 5% 2-acrylamido-2-methylpropanesulfonic acid, Tg = 81 ° C.)
Azo compound 23 1.8 parts of Bk toner 15 are shown in Table 5.

<Example of production of Bk toner 16>
A Bk toner 16 was obtained in the same manner as the Bk toner 15 except that the azo compound 23 in the production example of the Bk toner 15 was changed to the azo compound 19. Table 5 shows the Bk toner 16.
<Example of production of Bk toner 17>
-Toner binder resin B1 150 parts-Toner binder resin B1 83.5 parts-Carbon black (CB2) 22.5 parts (MA-100 [Mitsubishi Chemical Co., Ltd.])
Hydrocarbon wax 40 parts (Fischer-Tropsch wax; HNP-51, maximum endothermic peak = 78 ° C.)
Polar resin 2 2.5 parts (styrene-2-ethylhexyl acrylate copolymer containing 5% 2-acrylamido-2-methylpropanesulfonic acid, Tg = 81 ° C.)
-Azo compound 23 1.5 parts The above mixture was dispersed for 3 hours using an attritor (manufactured by Mitsui Kinzoku Co., Ltd.) to prepare a dispersion. On the other hand, after adding 225 parts of 0.1M-Na ₃ PO ₄ aqueous solution to 450 parts of ion-exchanged water in a 2 liter four-necked flask equipped with a high-speed stirring device TK-homomixer, the rotational speed of the homomixer was set to 10,000 rpm. Adjust and warm to 65 ° C. Thereafter, 15 parts of 1.0 M CaCl ₂ aqueous solution was gradually added to obtain an aqueous medium containing a calcium phosphate compound.
300 parts of the above dispersion was put into an aqueous medium and granulated at 65 ° C. at a rotation speed of 10,000 rpm for 15 minutes. Thereafter, the high-speed stirrer is changed to a normal propeller stirrer, the rotation speed of the stirrer is maintained at 150 rpm, the internal temperature is raised to 95 ° C. and held for 3 hours, the solvent is removed from the dispersion, and the toner particles Got.
To 100 parts by mass of the toner particles, 1.5 parts by mass (number average primary particle size: 10 nm) of hydrophobic silica fine powder surface-treated with hexamethyldisilazane is added, and 300 by a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). A mixing step was performed for 2 seconds to obtain Bk toner 17. Table 5 shows the Bk toner 17.

<Example of production of Bk toner 18>
A Bk toner 18 was obtained in the same manner as the Bk toner 17 except that the azo compound 23 in the production example of the Bk toner 17 was changed to the azo compound 19. Table 5 shows the Bk toner 18.

<Production Example of Comparative Bk Toner 1>
A comparative Bk toner 1 was obtained in the same manner as in the Bk toner 1 except that no azo compound was added in the production example of the Bk toner 1. The comparative Bk toner 1 is shown in Table 5.
<Production example of comparative Bk toner 2>
A comparative Bk toner 2 was obtained in the same manner as in the Bk toner 13 except that no azo compound was added in the production example of the Bk toner 13. The comparative Bk toner 2 is shown in Table 5.

<Production Example of Comparative Bk Toner 3>
A comparative Bk toner 3 was obtained in the same manner as in the Bk toner 17 except that no azo compound was added in the production example of the Bk toner 17. The comparative Bk toner 3 is shown in Table 5.

<Production example of comparative Bk toners 4 and 5>
Comparative Bk toners 4 and 5 were obtained in the same manner as in the Bk toner 1 except that the azo compound 1 in the production example of the Bk toner 1 was changed to the comparative azo compounds 1 and 2. The comparative Bk toners 4 and 5 are shown in Table 5.

