JP5696937B2 - Toner added with azacalixarene derivative - Google Patents

Description

  The present invention relates to a toner, and an image forming method and an image forming apparatus using the toner.

  In recent years, in the field of electrophotographic image forming technology, higher color full-color image formation has been demanded, and developers have been designed to improve image quality. In order to meet the demand for higher image quality, particularly full-color image quality, toners are increasingly becoming smaller in particle size and are being studied to faithfully reproduce latent images. In order to reduce the particle size, a toner production method using a polymerization method has been proposed as a means for controlling the toner to a desired toner shape and surface structure (for example, Patent Document 1 and Patent Document 1). 2). In the case of the polymerization toner, in addition to controlling the particle size of the toner particles, shape control is possible. In addition, by reducing the particle size together with this, the reproducibility of dots and fine lines can be improved, the pile height (image layer thickness) can be lowered, and higher image quality can be expected. The toner is usually composed of a binder resin, a colorant, a charge control agent, and other additives.

  Conventionally, various charge control agents have been proposed in order to impart good charging characteristics, stability over time, and environmental stability. In this case, since a colored material cannot be used for the charge control agent for full-color toner, a colorless, white, or light-color charge control agent that does not affect the hue must be used.

Examples of such charge control agents include metal complex compounds of salicylic acid derivatives (see Patent Document 3, Patent Document 4, Patent Document 5, and Patent Document 6), aromatic dicarboxylic acid metal salt compounds (see Patent Document 7). In addition, metal complex salt compounds of anthranilic acid derivatives (see Patent Document 8), organoboron compounds (see Patent Document 9 and Patent Document 10), and the like have been proposed.
However, these charge control agents are chromium-containing compounds that are concerned about environmental stability, and have drawbacks such as insufficient durability, insufficient charging effect, and insufficient environmental stability. The charge control agent did not have satisfactory performance.

  On the other hand, as a metal-free charge control agent, a phenol derivative condensate (Patent Document 11) or the like has been proposed, and these may satisfy the performance as a charge control agent, but a higher charge amount is required. In this case, improvement such as changing the main skeleton of the phenol derivative condensate is necessary.

  In addition, in the case of the polymerization toner, the charge control agent derived from the toner material is decomposed or it is difficult to disperse in the toner. Therefore, in many cases, the function as the charge control agent cannot be sufficiently exhibited. There is a problem. Therefore, by using and controlling the charge control agent applicable to the polymerized toner, it is expected that the toner has excellent chargeability, durability, and environmental stability, and is compatible with high image quality by reducing the particle size. A toner that can be used and its related technology have not been provided yet, and it is desired to promptly provide the toner.

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention is a full color image forming method in which toner is excellent in chargeability, charge rise, durability, and environmental stability by controlling and using a charge control agent applicable to polymerization toner. And a full color image forming method and an image forming apparatus using the toner.

但し、前記一般式（Ｉ）において、ｍ及びｎはそれぞれ整数であり、ｍ＋ｎは４〜８である。Ｒ₁は、水素原子、炭素数１〜５のアルキル基または―（ＣＨ₂）_qＣＯＯＲ₁₀（Ｒ₁₀は水素原子又は低級アルキル基を表し、ｑは１〜３の整数を示す）基である。Ｒ₂は、水素原子、ハロゲン原子、枝分かれがあってもよい炭素数１〜１２のアルキル基、アラルキル基、―ＮＯ₂、―ＮＨ₂、―Ｎ（Ｒ₇）₂（Ｒ₇は低級アルキル基）、―ＳＯ₃Ｒ₈（Ｒ₈は水素原子）、フェニル基、アルコキシ基、または―Ｓｉ（ＣＨ₃）₃である。Ｒ₃及びＲ₄は、水素原子、ハロゲン原子、炭素数１〜３のアルキル基、―ＮＨ₂、―Ｎ（Ｒ₉）₂（Ｒ₉は低級アルキル基）である。Ｒ₁₁は、水素原子、炭素数１〜５のアルキル基又は―（ＣＨ₂）_pＣＯＯＲ₂₀（Ｒ₂₀は水素原子又は低級アルキル基を表し、ｐは１〜３の整数を示す）基である。Ｒ₁₂は、水素原子、ハロゲン原子、枝分かれがあってもよい炭素数１〜１２のアルキル基、アラルキル基、―ＮＯ₂、―ＮＨ₂、―Ｎ（Ｒ₁₇）₂（Ｒ₁₇は低級アルキル基）、―ＳＯ₃Ｒ₁₈（Ｒ₁₈は水素原子）、フェニル基、アルコキシ基、又は―Ｓｉ（ＣＨ₃）₃である。Ｒ₁₃及びＲ₁₄は、水素原子、ハロゲン原子、炭素数１〜３のアルキル基、―ＮＨ₂、又は―Ｎ（Ｒ₁₉）₂（Ｒ₁₉は低級アルキル基）である。
＜２＞ 前記トナーが、少なくとも、結着樹脂とアザカリックスアレン誘導体とを含むトナー材料を有機溶媒に溶解又は分散させて前記トナー材料の溶解乃至分散液を調製する溶解乃至分散液調製工程Ａと、前記トナー材料の溶解乃至分散液を水系媒体中に添加し乳化乃至分散させて乳化乃至分散液を調製する乳化乃至分散液調製工程Ｂと、前記乳化乃至分散液から前記有機溶媒を除去する有機溶媒除去工程Ｃと、を含むトナーの製造方法によって製造されるトナーであることを特徴とする前記＜１＞に記載のトナー。
＜３＞ 前記乳化乃至分散液調製工程Ｂにおいて、トナー材料の溶解又は分散液を平均粒子径が５ｎｍ〜５０ｎｍのアニオン性の樹脂微粒子とアニオン性界面活性剤とを含む水系媒体中に添加して乳化乃至分散させて乳化乃至分散液を調製することを特徴とする前記＜２＞に記載のトナー。
＜４＞ 前記アザカリックスアレン誘導体のトナー材料の溶解又は分散液中での平均分散径が、１０ｎｍ〜５００ｎｍであることを特徴とする前記＜２＞又は＜３＞に記載のトナー。
＜５＞ 前記結着樹脂が、ポリエステル系樹脂であることを特徴とする前記＜１＞乃至＜４＞のいずれかに記載のトナー。
＜６＞ 前記トナー材料は、活性水素基含有化合物及び該活性水素基含有化合物と反応可能な変性ポリエステル樹脂を含むことを特徴とする前記＜２＞乃至＜５＞のいずれかに記載のトナー。
＜７＞ 前記トナーのアザカリックスアレン誘導体の含有量が、０．０１質量％〜５．０質量％であることを特徴とする前記＜１＞乃至＜６＞のいずれかに記載のトナー。
＜８＞ 前記トナーの帯電量が、−８０μＣ／ｇ〜−１０μＣ／ｇであることを特徴とする前記＜１＞乃至＜７＞のいずれかに記載のトナー。
＜９＞ 前記トナーの電気抵抗率Ｒ（Ωｃｍ）の常用対数値ＬｏｇＲが、１０．９ＬｏｇΩｃｍ〜１１．４ＬｏｇΩｃｍであることを特徴とする前記＜１＞乃至＜８＞のいずれかに記載のトナー。
＜１０＞ 前記トナーの体積平均粒径／個数平均粒径（Ｄｖ／Ｄｎ）が、１．０５〜１．２５であることを特徴とする前記＜１＞乃至＜９＞のいずれかに記載のトナー。
＜１１＞ 前記トナーの平均円形度が、０．９５０〜０．９９０であることを特徴とする前記＜１＞乃至＜１０＞のいずれかに記載のトナー。
＜１２＞ 電子写真感光体を帯電手段により帯電させる帯電工程と、前記帯電された電子写真感光体上に露光手段により静電潜像を形成する露光工程と、前記静電潜像をトナーにより現像されたトナー像を形成する現像工程と、前記トナー像を一次転写手段により中間転写体上に転写する一次転写工程と、前記中間転写体上に転写されたトナー像を二次転写手段により記録媒体上に転写する二次転写工程と、前記記録媒体上に転写されたトナー像を記録媒体上に定着させる定着工程と、前記一次転写手段によりトナー像を中間転写体上に転写した電子写真感光体の表面に付着している転写残トナーをクリーニングするクリーニング工程と、を含み、前記現像工程におけるトナーが前記＜１＞乃至＜１１＞のいずれかに記載のトナーであることを特徴とするフルカラー画像形成方法。
＜１３＞ 二次転写工程において、トナー像の記録材への転写の線速度は３００ｍｍ／ｓｅｃ〜１０００ｍｍ／ｓｅｃであり、二次転写手段のニップ部での転写時間は０．５ｍｓｅｃ〜２０ｍｓｅｃであることを特徴とする前記＜１２＞に記載のフルカラー画像形成方法。
＜１４＞ タンデム方式の電子写真画像形成プロセスを採用することを特徴とする前記＜１２＞又は＜１３＞に記載のフルカラー画像形成方法。
＜１５＞ 電子写真感光体と、前記電子写真感光体を帯電させる帯電手段と、前記帯電された電子写真感光体上に静電潜像を形成する露光手段と、前記電子写真感光体上に形成された静電潜像をトナーによりトナー像とする現像手段と、前記電子写真感光体上に形成されたトナー像を中間転写体を介して又は介さずに記録材上に転写する転写手段と、前記記録材上に転写されたトナー像を熱及び圧力定着部材により記録材上に定着させる定着手段と、前記転写手段によりトナー像を中間転写体又は記録材上に転写した後の電子写真感光体表面に付着している転写残トナーをクリーニングするクリーニング手段と、を備え、前記トナーが前記＜１＞乃至＜１１＞のいずれかに記載のトナーであることを特徴とする画像形成装置。
＜１６＞ 電子写真感光体と、該電子写真感光体上に形成された静電潜像をトナーを用いてトナー像とする現像手段とを少なくとも有し、画像形成装置本体に着脱可能なプロセスカートリッジであって、前記トナーが、前記＜１＞乃至＜１１＞のいずれかに記載のトナーあることを特徴とするプロセスカートリッジ。 Means for solving the problems are as follows. That is,
<1> A toner comprising at least a binder resin and an azacalixarene derivative, wherein the azacalixarene derivative is a compound represented by the following general formula (I):

However, in the said general formula (I), m and n are integers, respectively, and m + n is 4-8. R ₁ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a — (CH ₂ ) _q COOR ₁₀ (R ₁₀ represents a hydrogen atom or a lower alkyl group, and q represents an integer of 1 to 3). . R ₂ is a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 12 carbon atoms, an aralkyl group, —NO ₂ , —NH ₂ , —N (R ₇ ) ₂ (R ₇ is a lower alkyl group) ), —SO ₃ R ₈ (R ₈ is a hydrogen atom), a phenyl group, an alkoxy group, or —Si (CH ₃ ) ₃ . R ₃ and R ₄ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, —NH ₂ , —N (R ₉ ) ₂ (R ₉ is a lower alkyl group). R ₁₁ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or — (CH ₂ ) _p COOR ₂₀ (R ₂₀ represents a hydrogen atom or a lower alkyl group, and p represents an integer of 1 to 3). . R ₁₂ is a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 12 carbon atoms, an aralkyl group, —NO ₂ , —NH ₂ , —N (R ₁₇ ) ₂ (R ₁₇ is a lower alkyl group) ), —SO ₃ R ₁₈ (R ₁₈ is a hydrogen atom), a phenyl group, an alkoxy group, or —Si (CH ₃ ) ₃ . R ₁₃ and R ₁₄ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, —NH ₂ , or —N (R ₁₉ ) ₂ (R ₁₉ is a lower alkyl group).
<2> Dissolution or dispersion preparation step A in which the toner is prepared by dissolving or dispersing a toner material containing at least a binder resin and an azacalixarene derivative in an organic solvent to prepare a solution or dispersion of the toner material. An emulsion or dispersion preparation step B in which the toner material is dissolved or dispersed in an aqueous medium and emulsified or dispersed to prepare an emulsion or dispersion; and the organic solvent is removed from the emulsion or dispersion. The toner according to <1>, wherein the toner is produced by a toner production method including a solvent removal step C.
<3> In the emulsification or dispersion preparation step B, the toner material solution or dispersion is added to an aqueous medium containing anionic resin fine particles having an average particle diameter of 5 nm to 50 nm and an anionic surfactant. The toner according to <2>, wherein an emulsified or dispersed liquid is prepared by emulsifying or dispersing.
<4> The toner according to <2> or <3>, wherein an average dispersion diameter in a solution or dispersion of the toner material of the azacalixarene derivative is 10 nm to 500 nm.
<5> The toner according to any one of <1> to <4>, wherein the binder resin is a polyester resin.
<6> The toner according to any one of <2> to <5>, wherein the toner material includes an active hydrogen group-containing compound and a modified polyester resin capable of reacting with the active hydrogen group-containing compound.
<7> The toner according to any one of <1> to <6>, wherein the content of the azacalixarene derivative in the toner is 0.01% by mass to 5.0% by mass.
<8> The toner according to any one of <1> to <7>, wherein a charge amount of the toner is −80 μC / g to −10 μC / g.
<9> The toner according to any one of <1> to <8>, wherein the common logarithm LogR of the electrical resistivity R (Ωcm) of the toner is 10.9 LogΩcm to 11.4 LogΩcm.
<10> The volume average particle diameter / number average particle diameter (Dv / Dn) of the toner is 1.05 to 1.25, according to any one of <1> to <9>, toner.
<11> The toner according to any one of <1> to <10>, wherein the toner has an average circularity of 0.950 to 0.990.
<12> A charging step of charging the electrophotographic photosensitive member with a charging unit, an exposure step of forming an electrostatic latent image on the charged electrophotographic photosensitive member with an exposing unit, and developing the electrostatic latent image with toner A developing step for forming the toner image, a primary transfer step for transferring the toner image onto an intermediate transfer member by a primary transfer unit, and a toner image transferred on the intermediate transfer member by a secondary transfer unit A secondary transfer step of transferring the toner image onto the recording medium; a fixing step of fixing the toner image transferred onto the recording medium onto the recording medium; and an electrophotographic photosensitive member having the toner image transferred onto the intermediate transfer member by the primary transfer means. A cleaning process for cleaning residual toner adhering to the surface of the toner, wherein the toner in the development process is the toner according to any one of <1> to <11> A full color image forming method.
<13> In the secondary transfer step, the linear velocity of transfer of the toner image to the recording material is 300 mm / sec to 1000 mm / sec, and the transfer time at the nip portion of the secondary transfer means is 0.5 msec to 20 msec. The full-color image forming method according to <12>, wherein:
<14> The full-color image forming method according to <12> or <13>, wherein a tandem electrophotographic image forming process is employed.
<15> An electrophotographic photosensitive member, a charging means for charging the electrophotographic photosensitive member, an exposure means for forming an electrostatic latent image on the charged electrophotographic photosensitive member, and formed on the electrophotographic photosensitive member. Developing means for converting the electrostatic latent image formed into a toner image with toner; transfer means for transferring the toner image formed on the electrophotographic photosensitive member onto a recording material with or without an intermediate transfer member; Fixing means for fixing the toner image transferred onto the recording material onto the recording material by a heat and pressure fixing member, and an electrophotographic photosensitive member after the toner image is transferred onto the intermediate transfer member or the recording material by the transfer means An image forming apparatus comprising: a cleaning unit that cleans transfer residual toner adhering to a surface, wherein the toner is the toner according to any one of <1> to <11>.
<16> A process cartridge having at least an electrophotographic photosensitive member and a developing unit that uses a toner as an electrostatic latent image formed on the electrophotographic photosensitive member, and is detachable from the main body of the image forming apparatus The process cartridge is characterized in that the toner is the toner according to any one of <1> to <11>.

  According to the present invention, the conventional problems can be solved, the object can be achieved, and in the full-color image forming method, the toner is excellent in toner charging property, charge rising property, durability, and environmental stability. In addition, a full-color image forming method and an image forming apparatus using the toner can be provided.

FIG. 1 is a diagram showing an example of the structure of the toner of the present invention. FIG. 2 is a schematic configuration diagram of an example of a contact-type roller charging device. FIG. 3 is a schematic configuration diagram of an example of a contact-type brush charging device. FIG. 4 is a schematic configuration diagram of an example of a magnetic brush charging device. FIG. 5 is a schematic configuration diagram of an example of a developing device. FIG. 6 is a schematic configuration diagram of an example of the fixing device. FIG. 7 is a diagram illustrating an example of a layer configuration of the fixing belt. FIG. 8 is a schematic configuration diagram of an example of the process cartridge of the present invention. FIG. 9 is a schematic configuration diagram of an example of the image forming apparatus of the present invention. FIG. 10 is a schematic configuration diagram of another example of the image forming apparatus of the present invention.

(toner)
The toner of the present invention is produced by the dissolution or dispersion preparation step A, the emulsification or dispersion preparation step B, and the organic solvent removal step C. In step A, the toner represented by the following general formula (I) (Aza It is preferably obtained by adding a calixarene derivative).