<Production Example of Cyan (Cy) Toner 1>
[Master batch adjustment process]
・ Styrene 261 parts ・ Pigment Blue 15: 3 (PB1) 45 parts (ECB-308 [manufactured by Daiichi Seika Kogyo Co., Ltd.])
・ 4.5 parts of aluminum compound of 3,5-di-tert-butylsalicylic acid [Bontron E88 (manufactured by Orient Chemical Co., Ltd.)]
・ Azo compound 6 4.5 parts The above material was introduced into an attritor (Mitsui Mining Co., Ltd.), and stirred with 200 rpm at 25 ° C. for 300 minutes using zirconia beads (350 parts) with a radius of 2.5 mm. Batch dispersion 1 was prepared.
[Toner composition solution adjusting step]
・ Master batch dispersion 1 147 parts ・ Styrene monomer 45 parts ・ N-butyl acrylate monomer 54 parts ・ Hydrocarbon wax 22.5 parts (Fischer-Tropsch wax; HNP-51, maximum endothermic peak = 78 ° C.)
30 parts of polar resin 1 (copolymer of styrene, methacrylic acid, methyl methacrylate and 2-hydroxyethyl methacrylate, Mw = 14800, Tg = 89 ° C., acid value AV = 22 mgKOH / g, hydroxyl value OHv = 8 mgKOH / g)
Polar resin 2 1.5 parts (styrene-2-ethylhexyl acrylate copolymer containing 5% 2-acrylamido-2-methylpropanesulfonic acid, Tg = 81 ° C.)
The above materials were mixed and heated to 65 ° C., and uniformly dissolved and dispersed at 5,000 rpm for 60 minutes using a TK homomixer (manufactured by Tokushu Kika Kogyo) to obtain a toner composition solution. .
A Cy toner 1 was obtained in the same manner as in the production example of the Bk toner 1 except that the toner composition solution was used. Table 6 shows Cy toner 1.

<Production Example of Cy Toner 2>
Cy toner 2 was obtained in the same manner as Cy toner 1 except that the azo compound 6 in the production example of Cy toner 1 was changed to azo compound 9. Table 6 shows the Cy toner 2.

<Production Example of Comparative Cy Toner 1>
A comparative Cy toner 1 was obtained in the same manner as the Cy toner 1 except that the azo compound 6 was not used in the production example of the Cy toner 1. The comparative Cy toner 1 is shown in Table 6.

<Example of Production of Magenta (Mg) Toner 1>
[Master batch adjustment process]
・ Styrene 228 parts ・ Pigment Red 122 (PR1) 60 parts (Toner Mageta E [manufactured by Clariant)]
・ 6 parts of aluminum compound of 3,5-di-tert-butylsalicylic acid [Bontron E88 (manufactured by Orient Chemical Co., Ltd.)]
・ Azo compound 6 6 parts The above materials were introduced into an attritor (Mitsui Mining Co., Ltd.) and stirred for 300 minutes at 200 rpm and 25 ° C. using zirconia beads (350 parts) with a radius of 2.5 mm to disperse the magenta master batch. Liquid 1 was prepared.
[Toner composition solution adjusting step]
・ Master batch dispersion 1 135 parts ・ Styrene monomer 36 parts ・ N-butyl acrylate monomer 60 parts ・ Hydrocarbon wax 22.5 parts (Fischer-Tropsch wax; HNP-51, maximum endothermic peak = 78 ° C.)
45 parts of polar resin 1 (copolymer of styrene, methacrylic acid, methyl methacrylate and 2-hydroxyethyl methacrylate, Mw = 14800, Tg = 89 ° C., acid value AV = 22 mgKOH / g, hydroxyl value OHv = 8 mgKOH / g)
Polar resin 2 1.5 parts (styrene-2-ethylhexyl acrylate copolymer containing 5% 2-acrylamido-2-methylpropanesulfonic acid, Tg = 81 ° C.)
The above materials were mixed and heated to 65 ° C., and uniformly dissolved and dispersed at 5,000 rpm for 60 minutes using a TK homomixer (manufactured by Tokushu Kika Kogyo) to obtain a toner composition solution. .
An Mg toner 1 was obtained in the same manner as in the production example of the Bk toner 1 except that the toner composition solution was used. Table 6 shows the Mg toner 1.

<Example of production of Mg toner 2>
Pigment Red 122 (PR1) in the production example of Mg Toner 1 was changed to Pigment Red 150 (PR2) [Fuji Fast Carmine 522: Fuji Dye Co., Ltd.], and azo Compound 6 was changed to azo Compound 9. Except for the above, Mg toner 2 was obtained in the same manner as Mg toner 1. Table 6 shows the Mg toner 2.

<Example of production of Mg toner 3>
In the production example of Mg toner 1, 60 parts of Pigment Red 122 (PR1) was changed to 30 parts of Pigment Red 122 (PR1) and 30 parts of Pigment Red 150 (PR2), and azo Compound 6 was replaced with 30 parts of Pigment Red 150 (PR2). Except for the above, Mg toner 3 was obtained in the same manner as Mg toner 1. Table 6 shows the Mg toner 3.

<Production Example of Comparative Mg Toner 1>
A comparative Mg toner 1 was obtained in the same manner as the Mg toner 1 except that no azo compound was used in the production example of the Mg toner 1. The comparative Mg toner 1 is shown in Table 6.

<Production example of comparative Mg toner 2>
A comparative Mg toner 2 was obtained in the same manner as the Mg toner 2 except that no azo compound was used in the production example of the Mg toner 2. The comparative Mg toner 2 is shown in Table 6.

<Production Example of Yellow (Ye) Toner 1>
[Master batch adjustment process]
-Styrene 270 parts-Pigment Yellow 155 (PY1) 40 parts (Toner Yellow 4G [manufactured by Clariant)]
・ 4 parts of aluminum compound of 3,5-ditertiary butylsalicylic acid [Bontron E88 (manufactured by Orient Chemical Co., Ltd.)]
・ Azo compound 6 6 parts The above materials were introduced into an attritor (Mitsui Mining Co., Ltd.), and stirred with 200 rpm at 25 ° C. for 300 minutes using zirconia beads (350 parts) with a radius of 2.5 mm to disperse the yellow masterbatch. Liquid 1 was prepared.
[Toner composition solution adjusting step]
・ Master batch dispersion 1 112.5 parts ・ Styrene monomer 67.5 parts ・ N-butyl acrylate monomer 50.4 parts ・ Hydrocarbon wax 24 parts (Fischer-Tropsch wax; HNP-51, maximum endothermic peak) = 78 ° C)
48 parts of polar resin 1 (copolymer of styrene, methacrylic acid, methyl methacrylate and 2-hydroxyethyl methacrylate, Mw = 14800, Tg = 89 ° C., acid value AV = 22 mgKOH / g, hydroxyl value OHv = 8 mgKOH / g)
2.1 parts of polar resin 2 (styrene-2-ethylhexyl acrylate copolymer containing 5% 2-acrylamido-2-methylpropanesulfonic acid, Tg = 81 ° C.)
-Azo compound 6 1.2 parts The above materials are mixed and heated to 65 ° C, and uniformly dissolved and dispersed at 5,000 rpm for 60 minutes using a TK homomixer (manufactured by Tokushu Kika Kogyo). A toner composition solution was obtained.
A Ye toner 1 was obtained in the same manner as in the production example of the Bk toner 1 except that the toner composition solution was used. Table 6 shows Ye toner 1.

<Example of production of Ye toner 2>
[Master batch adjustment process]
-Styrene 270 parts-Pigment yellow 185 (PY2) 40 parts (Peiotol Yellow D1155 [made by BASF)]
・ 4 parts of aluminum compound of 3,5-ditertiary butylsalicylic acid [Bontron E88 (manufactured by Orient Chemical Co., Ltd.)]
・ Azo compound 9 6 parts The above materials are introduced into an attritor (made by Mitsui Mining Co., Ltd.), and stirred at 200 rpm, 25 ° C. for 300 minutes using zirconia beads (350 parts) with a radius of 2.5 mm, and dispersed in a yellow masterbatch. Liquid 1 was prepared.
[Toner composition solution adjusting step]
・ Master batch dispersion 1 192 parts ・ n-butyl acrylate monomer 52.7 parts ・ Hydrocarbon wax 22.5 parts (Fischer-Tropsch wax; HNP-51, maximum endothermic peak = 78 ° C.)
45 parts of polar resin 1 (copolymer of styrene, methacrylic acid, methyl methacrylate and 2-hydroxyethyl methacrylate, Mw = 14800, Tg = 89 ° C., acid value AV = 22 mgKOH / g, hydroxyl value OHv = 8 mgKOH / g)
2.1 parts of polar resin 2 (styrene-2-ethylhexyl acrylate copolymer containing 5% 2-acrylamido-2-methylpropanesulfonic acid, Tg = 81 ° C.)
The above materials were mixed and heated to 65 ° C., and uniformly dissolved and dispersed at 5,000 rpm for 60 minutes using a TK homomixer (manufactured by Tokushu Kika Kogyo) to obtain a toner composition solution. .
A Ye toner 2 was obtained in the same manner as in the production example of the Bk toner 1 except that the toner composition solution was used. Table 6 shows Ye toner 2.