但し、前記一般式（Ｉ）において、ｍ及びｎはそれぞれ整数であり、ｍ＋ｎは４〜８である。Ｒ₁は、水素原子、炭素数１〜５のアルキル基または―（ＣＨ₂）_ｑＣＯＯＲ₁₀（Ｒ₁₀は水素原子又は低級アルキル基を表し、ｑは１〜３の整数を示す）基である。Ｒ₂は、水素原子、ハロゲン原子、枝分かれがあってもよい炭素数１〜１２のアルキル基、アラルキル基、―ＮＯ₂、―ＮＨ₂、―Ｎ（Ｒ₇）₂（Ｒ₇は低級アルキル基）、―ＳＯ₃Ｒ₈（Ｒ₈は水素原子）、フェニル基、アルコキシ基、または―Ｓｉ（ＣＨ₃）₃である。Ｒ₃及びＲ₄は、水素原子、ハロゲン原子、炭素数１〜３のアルキル基、―ＮＨ₂、―Ｎ（Ｒ₉）₂（Ｒ₉は低級アルキル基）である。Ｒ₁₁は、水素原子、炭素数１〜５のアルキル基又は―（ＣＨ₂）_pＣＯＯＲ₂₀（Ｒ₂₀は水素原子又は低級アルキル基を表し、ｐは１〜３の整数を示す）基である。Ｒ₁₂は、水素原子、ハロゲン原子、枝分かれがあってもよい炭素数１〜１２のアルキル基、アラルキル基、―ＮＯ₂、―ＮＨ₂、―Ｎ（Ｒ₁₇）₂（Ｒ₁₇は低級アルキル基）、―ＳＯ₃Ｒ₁₈（Ｒ₁₈は水素原子）、フェニル基、アルコキシ基、又は―Ｓｉ（ＣＨ₃）₃である。Ｒ₁₃及びＲ₁₄は、水素原子、ハロゲン原子、炭素数１〜３のアルキル基、―ＮＨ₂、又は―Ｎ（Ｒ₁₉）₂（Ｒ₁₉は低級アルキル基）である。

However, in the said general formula (I), m and n are integers, respectively, and m + n is 4-8. R ₁ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a — (CH ₂ ) _q COOR ₁₀ (R ₁₀ represents a hydrogen atom or a lower alkyl group, and q represents an integer of 1 to 3). . R ₂ is a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 12 carbon atoms, an aralkyl group, —NO ₂ , —NH ₂ , —N (R ₇ ) ₂ (R ₇ is a lower alkyl group) ), —SO ₃ R ₈ (R ₈ is a hydrogen atom), a phenyl group, an alkoxy group, or —Si (CH ₃ ) ₃ . R ₃ and R ₄ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, —NH ₂ , —N (R ₉ ) ₂ (R ₉ is a lower alkyl group). R ₁₁ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or — (CH ₂ ) _p COOR ₂₀ (R ₂₀ represents a hydrogen atom or a lower alkyl group, and p represents an integer of 1 to 3). . R ₁₂ is a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 12 carbon atoms, an aralkyl group, —NO ₂ , —NH ₂ , —N (R ₁₇ ) ₂ (R ₁₇ is a lower alkyl group) ), —SO ₃ R ₁₈ (R ₁₈ is a hydrogen atom), a phenyl group, an alkoxy group, or —Si (CH ₃ ) ₃ . R ₁₃ and R ₁₄ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, —NH ₂ , or —N (R ₁₉ ) ₂ (R ₁₉ is a lower alkyl group).

<Dissolution or dispersion preparation step A>
In the dissolution or dispersion preparation step A, a toner material containing at least one of a binder resin and a binder resin precursor and the azacalixarene derivative is dissolved or dispersed in an organic solvent to dissolve or disperse the toner material. Is a step of preparing
Examples of the binder resin precursor include a polymer (prepolymer) capable of reacting with an active hydrogen group-containing compound. When the binder resin precursor is used instead of the binder resin, the emulsion or dispersion is used. In the preparation step B, the binder resin derived from the binder resin precursor is obtained by reacting with the active hydrogen group-containing compound.
The toner material is not particularly limited as long as it contains either a binder resin or a binder resin precursor and the azacalixarene derivative, and can be appropriately selected according to the purpose. For example, a colorant, If necessary, examples of other components include a release agent.
The organic solvent is removed in the organic solvent removal step C during or after granulation of the toner in the emulsification or dispersion preparation step B.

-Organic solvent-
The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner material, and can be appropriately selected according to the purpose. However, the toner can be easily removed during granulation or after granulation. In view of the properties, those having a boiling point of less than 150 ° C. are preferred, for example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, Dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like can be used. Further, ester solvents are preferable, and ethyl acetate is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as a compounding quantity of the said organic solvent, Although it can select suitably according to the objective, 40 mass parts-300 mass parts are preferable with respect to 100 mass parts of said toner materials, 60 mass parts-140 mass parts. Mass parts are more preferable, and 80 to 120 parts by mass are particularly preferable.
The toner material may be dissolved or dispersed in the organic solvent by using the binder resin, the active hydrogen group-containing compound, the polymer capable of reacting with the active hydrogen group-containing compound, or the azacalix allene. It can be carried out by dissolving or dispersing a toner material such as a derivative, the release agent, and the colorant.
In the toner material, the component used in the dissolution or dispersion process may include at least one of the binder resin and the binder resin precursor and the azacalixarene derivative. The other components may be added to and mixed in the aqueous medium in the preparation of the aqueous medium in the emulsification or dispersion preparation step, or the dissolution or dispersion of the toner material may be added to the aqueous medium. Further, it may be added to the aqueous medium together with the dissolved or dispersed liquid.

但し、前記一般式（Ｉ）において、ｍ及びｎはそれぞれ整数であり、ｍ＋ｎは４〜８である。Ｒ₁は、水素原子、炭素数１〜５のアルキル基または―（ＣＨ₂）_ｑＣＯＯＲ₁₀（Ｒ₁₀は水素原子又は低級アルキル基を表し、ｑは１〜３の整数を示す）基である。Ｒ₂は、水素原子、ハロゲン原子、枝分かれがあってもよい炭素数１〜１２のアルキル基、アラルキル基、―ＮＯ₂、―ＮＨ₂、―Ｎ（Ｒ₇）₂（Ｒ₇は低級アルキル基）、―ＳＯ₃Ｒ₈（Ｒ₈は水素原子）、フェニル基、アルコキシ基、または―Ｓｉ（ＣＨ₃）₃である。Ｒ₃及びＲ₄は、水素原子、ハロゲン原子、炭素数１〜３のアルキル基、―ＮＨ₂、―Ｎ（Ｒ₉）₂（Ｒ₉は低級アルキル基）である。Ｒ₁₁は、水素原子、炭素数１〜５のアルキル基又は―（ＣＨ₂）_pＣＯＯＲ₂₀（Ｒ₂₀は水素原子又は低級アルキル基を表し、ｐは１〜３の整数を示す）基である。Ｒ₁₂は、水素原子、ハロゲン原子、枝分かれがあってもよい炭素数１〜１２のアルキル基、アラルキル基、―ＮＯ₂、―ＮＨ₂、―Ｎ（Ｒ₁₇）₂（Ｒ₁₇は低級アルキル基）、―ＳＯ₃Ｒ₁₈（Ｒ₁₈は水素原子）、フェニル基、アルコキシ基、又は―Ｓｉ（ＣＨ₃）₃である。Ｒ₁₃及びＲ₁₄は、水素原子、ハロゲン原子、炭素数１〜３のアルキル基、―ＮＨ₂、又は―Ｎ（Ｒ₁₉）₂（Ｒ₁₉は低級アルキル基）である。 -Azacalixarene derivatives-
The azacalixarene derivative is added to the inside of the toner so as to be unevenly distributed in the vicinity of the toner surface without being decomposed into the toner material. The azacalixarene derivative is preferably added for the purpose of imparting charging characteristics to the toner and preferably has high chargeability. Examples of the azacalixarene derivative include compounds represented by the following general formula (I).

However, in the said general formula (I), m and n are integers, respectively, and m + n is 4-8. R ₁ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a — (CH ₂ ) _q COOR ₁₀ (R ₁₀ represents a hydrogen atom or a lower alkyl group, and q represents an integer of 1 to 3). . R ₂ is a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 12 carbon atoms, an aralkyl group, —NO ₂ , —NH ₂ , —N (R ₇ ) ₂ (R ₇ is a lower alkyl group) ), —SO ₃ R ₈ (R ₈ is a hydrogen atom), a phenyl group, an alkoxy group, or —Si (CH ₃ ) ₃ . R ₃ and R ₄ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, —NH ₂ , —N (R ₉ ) ₂ (R ₉ is a lower alkyl group). R ₁₁ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or — (CH ₂ ) _p COOR ₂₀ (R ₂₀ represents a hydrogen atom or a lower alkyl group, and p represents an integer of 1 to 3). . R ₁₂ is a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 12 carbon atoms, an aralkyl group, —NO ₂ , —NH ₂ , —N (R ₁₇ ) ₂ (R ₁₇ is a lower alkyl group) ), —SO ₃ R ₁₈ (R ₁₈ is a hydrogen atom), a phenyl group, an alkoxy group, or —Si (CH ₃ ) ₃ . R ₁₃ and R ₁₄ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, —NH ₂ , or —N (R ₁₉ ) ₂ (R ₁₉ is a lower alkyl group).

R ₁ can be appropriately selected from the above substituents, and among them, hydrogen is preferable.
R ₂ can be appropriately selected from the above substituents, and among them, an alkyl group, a phenyl group, an alkoxy group, and a halogen atom are preferable.
R ₃ can be appropriately selected from the above substituents, and among them, hydrogen is preferable.
R ₄ can be appropriately selected from the above substituents, and among them, hydrogen and a methyl group are preferable.
R ₁₁ can be appropriately selected from the above substituents. Among them, hydrogen is preferable.
R ₁₂ can be appropriately selected from the above substituents, and among them, an alkyl group, a phenyl group, an alkoxy group, and a halogen atom are preferable.
R ₁₃ can be appropriately selected from the above substituents. Among them, hydrogen is preferable.
R ₁₄ can be appropriately selected from the above substituents, and among them, hydrogen and a methyl group are preferable.

  The azacalixarene derivative can be arbitrarily contained in the resin phase in the toner particle body by utilizing the difference in affinity for the resin in the toner particle body. By containing the azacalixarene derivative in the resin phase in the vicinity of the surface of the toner particles, the spent of the charge control agent on other members such as a photoreceptor and a carrier can be suppressed.

  The azacalixarene derivative exhibits a further charge imparting effect by changing the methylene group portion of the normal calixarene derivative to an amino group. That is, by changing the electron-donating methylene group to an electron-withdrawing amino group, electrons existing between the toner and the carrier generated by frictional charging between the carrier and the toner are more fully converted into the calixarene derivative. Since it is stored, a high charging effect can be exhibited.

  The dispersion diameter of the azacalixarene derivative in the dissolution or dispersion prepared in the dissolution or dispersion preparation step A is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 nm to 500 nm. 100 nm to 500 nm is more preferable, and 150 nm or less is particularly preferable. If the dispersion diameter is less than 10 nm, the azacalixarene derivative is remarkably unevenly distributed on the toner surface, and the toner becomes atypical, which may cause an excessive charge amount. Moreover, there is a possibility that the charge imparting effect cannot be obtained sufficiently. When the dispersion diameter exceeds 500 nm, when the toner and the carrier are agitated, the azacalixarene derivative moves to the carrier and the carrier is contaminated, which may reduce the charge amount.

The dispersion diameter of the azacalixarene derivative can be measured, for example, by the following method. That is, 1 g of toner is immersed in 100 g of chloroform for 10 hours, and azacalixarene derivative dispersion at 5,500 rpm (9,545 g) using a centrifuge (H-9R manufactured by Kokusan Co., Ltd., LN angle rotor). Centrifuge. Azacalixarene derivative particles are present in the centrifuged supernatant. The particle size is measured using “LA-920” (manufactured by Horiba, Ltd.). In the measurement of LA-920, analysis is performed using the LA-920 dedicated application (Ver3.32) (manufactured by Horiba, Ltd.). Specifically, LA-920 is measured by adjusting the optical axis with chloroform and then measuring the background. Thereafter, circulation is started and the azacalixarene derivative dispersion liquid is dropped. After confirming that the transmittance is stable, an ultrasonic wave is irradiated under the following conditions. The dispersion particle diameter is measured under the condition that the transmittance value is in the range of 70% to 95% after irradiation. It is important that the measurement with the measuring device “LA-920” is performed under the condition that the transmittance value is in the range of 70% to 95% from the viewpoint of measurement reproducibility of the particle diameter. In addition, if the transmittance deviates from the above value after ultrasonic irradiation, it is necessary to perform measurement again. In order to obtain the transmittance value, it is necessary to adjust the dripping amount of the dispersion.
The measurement and analysis conditions are set as follows.
Data acquisition count: 15 times Relative refractive index: 1.20
Circulation: 5
Ultrasonic intensity: 7
The measurement method is to measure the dispersion diameter in the azacalixarene derivative contained in the manufactured toner. The azacalixarene derivative is not decomposed by the toner material and is contained in the toner. Therefore, the dispersion diameter according to the measurement can be applied as the dispersion diameter of the azacalixarene derivative in the dissolution or dispersion adjusted in the dissolution or dispersion preparation step A.

  The presence state of the azacalixarene derivative in the toner can be observed as follows. That is, the toner particles are exposed to the vapor of an aqueous ruthenium oxide solution, dyed for 3 minutes, left in the atmosphere for 30 minutes, and then embedded with a curable epoxy resin for 30 minutes. Next, using an ultramicrotome, a diamond knife (Ultra Sonic 35) is cut at a cutting thickness of 80 nm and a cutting speed of 0.4 mm / sec. Next, the section is fixed on the collodion membrane mesh, and observation by a bright field method can be performed with JEM-2100F (TEM manufactured by JEOL Ltd.) under the conditions of an acceleration voltage of 200 kV, SpotSize3, CL AP1, and OL AP3.

  There is no restriction | limiting in particular as the addition amount of the said azacalixarene derivative, Although it can select suitably according to the objective, 0.01 mass part-5.0 mass parts are preferable with respect to 100 mass parts of toner. If the amount of the azacalixarene derivative is less than 0.01 parts by mass, the deforming effect may not be sufficiently obtained. If the amount is more than 5.0 parts by mass, the chargeability of the toner increases. In other words, the effect of the main charge control agent may be reduced, and the electrostatic attraction force with the developing roller may increase, leading to a decrease in developer fluidity and a decrease in image density. Further, the surface properties of the toner are deteriorated, the carrier is contaminated, and sufficient chargeability cannot be maintained over a long period of time, and further, environmental stability may be hindered.

-Binder resin and binder resin precursor-
The binder resin is not particularly limited and can be appropriately selected according to the purpose. For example, polyester resin, silicone resin, styrene / acryl resin, styrene resin, acrylic resin, epoxy resin, diene resin, Examples thereof include phenol resin, terpene resin, coumarin resin, amideimide resin, butyral resin, urethane resin, and ethylene / vinyl acetate resin. Among these, polyester resins having sufficient flexibility even when the molecular weight is lowered are preferable in that they can be melted sharply during fixing and the image surface can be smoothed. When the polyester resin is used, another resin may be used in combination.

The polyester resin is one or more polyols represented by the following general formula (2),
A- (OH) r (2)
However, in said general formula (2), A represents either C1-C20 alkyl group, an alkylene group, the aromatic group which may have a substituent, and a heterocyclic aromatic group. r represents an integer of 2 to 4.
What polyesterified 1 type, or 2 or more types of polycarboxylic acid represented by following General formula (3) is preferable.
B- (COOH) s (3)
However, in said general formula (3), B represents either a C1-C20 alkyl group, an alkylene group, the aromatic group which may have a substituent, and a heterocyclic aromatic group. s represents an integer of 2 to 4.

  Specific polyols represented by the general formula (2) include, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neo Pentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1 , 2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycero 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct, hydrogenated bisphenol A propylene oxide adduct and the like.

  Specific examples of the polycarboxylic acid represented by the general formula (3) include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and adipic acid. , Sebacic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isooctyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, iso Octenyl succinic acid, isooctyl succinic acid, 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1, 2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecar Xipropane, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empole trimer acid, etc., cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid , Butanetetracarboxylic acid, diphenylsulfonetetracarboxylic acid, ethylene glycol bis (trimellitic acid), and the like.

  There is no restriction | limiting in particular as addition amount of the said binder resin, Although it can select suitably according to the objective, 1 mass part-25 mass parts are preferable with respect to 100 mass parts of said organic solvent dispersion liquids. If the binder resin is less than 1 part by mass, the dispersion diameter of the azacalixarene derivative may not be reduced. If the binder resin exceeds 25 parts by mass, aggregation occurs when added to the solution or dispersion of the toner material. Occurring, there is a possibility that the deforming and charge imparting effects cannot be obtained sufficiently. The organic solvent dispersion preferably contains 3 to 10 parts by mass of the azacalixarene derivative and 3 to 10 parts by mass of the binder resin with respect to 100 parts by mass of the organic solvent dispersion.

-Active hydrogen group-containing compound-
By including an active hydrogen group-containing compound and a modified polyester resin capable of reacting with the compound in the toner material, the mechanical strength of the resulting toner is increased, and the burying of the external additive can be suppressed. Further, the fluidity of the toner during heat fixing can be adjusted, and the fixing temperature range can be widened. In the present specification, the active hydrogen group-containing compound and the modified polyester resin capable of reacting with the active hydrogen group-containing compound correspond to a binder resin precursor.

  The active hydrogen group-containing compound is used as an extender, a crosslinking agent, etc. when the polymer capable of reacting with the active hydrogen group-containing compound undergoes an extension reaction, a crosslinking reaction, etc. in the aqueous medium in the emulsification or dispersion preparation step. Works. The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected according to the purpose. For example, a polymer capable of reacting with the active hydrogen group-containing compound is an isocyanate group. In the case of the containing polyester prepolymer (A), the amines (B) are preferable because they can have a high molecular weight by a reaction such as an elongation reaction or a crosslinking reaction with the isocyanate group-containing polyester prepolymer (A).

  The active hydrogen group is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected according to the purpose. Examples thereof include a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), amino group, carboxyl group, mercapto group. Groups, etc. can be used. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as said amine (B), According to the objective, it can select suitably, For example, diamine (B1), trivalent or more polyamine (B2), amino alcohol (B3), amino mercaptan ( B4), amino acids (B5), amino acids blocked in (B1) to (B5) (B6), and the like can be used. These may be used individually by 1 type and may use 2 or more types together. Among these, diamine (B1), a mixture of diamine (B1) and a small amount of a trivalent or higher polyamine (B2) is preferable.

Examples of the diamine (B1) include aromatic diamines, alicyclic diamines, and aliphatic diamines.
Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, and the like.
Examples of the alicyclic diamine include 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine.
Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.

Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.

  Examples of (B6) in which the amino group in (B1) to (B5) is blocked include (B6) a ketimine compound obtained from any of B1 to B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) And oxazolyzone compounds.

  In order to stop the elongation reaction, the crosslinking reaction, etc. between the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound, it is preferable to use a reaction terminator. When the reaction terminator is used, the molecular weight and the like of the adhesive substrate can be controlled within a desired range. There is no restriction | limiting in particular as said reaction terminator, For example, monoamine (diethylamine, dibutylamine, butylamine, laurylamine etc.), what blocked these (ketimine compound) etc. can be used.

The mixing ratio of the amines (B) and the isocyanate group-containing polyester prepolymer (A) is not particularly limited, but the isocyanate group [NCO] in the isocyanate group-containing prepolymer (A), The mixing equivalent ratio ([NCO] / [NHx]) of amino groups [NHx] in the amines (B) is preferably 1/3 to 3/1, and preferably 1/2 to 2/1. Is more preferable, and it is particularly preferable that the ratio is 1 / 1.5 to 1.5 / 1.
If the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may be reduced. If it exceeds 3/1, the molecular weight of the urea-modified polyester resin is reduced. Hot offset resistance may deteriorate.

--Polymer capable of reacting with active hydrogen group-containing compound--
The polymer capable of reacting with the active hydrogen group-containing compound (hereinafter referred to as “prepolymer”) is not particularly limited as long as it has at least a site capable of reacting with the active hydrogen group-containing compound. For example, a polyol resin, a polyacrylic resin, a polyester resin, an epoxy resin, or a derivative resin thereof can be used. Among these, a polyester resin is preferable in terms of high fluidity and transparency at the time of melting. In addition, these may be used individually by 1 type and may use 2 or more types together.

The site capable of reacting with the active hydrogen group-containing compound in the prepolymer is not particularly limited and may be appropriately selected from known substituents. For example, an isocyanate group, an epoxy group, a carboxylic acid, an acid A chloride group etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, an isocyanate group is preferable.
Among the prepolymers, it is easy to adjust the molecular weight of the polymer component, and oil-less low-temperature fixing characteristics in dry toners, in particular, good releasability and fixing even in the absence of a release oil coating mechanism for a heating medium for fixing. From the viewpoint of ensuring the properties, a urea bond-forming group-containing polyester resin (RMPE) containing a urea bond-forming group is preferable.

As said urea bond production | generation group, an isocyanate group etc. are mentioned, for example.
When the urea bond generating group in the urea bond generating group-containing polyester resin (RMPE) is the isocyanate group, the polyester resin (RMPE) is preferably an isocyanate group-containing polyester prepolymer (A) or the like.
The isocyanate group-containing polyester prepolymer (A) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC), In addition, there may be mentioned those obtained by reacting an active hydrogen group-containing polyester resin with polyisocyanate (PIC).
There is no restriction | limiting in particular as said polyol (PO), According to the objective, it can select suitably, For example, diol (DIO), trihydric or more polyol (TO), diol (DIO), and trihydric or more polyol And a mixture with (TO). These may be used individually by 1 type and may use 2 or more types together. Among these, diol (DIO) alone or a mixture of diol (DIO) and a small amount of trivalent or higher polyol (TO) is preferable.

Examples of the diol (DIO) include alkylene glycol, alkylene ether glycol, alicyclic diol, alkylene oxide adduct of alicyclic diol, bisphenol, alkylene oxide adduct of bisphenol, and the like.
The alkylene glycol is preferably one having 2 to 12 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol and the like. Can be mentioned.
Examples of the alkylene ether glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and the like.
Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.
Examples of the alkylene oxide adduct of the alicyclic diol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the alicyclic diol.
Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S.
Examples of the alkylene oxide adduct of the bisphenol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, and butylene oxide to the bisphenol.
Among these, alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols, and the like are preferable. Mixtures are particularly preferred.

The trivalent or higher polyol (TO) is preferably 3 to 8 or higher, for example, a trivalent or higher polyhydric aliphatic alcohol, a trivalent or higher polyphenol, a trivalent or higher polyphenol. And alkylene oxide adducts.
Examples of the trihydric or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like.
Examples of the trihydric or higher polyphenols include trisphenol bodies (such as Trisphenol PA manufactured by Honshu Chemical Industry Co., Ltd.), phenol novolacs, and cresol novolacs.
Examples of the alkylene oxide adduct of trihydric or higher polyphenols include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to trihydric or higher polyphenols.

  The mixing mass ratio (DIO: TO) of the diol (DIO) and the trihydric or higher polyol (TO) in the mixture of the diol (DIO) and the trihydric or higher polyol (TO) is 100: 0.01. To 10 is preferable, and 100: 0.01 to 1 is more preferable.

  There is no restriction | limiting in particular as said polycarboxylic acid (PC), Although it can select suitably according to the objective, For example, dicarboxylic acid (DIC), trivalent or more polycarboxylic acid (TC), dicarboxylic acid (DIC) ) And a tri- or higher valent polycarboxylic acid. These may be used individually by 1 type and may use 2 or more types together. Among these, dicarboxylic acid (DIC) alone or a mixture of dicarboxylic acid (DIC) and a small amount of trivalent or higher polycarboxylic acid (TC) is preferable.

Examples of the dicarboxylic acid (DIC) include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, and aromatic dicarboxylic acid.
Examples of the alkylene dicarboxylic acid include succinic acid, adipic acid, and sebacic acid.
As said alkenylene dicarboxylic acid, a C4-C20 thing is preferable, For example, a maleic acid, a fumaric acid, etc. are mentioned.
As said aromatic dicarboxylic acid, a C8-C20 thing is preferable, For example, a phthalic acid, an isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned.
Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable.

The trivalent or higher polycarboxylic acid (TC) is preferably 3 to 8 or higher, and examples thereof include aromatic polycarboxylic acids.
The aromatic polycarboxylic acid preferably has 9 to 20 carbon atoms, and examples thereof include trimellitic acid and pyromellitic acid.

The polycarboxylic acid (PC) is selected from dicarboxylic acid (DIC), trivalent or higher polycarboxylic acid (TC), and a mixture of dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid. Any acid anhydride or lower alkyl ester can also be used.
Examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.

  As a mixing mass ratio (DIC: TC) of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) in the mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC), There is no restriction | limiting in particular, According to the objective, it can select suitably, For example, 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

  The mixing ratio for the polycondensation reaction between the polyol (PO) and the polycarboxylic acid (PC) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the polyol (PO) The equivalent ratio ([OH] / [COOH]) of the hydroxyl group [OH] and the carboxyl group [COOH] in the polycarboxylic acid (PC) is preferably 2/1 to 1/1, and 1.5 / The ratio is more preferably 1-1 / 1, and particularly preferably 1.3 / 1-1.02 / 1.

  There is no restriction | limiting in particular as content in the isocyanate group containing polyester prepolymer (A) of the said polyol (PO), Although it can select suitably according to the objective, For example, 0.5 mass%-40 mass% are Preferably, 1% by mass to 30% by mass is more preferable, and 2% by mass to 20% by mass is particularly preferable. When the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner, and exceeds 40% by mass. In some cases, the low-temperature fixability may deteriorate.

There is no restriction | limiting in particular as said polyisocyanate (PIC), According to the objective, it can select suitably, For example, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurates And those blocked with these phenol derivatives, oxime, caprolactam and the like.
Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, Examples include tetramethylhexane diisocyanate.
Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate.
Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3- Examples thereof include methyldiphenylmethane-4,4′-diisocyanate, diphenyl ether-4,4′-diisocyanate and the like.
Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate.
Examples of the isocyanurates include tris-isocyanatoalkyl-isocyanurate, triisocyanatocycloalkyl-isocyanurate, and the like.
These may be used alone or in combination of two or more.

  The mixing ratio for reacting the polyisocyanate (PIC) with the active hydrogen group-containing polyester resin (for example, a hydroxyl group-containing polyester resin) is the isocyanate group [NCO] in the polyisocyanate (PIC) and the hydroxyl group-containing polyester. The mixing equivalent ratio ([NCO] / [OH]) with the hydroxyl group [OH] in the resin is preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1. Particularly preferred is 3/1 to 1.5 / 1. When the isocyanate group [NCO] exceeds 5, low-temperature fixability may be deteriorated, and when it is less than 1, offset resistance may be deteriorated.

  There is no restriction | limiting in particular as content in the isocyanate group containing polyester prepolymer (A) of the said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, 0.5 mass%-40 mass% Is preferable, 1% by mass to 30% by mass is more preferable, and 2% by mass to 20% by mass is particularly preferable. When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. When the content exceeds 40% by mass, Low temperature fixability may deteriorate.

  The average number of isocyanate groups contained per molecule of the isocyanate group-containing polyester prepolymer (A) is not particularly limited, but is preferably 1 or more, more preferably 1.2 to 5, and more preferably 1.5 to 4 Is more preferable. When the average number of the isocyanate groups is less than 1, the molecular weight of the polyester resin (RMPE) modified with a urea bond-forming group is lowered, and the hot offset resistance may be deteriorated.

  Although there is no restriction | limiting in particular as a weight average molecular weight (Mw) of the polymer (prepolymer) which can react with the said active hydrogen group containing compound, Molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF) 3,000 to 40,000 is preferable, and 4,000 to 30,000 is more preferable. When the weight average molecular weight (Mw) is less than 3,000, the heat resistant storage stability may be deteriorated, and when it exceeds 40,000, the low temperature fixability may be deteriorated.

The measurement of the molecular weight distribution by the gel permeation chromatography (GPC) can be performed, for example, as follows. That is, first, the column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) was flowed at this temperature as a column solvent at a flow rate of 1 ml / min to prepare a sample concentration of 0.05 to 0.6% by mass. Measurement is performed by injecting 50 to 200 μl of a tetrahydrofuran sample solution of the resin. In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve prepared by several monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, Pressure Chemical Co. Alternatively, Toyo Soda Kogyo's molecular weight is 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6. It is preferable to use those of × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ and use at least about 10 standard polystyrene samples. An RI (refractive index) detector can be used as the detector.

The binder resin is an adhesive that shows adhesion to a recording material such as paper, and is obtained by reacting the active hydrogen group-containing compound with a polymer capable of reacting with the active hydrogen group-containing compound in an aqueous medium. It preferably contains an adhesive polymer.
There is no restriction | limiting in particular as a weight average molecular weight of the said binder resin, Although it can select suitably according to the objective, 3,000 or more are preferable, 5,000-1,000,000 are more preferable, 7, 000 to 500,000 is particularly preferred. When the weight average molecular weight is less than 3,000, the hot offset resistance may be deteriorated.

There is no restriction | limiting in particular as glass transition temperature (Tg) of the said binder resin, Although it can select suitably according to the objective, For example, 30 to 70 degreeC is preferable and 40 to 65 degreeC is more preferable.
When the glass transition temperature (Tg) is less than 30 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability may not be sufficient. In the toner, since a polyester resin subjected to a crosslinking reaction and an elongation reaction coexists, the toner exhibits good storage stability even when the glass transition temperature is low as compared with the conventional polyester toner.

The glass transition point (Tg) is specifically determined by the following procedure. Measurement is performed under the following measurement conditions using TA-60WS and DSC-60 manufactured by Shimadzu Corporation.
Measurement conditions Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50 mL / min)
Temperature conditions Starting temperature: 20 ° C
Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
Holding time: None Temperature drop: 10 ° C / min
End temperature: 20 ° C
Holding time: None Temperature increase rate: 10 ° C / min
End temperature: 150 ° C

  The measurement result is analyzed using the data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation. The analysis method specifies a range of ± 5 ° C around the point showing the maximum peak on the lowest temperature side of the DrDSC curve, which is the DSC differential curve of the second temperature rise, and uses the peak analysis function of the analysis software to specify the peak temperature Ask for. Next, the maximum endothermic temperature of the DSC curve is determined using the peak analysis function of the analysis software in the range of the peak temperature + 5 ° C. and −5 ° C. in the DSC curve. The temperature shown here corresponds to the Tg of the toner.

Hereinafter, more specific production examples of the binder resin and the binder resin precursor will be described.
There is no restriction | limiting in particular as said binder resin, Although it can select suitably according to the objective, A polyester-type resin is especially suitable.
There is no restriction | limiting in particular as said polyester-type resin, Although it can select suitably according to the objective, For example, a urea modified polyester resin and an unmodified polyester resin are mentioned as a particularly suitable thing.
The urea-modified polyester resin comprises an amine (B) as an active hydrogen group-containing compound and an isocyanate group-containing polyester prepolymer (A) as a polymer that can react with the active hydrogen group-containing compound in an aqueous medium. It is obtained by reacting with
The urea-modified polyester resin may include a urethane bond in addition to the urea bond. In this case, the content molar ratio of the urea bond and the urethane bond (urea bond / urethane bond) is not particularly limited and may be appropriately selected depending on the intended purpose, but is 100/0 to 10/90. Preferably, 80/20 to 20/80 is more preferable, and 60/40 to 30/70 is particularly preferable. This is because when the urea bond is less than 10, the hot offset resistance may be deteriorated.

Preferable specific examples of the urea-modified polyester resin and the unmodified polyester resin include the following. That is,
(1) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate and uread with isophorone diamine, bisphenol A ethylene oxide 2 mol adduct and isophthalic acid It is a mixture with a polycondensate.
(2) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2-mole adduct and isophthalic acid with isophorone diisocyanate and uread with isophorone diamine, bisphenol A ethylene oxide 2-mole adduct and terephthalic acid It is a mixture with a polycondensate.
(3) A bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and a polyester prepolymer obtained by reacting a polycondensate of terephthalic acid with isophorone diisocyanate and urethanized with isophorone diamine, and bisphenol A ethylene It is a mixture of oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate.
(4) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate, and bisphenol A propylene It is a mixture of an oxide 2 mol adduct and a polycondensate of terephthalic acid.
(5) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2-mole adduct and terephthalic acid with isophorone diisocyanate and uread with hexamethylenediamine, bisphenol A ethylene oxide 2-mole adduct, and terephthalate It is a mixture with an acid polycondensate.

(6) Polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate and uread with hexamethylenediamine, and bisphenol A ethylene oxide 2 mol adduct / bisphenol A Mixture of propylene oxide 2 mol adduct and polycondensate of terephthalic acid (7) Polyester prepolymer obtained by reacting bisphenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate with isophorone diisocyanate was ureaated with ethylenediamine And a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid.
(8) Polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with diphenylmethane diisocyanate, and urethanized with hexamethylenediamine, bisphenol A ethylene oxide 2 mol adduct and isophthalic acid It is a mixture with the polycondensate.
(9) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride with diphenylmethane diisocyanate was uread with hexamethylenediamine. And a polycondensate of bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid.
(10) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with toluene diisocyanate and uread with hexamethylenediamine, bisphenol A ethylene oxide 2 mol adduct and isophthalic acid It is a mixture with the polycondensate.