<Example of production of Ye toner 3>
Ye toner 2 is the same as Ye toner 2 except that Pigment Yellow 185 (PY2) was changed to Pigment Yellow 180 (PY3) [Novoperm Yellow P-HG (manufactured by Clariant)]. 3 was obtained. Table 6 shows Ye toner 3.

<Production Example of Comparative Ye Toner 1>
Comparative Ye toner 1 was obtained in the same manner as Ye toner 1 except that no azo compound was used in the production example of Ye toner 1. The comparative Ye toner 1 is shown in Table 6.

<Production Example of Comparative Ye Toner 2>
Comparative Ye toner 2 was obtained in the same manner as Ye toner 2 except that no azo compound was used in the production example of Ye toner 2. The comparative Ye toner 2 is shown in Table 6.

As for the above toner, the coloring power of the toner, and the charge amount of the toner in a high temperature and high humidity environment (30 ° C./80% Rh) and the charge amount of the toner in a low temperature and low humidity environment (15 ° C./10% RH) The amount (LL environmental charge amount) was measured, and the environmental differences in coloring power, HH charge amount, LL charge amount, and charge amount were evaluated. The evaluation method is shown below.
<Evaluation method of toner coloring power>
A commercially available color laser printer, Satera LBP5050 (manufactured by Canon Inc.) was partially modified for evaluation. In remodeling, the fixing machine was removed and changed so that unfixed images could be output, and the image density could be adjusted by the controller. Furthermore, it has been modified to work even when only one color process cartridge is installed. The toner contained inside was removed from a commercially available cartridge, the interior was cleaned by air blow, and then the test toner (30 g) was filled.
The above cartridge is installed in the printer, and a 1cm x 1cm patch image is output to five points on the upper left, upper right, center, lower left and lower right of the transfer material. The amount of toner on each patch is 0.35g by the controller. It was adjusted to / ^{m 2.} Thereafter, a fixing device was attached, and a fixed image of the patch image was output. The toner coloring power was evaluated based on the image density of the five patch portions of the patch image. For the measurement of the image density, a “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co., Ltd.) was used to measure the relative density with respect to the printout image of the white background portion having an original density of 0.00, and the average of the five patches. The value was calculated. The evaluation criteria are as follows.
LETTER size HP Brochure Paper 150 g and Glossy paper (manufactured by Hewlett-Packard, 150 g / m ² ) were used as the transfer material.
(Evaluation criteria)
A: 1.50 or more B: 1.35 or more and less than 1.50 C: 1.20 or more and less than 1.35 D: less than 1.20