As a method for producing the urea-modified polyester resin, for example,
(1) A solution or dispersion of the toner material containing a polymer (for example, an isocyanate group-containing polyester prepolymer (A)) capable of reacting with an active hydrogen group-containing compound is used as the active hydrogen group-containing compound (for example, amines). (B)) and emulsifying or dispersing in the aqueous medium to form oil droplets, and then subjecting both to an extension reaction or a crosslinking reaction in the aqueous medium,
(2) The solution or dispersion of the toner material is emulsified or dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance to form oil droplets, and both are subjected to extension reaction or crosslinking in the aqueous medium. How to react,
(3) After the toner material solution or dispersion is added and mixed in the aqueous medium, the active hydrogen group-containing compound is added to form oil droplets. And a method of subjecting to elongation reaction or crosslinking reaction.
In the case of (3), the modified polyester resin is preferentially produced on the surface of the toner to be produced, and it becomes possible to provide a concentration gradient on the toner particles.

  The reaction conditions for producing the binder resin by emulsification or dispersion are not particularly limited, and are appropriately selected according to the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. can do. In addition, as reaction time, 10 minutes-40 hours are preferable, and 2 hours-24 hours are more preferable.

  In the aqueous medium, as a method for stably forming a dispersion containing a polymer capable of reacting with the active hydrogen group-containing compound (for example, an isocyanate group-containing polyester prepolymer (A)), for example, in the aqueous medium In addition, a toner such as a polymer that can react with the active hydrogen group-containing compound (for example, an isocyanate group-containing polyester prepolymer (A)), the colorant, the mold release agent, the charge control agent, and the unmodified polyester resin. Examples thereof include a method in which a solution or dispersion of a toner material prepared by dissolving or dispersing the material in an organic solvent is added and dispersed by shearing force.

  In the emulsification or dispersion, the amount of the aqueous medium used is preferably 50 parts by mass to 2,000 parts by mass, and more preferably 100 parts by mass to 1,000 parts by mass with respect to 100 parts by mass of the toner material. When the amount used is less than 50 parts by mass, the toner material is poorly dispersed, and toner particles having a predetermined particle diameter may not be obtained. When the amount exceeds 2,000 parts by mass, the production cost increases.

-Other ingredients-
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a coloring agent, a mold release agent, an inorganic fine particle, a fluid improvement agent, a cleaning property improvement agent, a magnetic material, metal soap , Etc.

--Colorant--
The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pogment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include degreen lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and litbon. These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as content in the toner of the said coloring agent, Although it can select suitably according to the objective, 1 mass%-15 mass% are preferable, and 3 mass%-10 mass% are more preferable.
When the content of the colorant is less than 1% by mass, a reduction in the coloring power of the toner is observed. When the content exceeds 15% by mass, poor dispersion of the pigment in the toner occurs, and the coloring power decreases. In some cases, the electrical characteristics of the toner may be degraded.

The colorant may be used as a resin composite master batch.
The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, polyester, styrene or a polymer thereof, a styrene copolymer, polymethyl methacrylate, poly Butyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic ring Aromatic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene, poly p-chlorostyrene, polyvinyl toluene, and the like. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene N-acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymers and the like.

The masterbatch can be produced by mixing or kneading the resin for the masterbatch and the colorant with a high shear force. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin.
The so-called flushing method is also suitable in that the wet cake of the colorant can be used as it is, and it does not need to be dried. This flushing method is a method in which an aqueous paste containing water of a colorant is mixed or kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used. The colorant can be optionally contained in both the first resin phase and the second resin phase by utilizing the difference in affinity for the two resins. It is well known that the colorant deteriorates the charging performance of the toner when it is present on the toner surface. Therefore, the charging performance (environmental stability, charge retention ability, charge amount, etc.) of the toner can be improved by selectively incorporating a colorant into the first resin phase present in the inner layer.

--- Mold release agent--
There is no restriction | limiting in particular as said mold release agent, Although it can select suitably according to the objective, Melting | fusing point has a low melting point mold release agent of 50 to 120 degreeC.
The low melting point release agent, when dispersed with the resin, effectively works between the fixing roller and the toner interface as the release agent, thereby oilless (the release roller such as oil is used in the fixing roller). Even if no agent is applied), the hot offset property is good.

Suitable examples of the mold release agent include waxes and waxes.
Examples of the waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; paraffin, And natural waxes such as petroleum waxes such as microcrystalline and petrolatum. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax; synthetic waxes such as esters, ketones and ethers; Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbons; poly-n-stearyl methacrylate and poly-n-lauryl which are low molecular weight crystalline polymer resins A homopolymer or copolymer of a polyacrylate such as methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.); a crystalline polymer having a long alkyl group in the side chain, or the like may be used. These may be used alone or in combination of two or more.

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 50 to 120 degreeC is preferable and 60 to 90 degreeC is more preferable. If the melting point is less than 50 ° C., the wax may adversely affect the heat-resistant storage stability, and if it exceeds 120 ° C., a cold offset may easily occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 cps to 1000 cps, more preferably 10 cps to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the wax. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1,000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.
There is no restriction | limiting in particular as content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 0 mass%-40 mass% are preferable, and 3 mass%-30 mass% are more preferable. . When the content exceeds 40% by mass, the fluidity of the toner may be deteriorated.

  The mold release agent utilizes the difference in affinity between two resins to make a toner core portion (first resin phase) composed of polyester resin and a toner shell portion (second resin phase) composed of resin fine particles. In any of the resin phases). When it is selectively contained in the second resin phase present in the toner outer layer, the release agent oozes out sufficiently even in a short heating time at the time of fixing, so that sufficient releasability can be obtained. Further, by selectively containing the release agent in the first resin phase present in the inner layer, it is possible to suppress the spent of the release agent to other members such as a photoreceptor and a carrier.

--Inorganic fine particles--
The inorganic fine particles are used as an external additive for imparting fluidity, developability, chargeability and the like to the toner particles.
The inorganic fine particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanate Strontium, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, carbonized Examples thereof include silicon and silicon nitride. These may be used individually by 1 type and may use 2 or more types together.

As the inorganic fine particles for assisting the fluidity, developability and chargeability of the toner, in addition to the large inorganic particles having a primary average particle size of 80 nm to 500 nm, small inorganic particles are preferable. Can be used.
The inorganic fine particles having a small particle diameter are preferably hydrophobic silica and / or hydrophobic titanium oxide.
The primary average particle diameter of the small inorganic particles is preferably 5 nm to 50 nm, more preferably 10 nm to 30 nm.
The BET specific surface area of the inorganic fine particles is not particularly limited, 20m ² / g~500m ² / g are preferred.
As a compounding quantity of the said inorganic fine particle, 0.01 mass%-5 mass% are preferable, and 0.01 mass%-2.0 mass% are more preferable.

--- Fluidity improver ---
The fluidity improver is an agent having a function of surface treatment to increase hydrophobicity and to prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, silylated Agents, silane coupling agents having a fluoroalkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like.
Silica and titanium oxide in the inorganic fine particles are preferably subjected to surface treatment with such a fluidity improver and used as hydrophobic silica and hydrophobic titanium oxide.

--- Cleanability improver--
The cleaning property improving agent is added to the toner in order to remove the developer after transfer remaining on the photoreceptor and the primary transfer medium.
Examples of the cleaning property improver include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles.
The polymer fine particles preferably have a relatively narrow particle size distribution, and the volume average particle size of the polymer fine particles is preferably 0.01 μm to 1 μm.

--- Magnetic material ---
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite etc. can be used. Among these, white is preferable in terms of color tone.

<Emulsification or dispersion preparation step B>
In the emulsification or dispersion preparation step B, the dissolution or dispersion is added to an aqueous medium and emulsified or dispersed to prepare an emulsification or dispersion.

A method for emulsifying or dispersing the solution or dispersion of the toner material in the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferable to disperse with stirring.
There is no restriction | limiting in particular as said dispersion | distribution method, According to the objective, it can select suitably, For example, it can carry out using a well-known disperser etc.
The disperser is not particularly limited, and examples thereof include a low speed shear disperser and a high speed shear disperser.
In the emulsification or dispersion, when the active hydrogen group-containing compound and a polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound are subjected to an extension reaction or a cross-linking reaction, an adhesive substrate (binder resin) Produces.

-Aqueous medium-
There is no restriction | limiting in particular as said aqueous medium, It can select suitably from well-known things, For example, water, a solvent miscible with water, these mixtures etc. can be used, Among these, water Is preferred.
The solvent miscible with water is not particularly limited as long as it is miscible with water. For example, alcohols, dimethylformamide, tetrahydrofuran, cellosolves, lower ketones, and the like can be used.
Examples of the alcohols include methanol, isopropanol, and ethylene glycol.
Examples of the lower ketones include acetone and methyl ethyl ketone.
These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as an aqueous medium in the said emulsification thru | or dispersion liquid preparation process B, Although it can select suitably according to the objective, It is preferable that anionic resin microparticles | fine-particles and an anionic surfactant are included.

In this case, the aqueous medium is preferably prepared by, for example, dispersing the anionic resin fine particles in an aqueous medium in the presence of the anionic surfactant.
There is no restriction | limiting in particular as addition amount with respect to the aqueous medium of the said anionic surfactant and the said anionic resin fine particle, According to the objective, it can select suitably, For example, 0.5 mass%-10 mass%, respectively. preferable.

--Anionic resin fine particles--
The anionic resin fine particles adhere to the toner surface, and are fused and fused to form a relatively hard surface. Further, since the anionic resin fine particles have an anionic property, they have an effect of adsorbing to the droplets containing the toner material and suppressing coalescence of the droplets, and are important for controlling the particle size distribution of the toner. Furthermore, the negative chargeability of the toner can be given. In order to exhibit these effects, the anionic resin fine particles have an average particle diameter of preferably 5 nm to 50 nm, more preferably 10 nm to 25 nm.
The average particle diameter corresponds to the average particle diameter of primary particles of anionic resin fine particles, and the average particle diameter of the primary particles can be measured by SEM, TEM, light scattering method, etc., for example, Horiba by laser scattering measurement method With LA-920 manufactured by Seisakusho, measurement can be performed by diluting to an appropriate concentration so as to fall within the measurement range.
The average particle diameter of the primary particles is obtained as a volume average diameter.

The resin for the anionic resin fine particles is not particularly limited as long as it can form an aqueous dispersion in the aqueous medium, and can be appropriately selected from known resins according to the purpose.
The resin is not particularly limited and may be a thermoplastic resin or a thermosetting resin. For example, a vinyl resin, a polyurethane resin, an epoxy resin, a polyester resin, a polyamide resin, a polyimide resin, a silicon resin, a phenol resin, Melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin, and the like can be used. These may be used individually by 1 type and may use 2 or more types together. Among these, at least one selected from vinyl resins, polyurethane resins, epoxy resins, and polyester resins is preferable because an aqueous dispersion of fine spherical resin fine particles can be easily obtained.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic acid ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.

The anionic resin fine particles are required to be anionic. This is because they are not aggregated when used together with the anionic surfactant shown above.
The anionic resin fine particles can be prepared by using an anionic activator by a production method described later or by introducing an anionic group such as a carboxylic acid group or a sulfonic acid group into the resin.

There is no restriction | limiting in particular as a preparation method of the said anionic resin fine particle, According to the objective, it can select suitably, The method of making it superpose | polymerize by a well-known polymerization method, The method of obtaining as an aqueous dispersion of resin fine particles is mentioned. Among these, a method of obtaining an aqueous dispersion of resin fine particles is preferable.
As a method for preparing the aqueous dispersion of resin fine particles, for example, the following method is preferable. That is,
(1) In the case of vinyl resin, aqueous dispersion of resin fine particles A directly by a polymerization reaction selected from a suspension polymerization method, an emulsion polymerization method, a seed polymerization method and a dispersion polymerization method using a vinyl monomer as a starting material This is a method for producing a liquid.
(2) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer, etc.) or a solvent solution thereof was dispersed in an aqueous medium in the presence of an appropriate dispersant. Then, it is a method for producing an aqueous dispersion of resin fine particles A by heating or adding a curing agent to cure.
(3) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., precursor (monomer, oligomer, etc.) or solvent solution thereof (preferably liquid. It may be liquefied by heating) In this method, a suitable emulsifier is dissolved therein, and then water is added to perform phase inversion emulsification.
(4) Resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) After the resin fine particles are obtained by pulverizing using, and then classified, they are dispersed in water in the presence of an appropriate dispersant.
(5) A spray of a resin solution prepared by previously dissolving a resin prepared in a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent. In this method, after the resin fine particles are obtained, the resin fine particles are dispersed in water in the presence of an appropriate dispersant.
(6) A poor solvent is added to a resin solution in which a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. Or by precipitating resin fine particles by cooling a resin solution previously dissolved in a solvent by heating, and then removing the solvent to obtain resin fine particles. Then, the resin fine particles are dispersed in water in the presence of an appropriate dispersant. It is a method to make it.
(7) A resin solution prepared by previously dissolving a resin prepared by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent is appropriately dispersed. In this method, the solvent is removed by heating or decompression after being dispersed in an aqueous medium in the presence of an agent.
(8) A suitable emulsifier in a resin solution in which a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. Is dissolved, and then water is added to perform phase inversion emulsification.

-Anionic surfactant-
The anionic surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, and the like, and fluoroalkyl groups Preferable examples include anionic surfactants having Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [ω-fluoroalkyl (having 6 to 6 carbon atoms). 11) Sodium oxy] -1-alkyl (C3-4) sulfonate, sodium 3- [ω-fluoroalkanoyl (C6-8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl ( Carbon number 11-20) carboxylic acid or metal salt thereof, perfluoroalkyl carboxylic acid (carbon number 7-13) or metal salt thereof, perfluoroalkyl (carbon number 4-12) sulfonic acid or metal salt thereof, perfluorooctane Sulfonic acid diethanolamide, N-propyl-N- (2-hydroxyethyl) par -Fluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number 6-6) 16) Ethyl phosphate, sodium dodecyl diphenyl ether disulfonate, and the like.

  As a commercial item of the anionic surfactant which has the said fluoroalkyl group, for example, Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC-129 (manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191, F-812, F-833 (Manufactured by Dainippon Ink Co., Ltd.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); Neos), etc.

In a toner obtained using an aqueous medium containing the anionic resin fine particles having an average particle diameter of 5 nm to 50 nm and the anionic surfactant, a toner material mainly composed of the colorant and the binder resin is used. The anionic resin fine particles adhere to the surface of the toner particle body as a nucleus.
The average particle size of the toner is prepared by emulsification or dispersion conditions such as stirring of the aqueous medium in the emulsification or dispersion preparation step B.

  The average particle diameter measured as the volume average particle diameter of the toner is not particularly limited, but is preferably 1 μm to 6 μm, and more preferably 2 μm to 5 μm. When the volume average particle diameter is less than 1 μm, toner dust is likely to occur in primary transfer and secondary transfer. When the volume average particle diameter exceeds 6 μm, dot reproducibility becomes insufficient, and the graininess of the halftone portion deteriorates and increases. Fine images may not be obtained.

  In addition to the anionic surfactant and the resin fine particles, the following inorganic compound dispersant and polymer protective colloid can be used in combination in the aqueous medium. Examples of the dispersant for the hardly water-soluble inorganic compound include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.

The polymer protective colloid is not particularly limited, and examples thereof include acids, (meth) acrylic monomers containing hydroxyl groups, vinyl alcohol or vinyl alcohol ether compounds, compounds containing vinyl alcohol and carboxyl groups. Esters, amide compounds or their methylol compounds, chlorides, homopolymers or copolymers such as those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, celluloses, and the like.
Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like.
Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerin monoacrylate, Examples thereof include glycerin monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide and the like.

Examples of the vinyl alcohol or the vinyl alcohol ether compound include vinyl methyl ether, vinyl ethyl ether, and vinyl propyl ether.
Examples of the esters of the compound containing vinyl alcohol and a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate.
Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, and these methylol compounds.
Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride.
Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine.
Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester.
Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

  When using a dispersion stabilizer that is soluble in acids and alkalis such as calcium phosphate, remove the calcium phosphate from the fine particles by dissolving the calcium phosphate with an acid such as hydrochloric acid and then washing with water or decomposing with an enzyme. It becomes possible to do.

<Organic solvent removal step C>
The organic solvent removing step C is a step of removing the organic solvent from the emulsified or dispersed liquid (emulsified slurry).
The method for removing the organic solvent is not particularly limited and may be appropriately selected according to the purpose. (1) The temperature of the entire reaction system is gradually raised to completely evaporate the organic solvent in the oil droplets. (2) A method in which the emulsified dispersion is sprayed in a dry atmosphere to completely remove the water-insoluble organic solvent in the oil droplets to form toner fine particles, and the aqueous dispersant is removed by evaporation. Etc.
When the organic solvent is removed, toner particles are formed. The formed toner particles are washed, dried, etc., and then classified as desired. The classification is performed, for example, by removing fine particle portions in a liquid by a cyclone, a decanter, centrifugation, or the like. The classification operation may be performed after obtaining the powder after drying.

The toner particles thus obtained are mixed with particles such as a colorant, a release agent, and a charge control agent, and further, a mechanical impact force is applied to the particles such as a release agent from the surface of the toner particles. Can be prevented from desorbing.
As the method for applying the mechanical impact force, for example, a method in which an impact force is applied to the mixture by blades rotating at a high speed, a mixture is introduced into a high-speed air stream and accelerated to appropriately collide particles or composite particles. The method of making it collide with a board is mentioned.
As an apparatus used for this method, for example, an ong mill (manufactured by Hosokawa Micron Co., Ltd.), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) and a pulverization air pressure are lowered, and a hybridization system (Nara Machinery Co., Ltd.) Co., Ltd.), Kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

<Toner characteristics>
The toner produced by the above steps has the following toner characteristics.
The average circularity of the toner is not particularly limited as long as it is 0.950 to 0.990, and can be appropriately selected according to the purpose. If the average circularity is less than 0.950, the image uniformity during development deteriorates, and the toner transfer efficiency from the electrophotographic photosensitive member to the intermediate transfer member or from the intermediate transfer member to the recording material decreases, resulting in uniform transfer. May not be obtained. If the average circularity exceeds 0.990, there is a possibility that the toner will rub through the cleaning blade, resulting in poor cleaning. Further, the toner is produced by emulsification in an aqueous medium, and such a production method is particularly suitable for reducing the particle size of color toner and obtaining the shape having the average circularity. It is effective.

  The average circularity of the toner is defined by an average circularity X = (peripheral length of a circle having the same area as the particle projection area / perimeter length of the particle projection image) × 100%. The average circularity can be measured by the following method. That is, it can be measured using a flow type particle image analyzer (“FPIA-2100”; manufactured by Sysmex Corporation) and can be performed using analysis software (FPIA-2100 Data Processing Program For FPIA Version 00-10). More specifically, 0.1% to 0.5 mL of 10% by weight surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku) is added to a 100 mL glass beaker, and 0.1 g of each toner is added. Add ~ 0.5 g, stir with microspatel, then add 80 ml of ion-exchanged water. The obtained dispersion is subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). The shape and distribution of the toner are measured by setting the concentration of the dispersion to 5,000 to 15,000 / μL using the FPIA-2100. In this measurement method, it is important that the concentration of the dispersion is 5,000 to 15,000 / μL from the viewpoint of measurement reproducibility of the average circularity. It is necessary to prepare by changing the amount of surfactant and the amount of toner to which the dispersion conditions for obtaining the dispersion concentration are added. The required amount of the surfactant varies depending on the degree of hydrophobicity of the toner, and if it is added in a large amount, noise due to bubbles is generated. If the amount is too small, the toner cannot be sufficiently wetted, so that the dispersion becomes insufficient. Further, the amount of the toner added varies depending on the toner particle size, and it is necessary to decrease the small particle size and increase the large particle size. When the toner particle size is 3 μm to 7 μm, the concentration of the dispersion can be adjusted to 5,000 to 15,000 / μL by setting the amount of toner added to 0.1 g to 0.5 g. Become.

  In the present invention, the charge amount of the toner is a charge amount Q obtained by stirring and mixing with carrier particles at a toner concentration of 7 mass% for 600 seconds, and is −10 μC / g to −80 μC / g. preferable. More preferably, it is −60 μC / g to −30 μC / g. If the absolute value of the charge amount Q is less than 10 μC / g, the adsorptive power with the magnetic carrier is low, and the amount of toner developed even with a low development electric field increases, so that a high-quality image with gradation is obtained. It may not be obtained. In addition, the amount of reversely charged toner increases, and the amount of toner developed on a white background portion is large, so that the image quality may deteriorate due to ground fogging. If the absolute value of the charge amount Q exceeds 80 μC / g, the attractive force with the magnetic carrier increases, and the amount of toner to be developed is small, and the image density may be lowered.

  The charge amount of the toner can be measured using a V blow-off device (manufactured by Ricoh Creative Development Co., Ltd.). The toner and the carrier are left as a developer having a toner concentration of 7% by mass in an environment of a temperature of 25 ° C. and a humidity of 40% for 2 hours. From 6 g of the initial agent mixed with stirring for 2 seconds, 1 g of developer is weighed, and the toner charge amount distribution is measured by a single mode method using a V blow-off device (manufactured by Ricoh Creative Development Co., Ltd.). When blowing, 635 mesh is used. The single mode method is the above-described V blow-off device (manufactured by Ricoh Creative Development Co., Ltd.), which selects the single mode according to the device manual, and the measurement conditions are 5 mm in height, suction 100, and double blow. It is.

  The ratio (Dv / Dn) between the volume average particle diameter (Dv) and the number average particle diameter (Dn) in the toner is not particularly limited and may be appropriately selected depending on the intended purpose. Is preferable, and 1.05-1.25 is more preferable. When the (Dv / Dn) is less than 1.05, in the two-component developer, the toner is fused to the surface of the carrier during long-term agitation in the developing device, and the charging ability of the carrier is lowered or the cleaning property is deteriorated. It is easy to connect to. In the case of a one-component developer, toner filming on the developing roller and toner fusion to a member such as a blade are likely to occur because the toner is thinned. When (Dv / Dn) exceeds 1.25, it becomes difficult to obtain a high-resolution and high-quality image, and the toner particle diameter varies when the balance of the toner in the developer is performed. May increase. In addition, since the toner charge amount distribution is wide, it is difficult to obtain a high-quality image. On the other hand, by setting the (Dv / Dn) to 1.25 or less, the charge amount distribution becomes uniform, and the background fog can be reduced. Further, when the ratio is (Dv / Dn) 1.05 to 1.25, the toner is easily excellent in all of storage stability, low-temperature fixability, and hot offset resistance. In particular, when used in a full-color copying machine, the glossiness of the image is excellent. Even if the toner balance over a long period of time is achieved with a two-component developer, the toner particle diameter in the developer is less likely to fluctuate, and good and stable developability can be obtained even with long-term agitation in the developing device. With toner balance, the fluctuation of the toner particle size is reduced, and there is no toner filming on the developing roller or toner fusion to a member such as a blade for thinning the toner. Good and stable developability can be obtained even during long-term use (stirring) of the apparatus, and high-quality images can be obtained.

  The volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner can be measured by the following methods. That is, it can be measured with a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.) with an aperture diameter of 100 μm and measured with analysis software (Beckman Coulter Multisizer 3 Version 3.51). More specifically, 0.5 mL of 10% by weight surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 mL glass beaker, 0.5 g of toner is added, and microspatel is used. Stir and then add 80 mL of ion exchanged water. The obtained dispersion is subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion is measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter) as the measurement solution. The measurement is performed by dropping the toner sample dispersion so that the concentration indicated by the apparatus is 8 ± 2%. In this measurement method, it is important that the density is 8 ± 2% from the viewpoint of the measurement reproducibility of the toner particle diameter. Within this concentration range, no error occurs in the particle size.

As the BET specific surface area of the toner is preferably 0.5m ² /g~4.0m ² / g, more preferably 0.5m ² /g~2.0m ² / g. When the BET specific surface area is less than 0.5 m ² / g, the entire toner surface is covered tightly, and the resin fine particles inhibit the adhesion between the binder resin component inside the toner and the fixing paper, and the fixing lower limit There is an increase in temperature. Further, the resin fine particles hinder the seepage of the wax, the wax releasability effect cannot be obtained, and offset may occur. When the BET specific surface area exceeds 4.0 m ² / g, the toner surface The organic fine particles remaining on the surface protrude greatly as convex portions, or the resin fine particles remain as a coarse multilayer, and the resin fine particles inhibit the adhesion between the binder resin component inside the toner and the fixing paper, and the minimum fixing temperature An increase is seen. In addition, the resin fine particles hinder the seepage of the wax, the wax releasability effect cannot be obtained, and the occurrence of offset may be observed. Further, the additive is raised, and the image quality is likely to be affected by the unevenness of the surface.

The common logarithm LogR of the electrical resistivity R (Ωcm) of the toner is preferably 10.9 LogΩcm to 11.4 LogΩcm. When the common logarithmic value LogR of the electrical resistivity R (Ωcm) of the toner is less than 10.9 LogΩcm, the conductivity becomes high, which leads to a poor charging and a tendency to increase dirt and toner scattering. If it exceeds 11.4 Log Ωcm, the resistance increases, the charge amount increases, and the image density may decrease.
The common logarithm value LogR of the electrical resistivity R of the toner was measured by first preparing a measurement sample in which 3 g of toner was molded into a pellet of about 2 mm thickness, and using this as a SE-70 type solid electrode (Ando Electric ( LogR when a 1 kHz alternating current is applied between the electrodes, TR-10C type dielectric loss measuring device, WBG-9 oscillator, BDA-9 equilibrium point detector (all are Ando Electric) It is possible to determine the LogR of the toner.

  FIG. 1 shows an outline of the toner structure of the present invention. As shown in FIG. 1, the toner 1 includes base particles 2 made of a toner material containing an azacalix curene derivative, and an external additive 3 that assists the fluidity, developability, and chargeability of the colored toner particles. The external additive 3 is formed on the outermost surface of the base particle 2. The toner structure is not limited to the structure shown in FIG. 1. For example, the toner structure may be deformed using a deforming agent.

<Developer>
The toner can be used as a two-component developer together with a carrier.
Although there is no restriction | limiting in particular as a weight average particle diameter of the said carrier, It is preferable that it is 15 micrometers-40 micrometers.
When the weight average particle size is less than 15 μm, carrier adhesion that causes the carrier to be transferred together in the transfer step is likely to occur. When the toner concentration is increased, there is a possibility that background stains are likely to occur. In addition, when the dot diameter of the latent image is small, the variation in dot reproducibility increases, and the graininess of the highlight portion may be deteriorated.

The developer is not particularly limited as long as it has the toner, and can be appropriately selected according to the purpose, and may further have a carrier component, for example, a one-component developer composed of the toner, the toner And a two-component developer composed of a carrier.
It is preferable to use a two-component developer in a high-speed printer or the like corresponding to the recent improvement in information processing speed from the viewpoint of improving the service life. Such a developer can be used in various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. When the developer is used as a one-component developer, even if the balance of the toner is performed, there is little fluctuation in the particle size of the toner, such as a filming of the toner on the developing roller and a blade for thinning the toner. The toner can be prevented from being fused to the member, and good and stable developability can be obtained even in the long-term use (stirring) of the developing device. In addition, when the developer is used as a two-component developer, even if the toner balance is maintained over a long period of time, there is little fluctuation in the particle size of the toner, and good and stable developability even with long-term stirring in the developing device. Is obtained.

  There is no restriction | limiting in particular as content of the carrier in the said two-component developer, Although it can select suitably according to the objective, It is preferable that it is 90 mass%-98 mass%, and 93 mass%-97 mass%. % Is more preferable. When the content of the carrier is in the more preferable range, it is advantageous in terms of development stability.

There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.
There is no restriction | limiting in particular as a material of the said core material, According to the objective, it can select suitably, For example, a manganese-strontium (Mn-Sr) type material of 50 emu / g-90 emu / g, manganese-magnesium (Mn -Mg) type material etc. are mentioned, 1 type may be used individually and 2 or more types may be used together. The core material is preferably a highly magnetized material such as iron powder (100 emu / g or more), magnetite (75 to 120 emu / g) in terms of ensuring image density. Further, as a core material, a copper-zinc (Cu-Zn) system (30 emu / g to 80 emu) is advantageous in that it can weaken the contact with the photoconductor in which the toner is in a spiked state and is advantageous in improving the image quality. / G) and the like are preferred.

There is no restriction | limiting in particular as a volume average particle diameter (D50) of the said core material, Although it can select suitably according to the objective, 10 micrometers-150 micrometers are preferable, and 20 micrometers-80 micrometers are more preferable.
When the D50 is less than 10 μm, fine particles increase in the particle size distribution of the carrier, so the magnetization per particle may decrease and carrier scattering may occur. When the D50 exceeds 150 μm, the carrier ratio The surface area may decrease and toner scattering may occur. As a result, the reproducibility of the solid portion may be deteriorated particularly in a full color with many solid portions.
When the content of the carrier is in the more preferable range, it is advantageous in terms of development stability.

  The material for the resin layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, polyester resins, and polycarbonate resins. , Polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride And fluoroterpolymers such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, and silicone resins. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as said amino-type resin, According to the objective, it can select suitably, For example, urea-formaldehyde resin, a melamine resin, a benzoguanamine resin, a urea resin, a polyamide resin, an epoxy resin etc. are mentioned.

  There is no restriction | limiting in particular as said polyvinyl-type resin, According to the objective, it can select suitably, For example, an acrylic resin, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral etc. are mentioned.

  There is no restriction | limiting in particular as said polystyrene resin, According to the objective, it can select suitably, For example, a polystyrene, a styrene-acryl copolymer, etc. are mentioned.

  There is no restriction | limiting in particular as said halogenated olefin resin, According to the objective, it can select suitably, For example, a polyvinyl chloride etc. are mentioned.

  The polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyethylene terephthalate and polybutylene terephthalate.

The resin layer may contain conductive powder or the like as necessary.
There is no restriction | limiting in particular as a material of the said electrically-conductive powder, According to the objective, it can select suitably, For example, a metal, carbon black, a titanium oxide, a tin oxide, a zinc oxide etc. are mentioned.
There is no restriction | limiting in particular as an average particle diameter of the said electrically-conductive powder, Although it can select suitably according to the objective, 1 micrometer or less is preferable. If the average particle size exceeds 1 μm, it may be difficult to control the electrical resistance.

The resin layer is formed, for example, by preparing a coating solution by dissolving a silicone resin or the like in a solvent, and then applying the coating solution to the surface of the core material by a known coating method, followed by drying and baking. be able to.
There is no restriction | limiting in particular as said application | coating method, According to the objective, it can select suitably, For example, the dipping method, the spray method, the brush coating method etc. are mentioned.
Moreover, there is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cersol butyl acetate etc. are mentioned.
Furthermore, the baking method is not particularly limited and may be appropriately selected depending on the purpose. Either an external heating method or an internal heating method may be used. Examples include a furnace, a rotary electric furnace, a burner furnace, and a method using a microwave.

  There is no restriction | limiting in particular as content of the resin layer in the said carrier, Although it can select suitably according to the objective, 0.01 mass%-5.0 mass% are preferable. When the content is less than 0.01% by mass, a uniform resin layer may not be formed on the surface of the core material. When the content exceeds 5.0% by mass, the resin layer becomes too thick and the carriers are combined. Granulation may occur and a uniform carrier may not be obtained.

The characteristics of the carrier can be measured by the following method.
<Weight average particle size>
The weight average particle diameter Dw of the carrier is calculated based on the particle diameter distribution (relationship between the number frequency and the particle diameter) of the particles measured on the basis of the number. The weight average particle diameter Dw in this case is represented by the formula (1).
Dw = {1 / Σ (nD ³ )} × {Σ (nD ⁴ )} (1)
In formula (1), D represents the representative particle size (μm) of the particles present in each channel, and n represents the total number of particles present in each channel. The channel indicates a length for equally dividing the particle size range in the particle size distribution diagram, and 2 μm is adopted in the present invention. In addition, as the representative particle size of the particles present in each channel, the lower limit value of the particle size of the particles stored in each channel was adopted.

The number average particle diameter Dp of the carrier and the core particles of the carrier is calculated based on the particle diameter distribution of the particles measured on the basis of the number. The number average particle diameter Dp in this case is represented by the formula (2).
Dp = (1 / ΣN) × (ΣnD) (2)
In formula (2), N represents the total number of particles measured, n represents the total number of particles present in each channel, and D represents the lower limit of the particle size of the particles stored in each channel (2 μm). Show.

As a particle size analyzer for measuring the particle size distribution, a microtrack particle size analyzer model HRA9320-X100 (manufactured by Honeywell) can be used. The measurement conditions are as follows.
[1] Particle size range: 8 to 100 μm
[2] Channel length (channel width): 2 μm
[3] Number of channels: 46
[4] Refractive index: 2.42

(Image forming method)
The image forming method of the present invention includes a charging step for charging an electrophotographic photosensitive member, an exposure step for forming an electrostatic latent image on the charged electrophotographic photosensitive member, and an electron on which the electrostatic latent image is formed. A development step for developing a toner image by using the toner of the present invention on a photographic photoreceptor, and a primary transfer step for primary transfer of the toner image formed on the electrophotographic photoreceptor onto an intermediate transfer member; A secondary transfer step of secondarily transferring the toner image transferred onto the intermediate transfer member onto the recording material, and the toner image transferred onto the recording material onto the recording material by fixing means including a heat and pressure fixing member. A fixing step of fixing the toner image on the surface of the electrophotographic photosensitive member having the toner image transferred onto the intermediate transfer member by the primary transfer unit, and a cleaning step of cleaning the transfer residual toner adhering to the surface of the electrophotographic photosensitive member.
The image forming method is not particularly limited and may be appropriately selected depending on the intended purpose, but is suitable as a full color image forming method.
The linear speed of transfer of the toner image onto the recording material in the secondary transfer process, so-called printing speed, is not particularly limited and can be appropriately selected according to the purpose, but is 300 mm / sec to 1,000 mm / sec. The transfer time in the secondary transfer step is preferably 0.5 msec to 20 msec. The transfer time indicates a transfer time at a nip portion of a transfer roller used for secondary transfer.