<Evaluation method of toner charge amount>
1.0 g of toner and 19.0 g of carrier (Nippon Imaging Society standard carrier [N-02]) are weighed into a plastic cup, and are used in a high temperature and high humidity environment (30 ° C./80% Rh) and a low temperature and low humidity environment (15 ° C. / (10% Rh) for 3 days to adjust the humidity. The humidity-adjusted toner was sealed in a plastic bottle with a 50 cc lid under each environment.
The plastic bottle was shaken for 1 minute at a speed of 4 reciprocations per second with a shaker (YS-LD: manufactured by Yayoi Co., Ltd.) to obtain a two-component developer.
With respect to the two-component developer, the HH environment (high temperature and high humidity environment) charge amount and the LL environment (low temperature and low humidity environment) charge amount were measured using the apparatus shown in FIG. Further, an environmental difference in the toner charge amount (LL charge amount−HH charge amount) was calculated.
(Measurement method of charge amount)
0.5 g of a two-component developer is put in a metal measuring container 9 having a 500 mesh screen 10 at the bottom, and a metal lid 11 is placed. The total mass of the measurement container 9 at this time is weighed and is defined as Ml (g). Next, it is placed on the suction device 8 (at least the part in contact with the measurement container 9 is an insulator) and suctioned from the suction port 14 to adjust the air volume control valve 13 so that the pressure of the vacuum gauge 12 is 250 mmAq. In this state, suction is performed for 1 minute to remove the toner by suction. The potential of the electrometer 16 at this time is set to V (volt). Here, 15 is a capacitor, and the capacity is C (μF). The mass of the entire measurement container after the suction is weighed and defined as M2 (g). The triboelectric charge amount (mC / kg) of the toner is calculated as follows.
Frictional charge (mC / kg) = (C × V) / (M1-M2)
The environmental difference between the toner charge amount and the toner charge amount under each environment was evaluated based on the following criteria.
[HH environmental charge and LL environmental charge]
A: 50 mC / kg or more and less than 65 mC / kg B: 40 mC / kg or more and less than 50 mC / kg or 65 mC / kg or more and less than 75 mC / kg C: 30 mC / kg or more and less than 40 mC / kg or 75 mC / kg or more and less than 80 mC / kg D: Less than 30 mC / kg or 80 mC / kg or more [Environmental difference in charge amount]
A: Less than 10 mC / kg B: 10 mC / kg or more and less than 15 mC / kg C: 15 mC / kg or more and less than 20 mC / kg D: 20 mC / kg or more

[Example 1]
The above evaluation was performed on Bk toner 1. The Macbeth concentration was 1.60, the HH environmental charge amount was 52 mC / kg, the LL environmental charge amount was 61 mC / kg, and the environmental difference in charge amount was 9 mC / kg. Excellent coloring power and excellent chargeability and charge stability. Table 7 shows the evaluation results.

[Examples 2 to 35]
The above evaluation was performed for Bk toners 2 to 27, Cy toners 1 and 2, Mg toners 1 to 3, and Ye toners 1 to 3. The evaluation results are as shown in Tables 7 and 8.

[Comparative Example 1]
The above evaluation was performed on the comparative Bk toner 1. The Macbeth concentration was 1.15, the HH environmental charge amount was 33 mC / kg, the LL environmental charge amount was 71 mC / kg, and the environmental difference in charge amount was 38 mC / kg. Sufficient performance was not demonstrated with respect to the addition amount of a coloring agent. The HH environment charge amount was not sufficient and the LL environment charge amount was excessive. The environmental difference was large and the charging stability was insufficient. Table 7 shows the evaluation results.

[Comparative Examples 2 to 10]
The above evaluation was performed on the comparative Bk toners 2 to 5, the comparative Cy toners 1 and 2, the comparative Mg toners 1 and 2, and the comparative Ye toners 1 and 2. The evaluation results are as shown in Tables 7 and 8.

  1 reference powder inlet, 2 inclined plate (sample stand), 3 reference powder, 4 tray, 5 insulating plate, 6 electrometer, 7 meter connection terminal, 8 suction machine, 9 measuring container, 10 screen, 11 lid, 12 Vacuum gauge, 13 Air flow control valve, 14 Suction port, 15 Condenser, 16 Electrometer

Claims (13)

A toner containing a binder resin, a pigment and an azo compound,
The azo compound is an azo compound represented by the following formula (1):