The image forming method is not particularly limited and may be appropriately selected according to the purpose. However, the charging process, the exposure process, the developing process, the primary transfer process, and the secondary transfer process are performed for one image formation. It is preferable that a plurality of image forming processes including a fixing process and a cleaning process are simultaneously performed by a tandem method.
In the tandem method, a plurality of the electrophotographic photosensitive members are provided, and one color is developed at each rotation.
According to the tandem image forming process, the charging process, the exposing process, the developing process, and the transferring process are performed for each color to form a toner image of each color. The difference from the full-color image forming speed is small, and there is an advantage that it can cope with high-speed printing.

In general, in a tandem image forming method, a toner image of each color is formed on a separate electrophotographic photosensitive member, and a full color image is formed by stacking (color superposition) of each color toner layer. If there are variations in characteristics, such as different chargeability, the difference in the development toner amount due to the toner particles of each color will occur, the change in the hue of the secondary color due to color superposition will increase, and the color reproducibility will deteriorate. is there. Stabilize the amount of developing toner to control the balance of each color (no variation among toner particles of each color), and uniform adhesion to the electrophotographic photosensitive member and recording material among toner particles of each color is necessary.
In this regard, according to the image forming method using the toner of the present invention in the developing step, the charging characteristics are uniform, there is no variation among the toner particles of each color, and the electrophotographic photosensitive member and the recording material between the toner particles of each color. Therefore, the advantages of the tandem image forming method can be fully exhibited.

In the charging step, although there is no particular limitation, it is preferable to apply a DC voltage on which at least an alternating voltage is superimposed. By applying a DC voltage on which the alternating voltage is superimposed, the surface voltage of the electrophotographic photosensitive member can be stabilized to a desired value as compared with the case where only the DC voltage is applied, so that it is more uniformly charged. Is possible.
The charging step is not particularly limited, but it is preferable to perform charging by bringing a charging member into contact with the electrophotographic photosensitive member and applying a voltage to the charging member. A charging member is brought into contact with the electrophotographic photosensitive member, and charging is performed by applying a voltage to the charging member, thereby particularly improving the uniform charging effect obtained by applying a DC voltage superimposed with the alternating voltage. It becomes possible to make it.

  The fixing step is not particularly limited, and includes a heating roller made of magnetic metal and heated by electromagnetic induction, a fixing roller arranged in parallel with the heating roller, the heating roller and the fixing roller. A heating belt as an endless belt-like toner heating medium that is stretched and heated by the heating roller and rotated by the heating roller and the fixing roller, and is pressed against the fixing roller via the heating belt It is preferable that the fixing unit includes a pressure roller that rotates in the forward direction with respect to the heating belt to form a fixing nip portion. According to the fixing step, the temperature of the fixing belt rises in a short time, and stable temperature control is possible. Even when a recording material having a rough surface is used, the fixing belt acts in a state corresponding to the surface of the transfer paper to some extent at the time of fixing, so that sufficient fixing property can be obtained.

The fixing unit is not particularly limited, but is preferably an oilless type or a type of fixing unit that applies a small amount of oil. In order to achieve this, it is preferable to fix a toner containing a release agent (WAX) in which the release agent is finely dispersed in the toner particles. The toner in which the release agent is dispersed in a small amount in the toner particles makes it easy for the release agent to ooze out during fixing, and the oil application effect is reduced when using an oil-less fixing device or in a trace amount oil application fixing device. Even in this case, the transfer of the toner to the belt side can be suppressed.
In order for the release agent to exist in a dispersed state in the toner particles, it is preferable that the release agent and the binder resin are not compatible. In order to finely disperse the release agent in the toner particles, for example, there is a method using a shearing force at the time of toner granulation in an aqueous medium at the time of toner production. The dispersion state of the release agent can be determined by observing a thin film slice of toner particles with a TEM. There is no restriction | limiting in particular as the dispersion diameter of the said mold release agent, The smaller one is preferable, However, When too small, the ooze-out at the time of fixing may be inadequate. Therefore, if the release agent can be confirmed at a magnification of 10,000, it is determined that the release agent exists in a dispersed state. If the size is 10,000 times and the release agent cannot be confirmed, even if finely dispersed, there is a case where the bleeding at the time of fixing is insufficient.

  Each step in the image forming method will be described in more detail with reference to the drawings together with means for performing each step.

  As the charging device used in the charging step, for example, a contact charging device such as a roller charging device shown in FIG. 2 and a fur brush charging device shown in FIG. 3 can be used.

  FIG. 2 shows a schematic configuration of an example of a roller charging device 500 which is a kind of contact charging device. A photosensitive member 505 as an image bearing member, which is a member to be charged, is driven to rotate at a predetermined speed (process speed) in the direction of the arrow. The charging roller 501, which is a charging member brought into contact with the photosensitive member 505, basically includes a cored bar 502 and a conductive rubber layer (503) formed on the roller and concentrically on the outer periphery of the cored bar 502. Is held freely by a bearing member (not shown) and is pressed against the photosensitive drum by a pressing means (not shown) with a predetermined pressure. In this case, the charging roller 501 rotates the photosensitive member 505. Rotates following the drive. The charging roller 501 is formed to have a diameter of 16 mm by coating a medium resistance conductive rubber layer 503 of about 100,000 Ω · cm on a core metal having a diameter of 9 mm. The cored bar 502 of the charging roller 501 and the illustrated power source 504 are electrically connected, and a predetermined bias is applied to the charging roller 501 by the power source 504. As a result, the peripheral surface of the photoconductor 505 is uniformly charged to a predetermined polarity and potential.

  The charging device may take any form such as a magnetic brush type charging device or a fur brush type charging device in addition to the roller type charging device, and can be selected according to the specifications and form of the electrophotographic apparatus. . When a magnetic brush charging device is used, the magnetic brush is composed of various ferrite particles such as Zn-Cu ferrite as a charging member, a non-magnetic conductive sleeve for supporting the charging member, and a magnet roll included therein. The Further, when using a fur brush type charging device, for example, as a material of the fur brush, a fur treated with carbon, copper sulfide, metal, and metal oxide is used, and this is treated with a metal or other conductive treated core. A charging device is formed by winding or sticking on gold.

  FIG. 3 shows a schematic configuration of an example of the contact-type brush charging device 510. A photoconductor 515 as an image carrier as a member to be charged is driven to rotate at a predetermined speed (process speed) in the direction of the arrow. A fur brush roller 511 constituted by a fur brush is brought into contact with the photoreceptor 515 with a predetermined nip width with a predetermined pressing force against the elasticity of the brush portion 513.

  A fur brush roller 511 as a contact type charging device is a tape in which a conductive core rayon fiber REC-B manufactured by Unitika Co., Ltd. is used as a brush portion 513 on a metal cored bar 512 having a diameter of 6 mm which also serves as an electrode. The roll brush is wound in a spiral shape and has an outer diameter of 14 mm and a longitudinal length of 250 mm. The brush of the brush part 513 has a density of 300 denier / 50 filaments and 155 brushes per square millimeter. This roll brush is inserted into a pipe having an inner diameter of 12 mm while being rotated in one direction, set so that the brush and the pipe are concentric, and left in a high-temperature and high-humidity atmosphere to bend and bevel.

The resistance value of the fur brush roller 511 is 1 × 10 ⁵ Ω at an applied voltage of 100V. This resistance value is converted from a current that flows when a fur brush roller is brought into contact with a metal drum having a diameter of 30 mm with a nip width of 3 mm and a voltage of 100 V is applied. The resistance value of the brush-type charging device 510 is such that, even when a low-voltage defective portion such as a pinhole occurs on the photosensitive member 515 that is a charged body, an excessive leakage current flows into this portion, and the charging nip portion is charged In order to prevent defective image defects, it is necessary to be 10 ⁴ Ω or more, and in order to sufficiently inject charges onto the surface of the photoreceptor 515, it is necessary to be 10 ⁷ Ω or less.

  As a material for the brush, in addition to REC-B manufactured by Unitika Ltd., REC-C, REC-M1, REC-M10, SA-7 manufactured by Toray Industries, Inc., manufactured by Nippon Kashiwa Co., Ltd. Possible examples include Sanderlon, Kanebo Beltron, Kuraray Co., Ltd., Krabobo, carbon dispersion in rayon, Mitsubishi Rayon Co., Ltd. global. One brush is 3 to 10 denier, and preferably has a density of 10 to 100 filaments / bundle and 80 to 600 brushes / mm. The hair foot is preferably 1 to 10 mm.

The fur brush roller 511 is rotationally driven at a predetermined peripheral speed (surface speed) in a direction opposite to the rotation direction (counter) of the photoconductor 515 and contacts the photoconductor surface with a speed difference. By applying a predetermined charging voltage from the power source 514 to the brush roller 511, the surface of the rotating photosensitive member is uniformly contact-charged to a predetermined polarity and potential.
Contact charging of the photoconductor 515 by the fur brush roller 511 is performed by direct injection charging, and the surface of the rotating photoconductor is charged to a potential substantially equal to the charging voltage applied to the fur brush roller 511.
In addition to the fur brush roller 511, the charging member may take any form such as a charging roller or a fur brush, and can be selected according to the specifications and form of the electrophotographic apparatus. When using a charging roller, it is common to coat a medium resistance rubber layer of about 100,000 Ω · cm on a cored bar. In the case of using a magnetic brush, the magnetic brush is composed of various ferrite particles such as Zn—Cu ferrite as a charging member, a non-magnetic conductive sleeve for supporting it, and a magnet roll included therein.

  FIG. 4 shows a schematic configuration of an example of a magnetic brush charging device. A photosensitive member 525 serving as a member to be charged and an image carrier is driven to rotate at a predetermined speed (process speed) in the direction of the arrow. A brush roller 521 formed of a magnetic brush is brought into contact with the photoreceptor 525 with a predetermined nip width with a predetermined pressing force against the elasticity of the brush portion 523.

As a magnetic brush as a contact charging member, for example, Zn—Cu ferrite particles having an average particle diameter of 25 μm and Zn—Cu ferrite particles having an average particle diameter of 10 μm are mixed at a mass ratio of 1: 0.05, respectively. Magnetic particles having a peak at the position of the average particle diameter and having ferrite particles with an average particle diameter of 25 μm coated with a medium resistance resin layer are used.
The contact charging member is composed of, for example, the coated magnetic particles, a nonmagnetic conductive sleeve for supporting the coated magnetic particles, and a magnet roll included therein, and the coated magnetic particles are formed on the sleeve with a thickness of 1 mm. To form a charging nip having a width of about 5 mm between the photosensitive member and the photosensitive member. The gap between the magnetic particle holding sleeve and the photosensitive member is, for example, about 500 μm. Further, the magnet roll is rotated so that, for example, the sleeve surface slides in the opposite direction at a speed twice that of the circumferential speed of the surface of the photoconductor, so that the photoconductor and the magnetic brush are made uniform. Make contact.

  In the development step, it is preferable to apply an alternating electric field. FIG. 5 shows an example of a developing device that applies an alternating electric field. In the developing device 600 shown in FIG. 5, during development, a vibration bias voltage obtained by superimposing an AC voltage on a DC voltage is applied to the developing sleeve 601 as a developing bias by the power source 602. The background portion potential and the image portion potential are located between the maximum value and the minimum value of the vibration bias potential. As a result, an alternating electric field whose direction changes alternately is formed in the developing unit 603. In this alternating electric field, the toner and carrier of the developer vibrate vigorously, and the toner 605 flies off the electrostatic binding force to the developing sleeve 601 and the carrier and flies to the photoconductor 604, corresponding to the latent image on the photoconductor. Adhere to. The toner 605 is the toner of the present invention.

  The difference (maximum peak voltage) between the maximum value and the minimum value of the vibration bias voltage is preferably 0.5 to 5 kV, and the frequency is preferably 1 to 10 kHz. As the waveform of the vibration bias voltage, a rectangular wave, a sine wave, a triangular wave, or the like can be used. As described above, the DC voltage component of the vibration bias is a value between the background part potential and the image part potential, but the value closer to the background part potential than the image part potential is more likely to cover the background part potential region. This is preferable for preventing toner adhesion.

  When the vibration bias voltage waveform is a rectangular wave, the duty ratio is preferably 50% or less. Here, the duty ratio is a ratio of time during which the toner is directed to the photosensitive member during one period of the vibration bias. By doing so, the difference between the peak value at which the toner is directed to the photoreceptor and the time average value of the bias can be increased, so that the movement of the toner is further activated and the potential of the latent image surface is increased. It can adhere to the distribution and improve the roughness and resolution. In addition, since the difference between the peak value of the carrier having a charge opposite to that of the toner and the time average value of the bias toward the photosensitive member can be reduced, the movement of the carrier is reduced, and the background portion of the latent image is reduced. The probability of carriers adhering to the substrate can be greatly reduced.

  As the fixing device used in the fixing step, for example, the fixing device shown in FIG. 6 can be used. The fixing device shown in FIG. 6 includes a heating roller 710 that is heated by electromagnetic induction of induction heating means 760, a fixing roller 720 (opposite rotating body) arranged in parallel with the heating roller 710, a heating roller 710, and a fixing roller 720. And an endless belt-like fixing belt (heat-resistant belt, toner heating medium) 730 that is heated by a heating roller 710 and rotated in the direction of arrow A by at least one of these rollers, and a fixing belt 730 And a pressure roller 740 (pressure rotator) that is in pressure contact with the fixing roller 720 and rotates in the forward direction with respect to the fixing belt 730.

The heating roller 710 is made of a hollow cylindrical magnetic metal member such as iron, cobalt, nickel, or an alloy of these metals, and has a low heat capacity with an outer diameter of, for example, 20 to 40 mm and a wall thickness of, for example, 0.3 to 1.0 mm. The temperature rises quickly.
The fixing roller 720 (opposing rotating body) includes a metal core 721 made of, for example, stainless steel, and an elastic member 722 in which a heat resistant silicone rubber is solid or foamed and covered with the core 721. In order to form a contact portion having a predetermined width between the pressure roller 740 and the fixing roller 720 by the pressing force from the pressure roller 740, the outer shape is set to about 20 to 40 mm, which is larger than the heating roller 710. The elastic member 722 has a thickness of about 4 to 6 mm. With this configuration, the heat capacity of the heating roller 710 is smaller than the heat capacity of the fixing roller 720, so that the heating roller 710 is rapidly heated and the warm-up time is shortened.

  The fixing belt 730 stretched between the heating roller 710 and the fixing roller 720 is heated at a contact portion W1 with the heating roller 710 heated by the induction heating unit 760. The inner surface of the fixing belt 730 is continuously heated by the rotation of the heating roller 710 and the fixing roller 720, and as a result, the entire belt is heated.

FIG. 7 shows a layer structure of the fixing belt 730. The belt 730 has the following four layers from the inner layer to the surface layer, and can be configured as follows.
-Base 731: Resin layer such as polyimide (PI) resin-Heat generation layer 732: Conductive material layer such as Ni, Ag, SUS-Intermediate layer 733: Elastic layer for uniform fixing-Release layer 734: Release effect Resin layer such as fluorine resin material for oil-less

  The thickness of the release layer 734 is preferably 10 μm to 300 μm, and particularly preferably about 200 μm. In this way, in the fixing device 700 as shown in FIG. 6, the toner image T formed on the recording material 770 is sufficiently wrapped by the surface layer portion of the fixing belt 730, so that the toner image T is uniformly heated and melted. It becomes possible. The thickness of the release layer 734, that is, the surface release layer, needs to be at least 10 μm in order to ensure wear resistance over time. Further, when the thickness of the release layer 734 is larger than 300 μm, the heat capacity of the fixing belt 730 increases and the time required for warm-up becomes longer. Further, the surface temperature of the fixing belt 730 is hardly lowered in the toner image fixing step, and the aggregation effect of the melted toner at the fixing portion outlet is not obtained, and the releasability of the fixing belt 730 is lowered, and the toner image T The toner adheres to the fixing belt 730 and so-called hot offset occurs. The heat generating layer 732 made of the metal may be used as the base of the fixing belt 730, but a heat-resistant resin such as a fluorine resin, a polyimide resin, a polyamide resin, a polyamideimide resin, a PEEK resin, a PES resin, or a PPS resin. Layers may be used.

  The pressure roller 740 includes, for example, a metal core 741 made of a metal cylindrical member having high thermal conductivity such as copper or aluminum, and an elastic member having high heat resistance and toner releasability provided on the surface of the metal core 741. 742. In addition to the metal, SUS may be used for the core metal 741. The pressure roller 740 presses the fixing roller 720 via the fixing belt 730 to form the fixing nip portion N, but in this embodiment, the pressure roller 740 is harder than the fixing roller 720. As a result, the pressure roller 740 bites into the fixing roller 720 (and the fixing belt 730), and the recording material 770 follows the circumferential shape of the surface of the pressure roller 740 due to this biting, so that the recording material 770 is fixed to the fixing belt 730. It has the effect of facilitating separation from the surface. The outer diameter of the pressure roller 740 is about 20 mm to 40 mm, which is the same as that of the fixing roller 720, but the wall pressure is about 0.5 mm to 2.0 mm, which is thinner than the fixing roller 720.

  As shown in FIG. 6, the induction heating means 760 that heats the heating roller 710 by electromagnetic induction has an excitation coil 761 that is a magnetic field generation means, and a coil guide plate 762 around which the excitation coil 761 is wound. Yes. The coil guide plate 762 has a semi-cylindrical shape disposed close to the outer peripheral surface of the heating roller 710, and the exciting coil 761 is formed by passing a long exciting coil wire along the coil guide plate 762 in the axial direction of the heating roller 710. It is one that is wound around alternately. The exciting coil 761 has an oscillation circuit connected to a drive power source (not shown) whose frequency is variable. Outside the excitation coil 761, a semi-cylindrical excitation coil core 763 made of a ferromagnetic material such as ferrite is fixed to the excitation coil core support member 764 and is disposed close to the excitation coil 761.

(Process cartridge)
The process cartridge includes an electrophotographic photosensitive member, a charging unit that charges the electrophotographic photosensitive member, an exposure unit that forms an electrostatic latent image on the charged electrophotographic photosensitive member, and the electrophotographic photosensitive member. Developing means for converting the electrostatic latent image formed on the toner into a toner image using the toner, a primary transfer means for primarily transferring the toner image formed on the electrophotographic photosensitive member onto the intermediate transfer body, and the intermediate A secondary transfer means for secondary transfer of the toner image primarily transferred onto the transfer material onto the recording material; and heat and pressure applied to the toner image secondary transferred onto the recording material to At least the electric power among the fixing means for fixing the toner to the surface and the cleaning means for cleaning the transfer residual toner adhering to the surface of the electrophotographic photoreceptor either after the primary transfer or after the secondary transfer. A photosensitive member, and said developing means, in which the detachable to the image forming apparatus main body integrally supported.
As the developing means and the charging means, the developing device and the charging device can be preferably used.

  An example of the process cartridge is shown in FIG. A process cartridge 800 shown in FIG. 8 includes a photoreceptor 801, a charging unit 802, a developing unit 803, and a cleaning unit 806. The operation of the process cartridge 800 will be described. The photosensitive member 801 is rotationally driven at a predetermined peripheral speed. In the rotating process, the photosensitive member 801 is uniformly charged with a predetermined positive or negative potential on its peripheral surface by the charging unit 802, and then image exposure light from an image exposure unit (not shown) such as slit exposure or laser beam scanning exposure. In this way, an electrostatic latent image is sequentially formed on the peripheral surface of the photoreceptor 801. The formed electrostatic latent image is then converted into a toner image by the developing means 805 and the developer 804 containing the toner of the present invention. The developed toner image is sequentially transferred from the sheet feeding unit to the recording material fed between the photosensitive member 801 and a transfer unit (not shown) in synchronization with the rotation of the photosensitive member 801 by the transfer unit. . The recording material that has undergone image transfer is separated from the photoreceptor surface, introduced into an image fixing means (not shown), image-fixed, and printed out as a copy (copy). The surface of the photoconductor 801 after the image transfer is cleaned by the removal of the transfer residual toner by the cleaning unit 806, and after being further discharged, it is repeatedly used for image formation.

(Image forming device)
As a full-color image forming apparatus used in the image forming method, for example, the tandem image forming apparatus 100 shown in FIGS. 9 and 10 can be used. In FIG. 9, an image forming apparatus 100 includes an image writing unit (120Bk, 120C, 120M, 120Y), an image forming unit (130Bk, 130C, 130M, 130Y), and a paper feeding unit for performing color image formation by electrophotography. 140 is mainly composed. Based on the image signal, image processing is performed by an image processing unit (not shown), and converted into black Bk, cyan C, magenta M, and yellow Y color signals for image formation, and image writing units (120Bk, 120C). , 120M, 120Y). The image writing unit (120Bk, 120C, 120M, 120Y) is, for example, a laser scanning optical system including a laser light source, a deflector such as a rotary polygon mirror, a scanning imaging optical system, and a mirror group (none of which are shown). There are four writing optical paths corresponding to the respective color signals, and image writing corresponding to the respective color signals is performed in the image forming units (130Bk, 130C, 130M, 130Y).

  The image forming unit (130Bk, 130C, 130M, 130Y) includes photoconductors (210Bk, 210C, 210M, 210Y) for black, cyan, magenta, and yellow, and photoconductors (210Bk, 210C, 210M and 210Y) are usually OPC photoreceptors. Around each photoconductor (210Bk, 210C, 210M, 210Y), there are a charging device (215Bk, 215C, 215M, 215Y), and an exposure unit for laser light from the image writing unit (120Bk, 120C, 120M, 120Y). , Developing devices for respective colors (200Bk, 200C, 200M, 200Y), primary transfer devices (230Bk, 230C, 230M, 230Y), cleaning devices (300Bk, 300C, 300M, 300Y), static eliminators (not shown), etc. Is arranged. The developing device (200Bk, 200C, 200M, 200Y) uses a two-component magnetic brush developing system. An intermediate transfer belt 220 is interposed between each photoconductor (210Bk, 210C, 210M, 210Y) and a primary transfer device (230Bk, 230C, 230M, 230Y). The toner images of the respective colors are sequentially superimposed and transferred to carry the toner images on the respective photoconductors.

  In some cases, it is preferable that a pre-transfer charger as a pre-transfer charging unit is disposed outside the intermediate transfer belt 220 at a position after passing through the primary transfer position of the final color and before passing through the secondary transfer position. This pre-transfer charger uniformly transfers the toner image to the same polarity as the toner image before transferring the toner image on the intermediate transfer belt 220 transferred to the photosensitive member 210 in the primary transfer portion onto a transfer sheet as a recording material. Is charged.

  The toner image on the intermediate transfer belt 220 transferred from each photoconductor (210Bk, 210C, 210M, 210Y) includes a halftone portion and a solid portion, or includes portions having different amounts of toner overlap. The charge amount may vary. Further, there may be a case where a variation in the charge amount occurs in the toner image on the intermediate transfer belt 220 after the primary transfer due to the peeling discharge generated in the gap adjacent to the downstream side of the primary transfer portion in the intermediate transfer belt moving direction. . Such variation in the charge amount in the same toner image lowers the transfer margin in the secondary transfer portion that transfers the toner image on the intermediate transfer belt 220 onto the transfer paper. Therefore, the toner image before being transferred to the transfer paper by the pre-transfer charger is uniformly charged to the same polarity as the toner image, thereby eliminating the variation in the charge amount in the same toner image and the transfer margin in the secondary transfer portion. Has improved.

  As described above, according to this image forming method, the toner image on the intermediate transfer belt 220 transferred from each photoconductor (210Bk, 210C, 210M, 210Y) is uniformly charged by the pre-transfer charger, so that the image on the intermediate transfer belt 220 is obtained. Even if there is a variation in the charge amount in the toner image, the transfer characteristics at the secondary transfer portion can be made substantially constant over the respective portions of the toner image on the intermediate transfer belt 220. Therefore, it is possible to suppress a decrease in transfer margin when transferring to transfer paper and to stably transfer a toner image.

  In this image forming method, the amount of charge charged by the pre-transfer charger varies depending on the moving speed of the intermediate transfer belt 220 that is the object to be charged. For example, if the moving speed of the intermediate transfer belt 220 is slow, the time for the same portion of the toner image on the intermediate transfer belt 220 to pass through the charging region by the pre-transfer charger becomes long, and the charge amount increases. Conversely, when the moving speed of the intermediate transfer belt 220 is fast, the charge amount of the toner image on the intermediate transfer belt 220 becomes small. Therefore, when the moving speed of the intermediate transfer belt 220 changes while the toner image on the intermediate transfer belt 220 passes through the charging position by the pre-transfer charger, the transfer speed depends on the moving speed of the intermediate transfer belt 220. Therefore, it is desirable to control the pre-transfer charger so that the charge amount for the toner image does not change during the process.

  Conductive rollers 241, 242, and 243 are provided between the primary transfer devices (230Bk, 230C, 230M, and 230Y). The transfer sheet is fed from the sheet feeding unit 140 and then carried on the transfer belt 180 via the registration roller pair 160. The intermediate transfer belt 170 is moved by the secondary transfer roller 170 when the intermediate transfer belt 220 and the transfer belt 180 are in contact with each other. The toner image on 220 is transferred to transfer paper, and a color image is formed.

  The transfer paper after image formation is conveyed to the fixing device 150 by the secondary transfer belt 180, and the image is fixed to obtain a color image. The toner on the intermediate transfer belt 220 remaining without being transferred is removed from the belt by the intermediate transfer belt cleaning devices 261 and 262.

  Since the toner polarity on the intermediate transfer belt 220 before transfer onto the transfer paper is the same negative polarity as that during development, a positive transfer bias voltage is applied to the secondary transfer roller 170, and the toner is transferred onto the transfer paper. The The nip pressure at this portion affects the transfer property and greatly affects the fixability. Further, the toner on the intermediate transfer belt 220 remaining without being transferred is discharged and charged to the positive polarity side and charged to 0 to the positive side at the moment when the transfer paper and the intermediate transfer belt 220 are separated. Note that the toner image formed when the transfer paper is jammed or in the non-image area is not affected by the secondary transfer, and therefore remains negative.

  The thickness of the photosensitive layer is 30 μm, the beam spot diameter of the optical system is 50 × 60 μm, and the light quantity is 0.47 mW. The developing process is performed with the charging (exposure side) potential V0 of the photoreceptor (black) 210Bk being −700V, the post-exposure potential VL being −120V, the developing bias voltage being −470V, that is, the developing potential 350V. The visible image of the toner (black) formed on the photoconductor (black) 210Bk is then transferred (intermediate transfer belt and transfer paper) and completed as an image through a fixing process. First, all colors are transferred from the primary transfer device (230Bk, 230C, 230M, 230Y) to the intermediate transfer belt 220, and then transferred onto a transfer sheet by applying a bias to another secondary transfer roller 170.

  Next, the photoconductor cleaning device will be described in detail. In FIG. 9, each developing device (200Bk, 200C, 200M, 200Y) and each cleaning device (300Bk, 300C, 300M, 300Y) are connected to each other by a toner transfer pipe (250Bk, 250C, 250M, 250Y). (Dotted line in FIG. 9). Each toner transfer pipe (250Bk, 250C, 250M, 250Y) contains a screw (not shown), and the toner collected by each cleaning device (300Bk, 300C, 300M, 300Y) Each developing device (200Bk, 200C, 200M, 200Y) is transferred.

  In the direct transfer method using a combination of the four photosensitive drums and the belt conveyance, paper dust adheres when the photoconductor and the transfer paper come into contact with each other, and the paper dust is contained when the toner is collected. Sometimes image deterioration such as toner loss occurs and cannot be used. In addition, in a system that combines a single photosensitive drum and intermediate transfer, the use of an intermediate transfer member eliminates paper dust from adhering to the photosensitive member during transfer paper transfer. When it is done, it is practically impossible to separate the mixed color toner. In addition, there is an image forming method using mixed color toner as black toner, but even if all colors are mixed, it does not become black, and the color changes depending on the print mode. Therefore, it is impossible to recycle the toner with one photoconductor configuration. .

  On the other hand, in this full-color image forming apparatus, since the intermediate transfer belt 220 is used, paper dust is less mixed and paper dust is prevented from adhering to the intermediate transfer belt 220 during paper transfer. Since each photoconductor (210Bk, 210C, 210M, 210Y) uses independent color toner, it is not necessary to contact or separate each photoconductor cleaning device (300Bk, 300C, 300M, 300Y), and only the toner is reliably collected. can do.

  The positively charged toner remaining on the intermediate transfer belt 220 is cleaned by a conductive fur brush 262 to which a negative voltage is applied. The method of applying a voltage to the conductive fur brush 262 is exactly the same as the conductive fur brush 261 except that the polarity is different. The toner remaining without being transferred is also almost cleaned by the two conductive fur brushes 261 and 262. Here, toner, paper powder, talc, and the like remaining without being cleaned by the conductive fur brush 262 are negatively charged by the negative voltage of the conductive fur brush 262. The next black primary transfer is a transfer with a positive voltage, and negatively charged toner or the like is attracted to the intermediate transfer belt 220 side, so that the transfer to the photoreceptor (black) 210Bk side can be prevented.

  Next, the intermediate transfer belt 220 used in the image forming apparatus will be described. As described above, the intermediate transfer belt is preferably a single resin layer, but may have an elastic layer or a surface layer as necessary.

  The resin material constituting the resin layer is not particularly limited. For example, polycarbonate, fluororesin (ETFE, PVDF), polystyrene, chloropolystyrene, poly-α-methylstyrene, styrene-butadiene copolymer, styrene- Vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene -Butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-phenyl acrylate copolymer, etc.), styrene-methacrylic acid ester copolymer (styrene-methyl methacrylate copolymer, styrene-methacrylic acid) Ethyl copolymer, styrene-methacrylic acid Copolymer), styrene resins such as styrene-α-chloroacrylic acid methyl copolymer, styrene-acrylonitrile-acrylic acid ester copolymer (monopolymer or copolymer containing styrene or styrene-substituted product) , Methyl methacrylate resin, butyl methacrylate resin, ethyl acrylate resin, butyl acrylate resin, modified acrylic resin (silicone modified acrylic resin, vinyl chloride resin modified acrylic resin, acrylic / urethane resin, etc.), vinyl chloride resin, styrene- Vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, rosin-modified maleic acid resin, phenol resin, epoxy resin, polyester resin, polyester polyurethane resin, polyethylene, polypropylene, polybutadiene, polyvinylidene chloride, ionomer resin, polyurethane Selected from the group consisting of tan resin, silicone resin, ketone resin, ethylene-ethyl acrylate copolymer, xylene resin and polyvinyl butyral resin, polyamide resin, modified polyphenylene oxide resin, etc., these may be used alone. Two or more kinds may be used in combination.

  Moreover, there is no restriction | limiting in particular as an elastic material (elastic material rubber | gum, elastomer) which comprises the said elastic layer, For example, butyl rubber, fluorine-type rubber, acrylic rubber, EPDM, NBR, acrylonitrile butadiene styrene rubber natural rubber, isoprene Rubber, styrene-butadiene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-propylene terpolymer, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydrin series Rubber, Ricone rubber, Fluoro rubber, Polysulfide rubber, Polynorbornene rubber, Hydrogenated nitrile rubber, Thermoplastic elastomer (eg polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyamide, Urea, polyester, selected from the group consisting of fluorine resin) or the like, it may be used singly or in combination of two or more thereof.

  Further, the material for the surface layer is not particularly limited, but a material for reducing the adhesive force of the toner to the surface of the intermediate transfer belt and improving the secondary transfer property is required. For example, materials that use one or more of polyurethane, polyester, epoxy resin, etc. to reduce surface energy and improve lubricity, such as powders of fluororesins, fluorine compounds, fluorocarbons, titanium dioxide, silicon carbide, etc. One body, two or more kinds of particles or particles having different particle diameters can be dispersed and used. Further, it is also possible to use a material having a surface energy reduced by forming a fluorine-rich layer on the surface by heat treatment, such as a fluorine-based rubber material.

As the resin layer and the elastic layer, a resistance value adjusting conductive agent is preferably added.
The resistance value adjusting conductive agent is not particularly limited. For example, carbon black, graphite, metal powder such as aluminum and nickel, tin oxide, titanium oxide, antimony oxide, indium oxide, potassium titanate, antimony oxide-oxidation Examples thereof include conductive metal oxides such as tin composite oxide (ATO) and indium oxide-tin oxide composite oxide (ITO).
The conductive metal oxide may be coated with insulating fine particles such as barium sulfate, magnesium silicate, and calcium carbonate.

  FIG. 10 shows another example of an image forming apparatus used in the full-color image forming method of the present invention, which is a copying apparatus 100 provided with a tandem indirect transfer type electrophotographic image forming apparatus. In FIG. 10, 110 is a copying apparatus main body, 200 is a paper feed table on which it is placed, 300 is a scanner mounted on the copying apparatus main body 110, and 400 is an automatic document feeder (ADF) mounted thereon. The copying machine main body 110 is provided with an endless belt-shaped intermediate transfer member 50 at the center.

  Then, as shown in FIG. 10, in this example, it is wound around three support rollers 14, 15, and 16 so as to be able to rotate and convey clockwise in the figure. In this illustrated example, an intermediate transfer body cleaning device 17 that removes residual toner remaining on the intermediate transfer body 50 after image transfer is provided to the left of the second support roller 15 among the three. Further, among the three images, four images of yellow, cyan, magenta, and black are arranged on the intermediate transfer member 50 stretched between the first support roller 14 and the second support roller 15 along the conveyance direction. The tandem image forming apparatus 120 is configured by arranging the forming units 18 side by side.