[In the general formula (1), any one of R ₁ , R ₂ , and Ar has a structure in which a polymer component is bonded through a single bond or a linking group,
R ₁ represents an alkyl group, a phenyl group, an OR ₄ group or an NR ₅ R ₆ group, and R _{4 to} R ₆ each independently represent a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. When R ₁ is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to R ₁ is an amide group, ester group, urethane group, urea group, alkylene group, phenylene group, -O A divalent linking group selected from the group consisting of —, —NR ₃ — and —NHCH (CH ₂ OH) —, and R ₃ represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group;
R ₂ represents an alkyl group, a phenyl group, an OR ₈ group or an NR ₉ R ₁₀ group, and R _{8 to} R ₁₀ each independently represent a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. When R ₂ is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to R ₂ is an alkylene group, a phenylene group, —O—, —NR ₇ — and —NHCH (CH ₂ OH)-is a divalent linking group selected from the group consisting of-, and R ₇ represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
Ar represents an aryl group, and when Ar is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to Ar is an amide group, an ester group, a urethane group, a urea group, or an alkylene group. , A phenylene group, —O—, —NR ₃ — and —NHCH (CH ₂ OH) —, a divalent linking group selected from the group consisting of R ₃ is a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. Represents.
When the single bond or linking group is bonded to R ₁ , R ₂ , or Ar, it is bonded to a hydrogen atom of R ₁ , R ₂ , or Ar. ]
A toner having a charge amount of 5 μC / g or less in gradient charge measurement using an inclined aluminum plate coated with the azo compound.   When the acid value of the azo compound is AV and the amine value of the azo compound is AmV, the ratio [AmV / AV] of the AmV to AV is 0 or more and 0.50 or less. Item 2. The toner according to Item 1.   3. The toner according to claim 1, wherein a number average molecular weight of the azo compound measured using a size exclusion chromatograph is 3000 or more and 30000 or less.   The toner according to claim 1, wherein the acid value of the azo compound is 30 mg KOH / g or less.   5. The toner according to claim 1, wherein the amine value of the azo compound is 5 mg KOH / g or less. When the binder resin contains a vinyl resin, the polymer component contains a vinyl resin,
The toner according to claim 1, wherein when the binder resin contains a polyester resin, the polymer component contains a polyester resin. The toner according to any one of claims 1 to 6, wherein the azo compound represented by the general formula (1) is an azo compound represented by the following general formula (2).

[In the general formula (2), any one of R ₁ , R ₂ , R _{11 to} R ₁₅ has a structure in which a polymer component is bonded via a single bond or a linking group, and R ₁ and R ₂ , and , R ₁ and R ₂ have the same linking group as that represented by the general formula (1). R _{11 to} R ₁₅ each independently represents a hydrogen atom, a COOR ₁₆ group, or a CONR ₁₇ R ₁₈ group. R _{16 to} R ₁₈ each independently represents a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group. When R _{11 to} R ₁₅ are bonded to the polymer component, they are bonded through a single bond or a linking group, and the linking group bonded to R _{11 to} R ₁₅ is an amide group, an ester group, a urethane group, a urea group, or an alkylene group. , A phenylene group, —O—, —NH—, and —NHCH (CH ₂ OH) —. When the single bond or linking group is bonded to R ₁ , R ₂ , R _{11 to} R ₁₅ , it is bonded to a hydrogen atom of R ₁ , R ₂ , R _{11 to} R ₁₅ . ] 8. The method according to claim 1, wherein R ₂ in the general formula (1) is an NR ₉ R ₁₀ group, R ₉ is a hydrogen atom, and R ₁₀ is a phenyl group. Toner. In the general formula (1), R ₂ is an NR ₉ R ₁₀ group, R ₉ is a hydrogen atom, R ₁₀ is a phenyl group, and the phenyl group is connected to the polymer component via a divalent linking group. The toner according to claim 1, wherein the toner is bonded to the toner. The toner according to claim 7, wherein at least one of R _{11 to} R ₁₅ is a COOR ₁₆ group or a CONR ₁₇ R ₁₈ group. When any one of R ₁ , R ₂ , and Ar is bonded to the polymer component, the bonding group bonded through the linking group and bonded to R ₁ , R ₂ , or Ar is —O— or — The toner according to claim 1, wherein the toner is NH−. The toner according to any one of claims 1 to 11, wherein the azo compound represented by the general formula (1) is an azo compound represented by the following general formula (3).

[In said general formula (3), L represents the bivalent coupling group for couple | bonding with the said polymer component. ] The toner according to any one of claims 1 to 11, wherein the azo compound represented by the general formula (1) is an azo compound represented by the following general formula (4).

[In said general formula (4), L represents the bivalent coupling group for couple | bonding with the said polymer component. ]

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