  An exposure apparatus 21 is further provided on the tandem image forming apparatus 120 as shown in FIG. On the other hand, a secondary transfer device 22 is provided on the side opposite to the tandem image forming device 120 with the intermediate transfer member 50 interposed therebetween. In the illustrated example, the secondary transfer device 22 is configured by spanning a secondary transfer belt 24, which is an endless belt, between two rollers 23, and is pressed against the third support roller 16 via an intermediate transfer member 50. The image on the intermediate transfer member 50 is transferred to a sheet. A fixing device 25 for fixing the transfer image on the sheet is provided beside the secondary transfer device 22. The fixing device 25 is configured by pressing a pressure roller 27 against a fixing belt 26 that is an endless belt. The secondary transfer device 22 described above is also provided with a sheet transport function for transporting the image-transferred sheet to the fixing device 25. Of course, a transfer roller or a non-contact charger may be disposed as the secondary transfer device 22, and in such a case, it is difficult to provide this sheet conveying function together. In the illustrated example, a sheet reversing device 28 for reversing the sheet so as to record an image on both sides of the sheet is provided below the secondary transfer device 22 and the fixing device 25 in parallel with the tandem image forming device 120 described above. Is provided.

  Now, when making a copy using this color electrophotographic apparatus, a document is set on the document table 130 of the automatic document feeder 400. Alternatively, the automatic document feeder 400 is opened, a document is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed and pressed by it.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the other contact glass 32. At that time, the scanner 300 is immediately driven to travel the first traveling body 33 and the second traveling body 34. Then, the first traveling body 33 emits light from the light source and further reflects the reflected light from the document surface toward the second traveling body 34, and is reflected by the mirror of the second traveling body 34 and passes through the imaging lens 35. The document is placed in the reading sensor 36 and the original content is read.

  When a start switch (not shown) is pressed, one of the support rollers 14, 15 and 16 is rotationally driven by a drive motor (not shown), the other two support rollers are driven to rotate, and the intermediate transfer member 50 is rotated and conveyed. To do. At the same time, the individual image forming means 18 rotates the photoconductor 10 to form black, yellow, magenta, and cyan single-color images on the photoconductors (10Y, 10C, 10M, and 10K), respectively. Then, along with the conveyance of the intermediate transfer member 50, these single color images are sequentially transferred to form a composite color image on the intermediate transfer member 50.

  On the other hand, when a start switch (not shown) is pressed, one of the paper feed rollers 142 of the paper feed table 200 is selectively rotated, and a sheet is fed out from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and the separation roller 145. Are separated one by one into the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 100, and abutted against the registration roller 49 and stopped.

  Alternatively, the sheet feed roller 67 is rotated to feed out the sheets on the manual feed tray 51, separated one by one by the separation roller 58, put into the manual feed path 53, and abutted against the registration roller 49 and stopped.

  Then, the registration roller 49 is rotated in synchronization with the composite color image on the intermediate transfer member 50, the sheet is fed between the intermediate transfer member 50 and the secondary transfer device 22, and transferred by the secondary transfer device 22. A color image is recorded on the sheet.

  The image-transferred sheet is conveyed by the secondary transfer device 22 and sent to the fixing device 25. The fixing device 25 applies heat and pressure to fix the transferred image, and then the switching roller 55 is used to switch the discharge roller. The paper is discharged at 56 and stacked on the paper discharge tray 57. Alternatively, it is switched by the switching claw 55 and put into the sheet reversing device 28, where it is reversed and guided again to the transfer position, and an image is recorded also on the back surface, and then discharged onto the discharge tray 57 by the discharge roller 56.

  On the other hand, the intermediate transfer member 50 after image transfer is removed by the intermediate transfer member cleaning device 17 to remove residual toner remaining on the intermediate transfer member 50 after image transfer, and is prepared for re-image formation by the tandem image forming device 120. Here, the registration roller 49 is generally used while being grounded, but it is also possible to apply a bias for removing paper dust from the sheet.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to the Example and comparative example illustrated here. In addition, the part in an Example represents a mass part unless there is particular description.

<Preparation of solution or dispersion of toner material>
-Synthesis of azacalixarene derivatives-
Of aza calixarene derivative having the general formula (I), m is 8, n is _{0, R 1, R 3,} R 4 is a hydrogen atom, R ₂ is aza calixarene derivatives substituted with tert- butyl group A1 Was synthesized.

-Synthesis of unmodified polyester (low molecular weight polyester)-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 67 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 84 parts by mass of bisphenol A propion oxide 3 mol adduct, 274 parts by mass of terephthalic acid, and dibutyltin oxide 2 parts by mass were added and reacted at 230 ° C. under normal pressure for 8 hours. Next, the reaction solution was reacted under reduced pressure of 10 to 15 mmHg for 5 hours to synthesize an unmodified polyester. The obtained unmodified polyester had a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 5,600, and a glass transition temperature (Tg) of 55 ° C.

-Preparation of masterbatch (MB)-
1000 parts by weight of water, 540 parts by weight of carbon black (“Printex35”; manufactured by Degussa, DBP oil absorption = 42 ml / 100 g, pH = 9.5), and 1,200 parts by weight of the unmodified polyester were added to a Henschel mixer ( (Mitsui Mining Co., Ltd.). The mixture was kneaded for 30 minutes at 150 ° C. with two rolls, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron) to prepare a master batch.

-Synthesis of prepolymer-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, trimellitic anhydride 22 parts by mass of acid and 2 parts by mass of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Subsequently, it was made to react under reduced pressure of 10-15mHg for 5 hours, and the intermediate polyester was synthesize | combined. The resulting intermediate polyester has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,600, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5, and a hydroxyl value of 49. Next, 411 parts by mass of the intermediate polyester, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate are charged in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. Thus, a prepolymer (polymer capable of reacting with the active hydrogen group-containing compound) was synthesized. The free isocyanate content of the obtained prepolymer was 1.60% by mass, and the solid content concentration of the prepolymer (after standing at 150 ° C. for 45 minutes) was 50% by mass.

<Preparation of resin fine particles>
In a reaction vessel in which a stir bar and a thermometer are set, 683 parts of water, 16 parts by weight of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 83 parts by weight of styrene, 83 parts of methacrylic acid When a mass part, 110 mass parts of butyl acrylate, and 1 mass part of ammonium persulfate were prepared and stirred for 15 minutes at 400 rpm, a white emulsion was obtained. The emulsion was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts by mass of 1% ammonium persulfate aqueous solution was added to the emulsion, and aged at 75 ° C. for 5 hours to give a vinyl resin (styrene salt of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate). An aqueous dispersion (resin fine particle dispersion A) was obtained. The volume average particle size (measured with LA-920, manufactured by Horiba, Ltd.) of the dispersed particles of [resin fine particle dispersion A] was 42 nm.

Example 1
<Manufacture of toner a>
<< Solution or Dispersion Step A >>
-Preparation of Azacalixarene Derivative A1 Dispersion-
Azacalix allene derivative A1 was charged in a beaker with 5 parts by mass, 15 parts by mass of the unmodified polyester and 30 parts by mass of ethyl acetate, and using a bead mill ("Ultraviscomil"; manufactured by Imex Co., Ltd.), a liquid feed rate of 1 kg / An azacalixarene derivative A1 dispersion was prepared by three passes under the conditions of hr, a disk peripheral speed of 6 m / s, and 80% by volume of 0.5 mm zirconia beads. The average particle diameter (dispersion diameter) of the azacalixarene derivative A1 in the dispersion was 140 nm.

-Preparation of toner material phase-
In a beaker, 100 parts by mass of the unmodified polyester and 130 parts by mass of ethyl acetate were stirred and dissolved. Subsequently, 10 parts by mass of carnauba wax (molecular weight = 1,800, acid value = 2.5, penetration = 1.5 mm (40 ° C.)), 10 parts by mass of the master batch, and dispersion of the azacalixarene derivative A1 1 part by weight of a liquid was charged, and a bead mill (“Ultra Visco Mill”; manufactured by Imex Co., Ltd.) was used to fill a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / s, and 80% by volume of 0.5 mm zirconia beads. 3 passes to prepare a raw material solution, 40 parts by weight of the prepolymer was added and stirred, and then a toner material solution or dispersion was prepared.

<< Emulsification or dispersion preparation step B >>
-Preparation of aqueous medium phase-
660 parts by mass of water, 1.25 parts by mass of a resin fine particle dispersion, 25 parts by mass of a 48.5% by mass aqueous solution of sodium dodecyldiphenyl ether disulfonate (“Eleminol MON-7”; manufactured by Sanyo Chemical Industries), and 60 parts by mass of ethyl acetate The parts were mixed and stirred to obtain a milky white liquid (aqueous phase).

-Preparation of emulsification or dispersion A-
150 parts by mass of the aqueous medium phase is placed in a container, and stirred at a rotational speed of 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). The mixture was added and mixed for 10 minutes to prepare an emulsification or dispersion A (emulsion slurry).

<< Organic solvent removal step C >>
-Removal of organic solvent-
A flask equipped with a degassing pipe, a stirrer and a thermometer was charged with 100 parts by mass of the emulsified or dispersed liquid A, and the solvent was removed by removing the solvent under reduced pressure at 30 ° C. for 12 hours while stirring at a stirring peripheral speed of 20 m / min. A slurry A was obtained.

-Cleaning and drying-
After filtering the whole amount of the solvent-removed slurry A under reduced pressure, 300 parts by mass of ion-exchanged water was added to the filter cake, mixed and redispersed (at 12,000 rpm for 10 minutes) with a TK homomixer, and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added and mixed with a TK homomixer (at 12,000 rpm for 10 minutes) and then filtered three times. The obtained filter cake was dried at 45 ° C. for 48 hours with a forward air dryer and sieved with a mesh having a mesh size of 75 μm to obtain toner base particles a.

-External treatment-
To 100 parts by mass of toner base particles a, 0.6 parts by mass of hydrophobic silica having an average particle size of 100 nm, 1.0 part by mass of titanium oxide having an average particle size of 20 nm, and hydrophobic silica fine powder having an average particle size of 15 nm Toner a was obtained by mixing 0.8 parts by mass of the toner with a Henschel mixer.

(Example 2)
<Manufacture of toner b>
Toner b was prepared in the same manner as in Example 1, except that the dispersion diameter of the azacalixarene derivative A1 was changed to 140 nm and the 76 nm azacalixarene derivative A1 was used. The average dispersion diameter of the azacalixarene derivative A1 used for the toner b was prepared as follows.
-Preparation of Azacalixarene Derivative A1 Dispersion-
Azacalix allene derivative A1 was charged in a beaker with 5 parts by mass, 15 parts by mass of the unmodified polyester and 30 parts by mass of ethyl acetate, and using a bead mill ("Ultraviscomil"; manufactured by Imex Co., Ltd.), a liquid feed rate of 1 kg / An azacalixarene derivative A1 dispersion was prepared by performing 5 passes under the conditions of hr, a disk peripheral speed of 6 m / s, and 80% by volume of 0.5 mm zirconia beads.

[Example 3]
<Manufacture of toner c>
Toner c was prepared in the same manner as in Example 1, except that the dispersion diameter of azacalixarene derivative A1 was changed to 140 nm and a 288 nm azacalixarene derivative A1 was used. The average dispersion diameter of the azacalixarene derivative A1 used for the toner c was prepared as follows.
-Preparation of Azacalixarene Derivative A1 Dispersion-
Azacalix allene derivative A1 was charged in a beaker with 5 parts by mass, 15 parts by mass of the unmodified polyester and 30 parts by mass of ethyl acetate, and using a bead mill ("Ultraviscomil"; manufactured by Imex Co., Ltd.), a liquid feed rate of 1 kg / An azacalixarene derivative A1 dispersion was prepared by two passes under the conditions of hr, a disk peripheral speed of 6 m / s, and 80% by volume of 0.5 mm zirconia beads.

[Example 4]
-Synthesis of azacalixarene derivative A2-
In the above general formula (I), m is 8, n is _{0, R 1, R 3,} R 4 were synthesized aza calixarene derivative A2 hydrogen atom, R ₂ is substituted with a phenyl group.
-Preparation of Azacalixarene Derivative A2 Dispersion-
Azacalix allene derivative A2 was charged in a beaker with 5 parts by mass, 15 parts by mass of the unmodified polyester and 30 parts by mass of ethyl acetate, and using a bead mill (“Ultra Visco Mill”; manufactured by Imex Corporation), a liquid feeding speed of 1 kg / An azacalixarene derivative A2 dispersion was prepared by 6 passes under the conditions of hr, disk peripheral speed 6 m / s, and 80% by volume of 0.5 mm zirconia beads. The average dispersion diameter of the azacalixarene derivative A2 was 63 nm.

<Manufacture of toner d>
A toner d was prepared in the same manner as in Example 1 except that instead of the azacalixarene derivative A1 in the example 1, the azacalixarene derivative A2 having an average dispersion diameter of 63 nm was used.

[Example 5]
-Synthesis of azacalixarene derivative A3-
In the general formula (I), m + n is 8, m: n is 1: 1, R _1, R _3, R _4, R _11, R _{13 and} R ₁₄ are hydrogen atoms, R ₂ is a tert-butyl group, R _An azacalixarene derivative A3 in which ₁₂ was substituted with a phenyl group was synthesized.
-Preparation of Azacalixarene Derivative A3 Dispersion-
Azacalix allene derivative A3 was charged in a beaker with 5 parts by mass, 15 parts by mass of the unmodified polyester and 30 parts by mass of ethyl acetate, and using a bead mill (“Ultra Visco Mill”; manufactured by Imex Corporation), a liquid feeding speed of 1 kg / An azacalixarene derivative A3 dispersion was prepared by 6 passes under the conditions of hr, disk peripheral speed 6 m / s, and 80% by volume of 0.5 mm zirconia beads. The average dispersion diameter of the azacalixarene derivative A3 was 55 nm.

<Manufacture of toner e>
A toner e was produced in the same manner as in Example 1 except that instead of the azacalixarene derivative A1 in the example 1, the azacalixarene derivative A3 having an average dispersion diameter of 55 nm was used.

[Example 6]
-Synthesis of azacalixarene derivative A4-
An azacalixarene derivative A4 in which m is 8, n is 0, R _1, R _{3 and} R ₄ are hydrogen atoms and R ₂ is substituted with a methoxy group in the general formula (I) was synthesized.
-Preparation of Azacalixarene derivative A4 dispersion-
Azacalix allene derivative A4 was charged in a beaker with 5 parts by mass, 15 parts by mass of the unmodified polyester, and 30 parts by mass of ethyl acetate, and using a bead mill ("Ultraviscomil"; manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / An azacalixarene derivative A4 dispersion was prepared by performing four passes under the conditions of hr, a disk peripheral speed of 6 m / s, and 80% by volume of 0.5 mm zirconia beads. The average dispersion diameter of the azacalixarene derivative A4 was 117 nm.

<Manufacture of toner f>
A toner f was produced in the same manner as in Example 1 except that instead of the azacalixarene derivative A1 in the example 1, the azacalixarene derivative A4 having an average dispersion diameter of 117 nm was used.

[Example 7]
-Synthesis of azacalixarene derivative A5-
In the general formula (I), m + n is 8, m: n is 1: 1, R _1, R _3, R _4, R _11, R _{13, and} R ₁₄ are hydrogen atoms, R ₂ is a methoxy group, and R ₁₂ is An azacalixarene derivative A5 substituted with a tert-butyl group was synthesized.
-Preparation of Azacalixarene Derivative A5 Dispersion-
Azacalix allene derivative A5 was charged in a beaker with 5 parts by mass, 15 parts by mass of the unmodified polyester and 30 parts by mass of ethyl acetate, and using a bead mill (“Ultra Visco Mill”; manufactured by Imex Co., Ltd.), a liquid feed rate of 1 kg / An azacalixarene derivative A5 dispersion was prepared by three passes under the conditions of hr, a disk peripheral speed of 6 m / s, and 80% by volume of 0.5 mm zirconia beads. The average dispersion diameter of the azacalixarene derivative A5 was 183 nm.

<Manufacture of toner g>
A toner g was prepared in the same manner as in Example 1 except that instead of the azacalixarene derivative A1 in the example 1, the azacalixarene derivative A5 having an average dispersion diameter of 183 nm was used.

[Example 8]
-Synthesis of Azacalixarene Derivative A6-
In the general formula (I), m + n is 8, m: n is 1: 1, R _1, R _3, R _4, R _11, R _{13, and} R ₁₄ are hydrogen atoms, R ₂ is a methoxy group, and R ₁₂ is An azacalixarene derivative A6 substituted with a phenyl group was synthesized.
-Preparation of Azacalixarene Derivative A6 Dispersion-
Azacalix allene derivative A6 was charged in a beaker with 5 parts by mass, 15 parts by mass of the unmodified polyester and 30 parts by mass of ethyl acetate, and using a bead mill ("Ultraviscomil"; manufactured by Imex Co., Ltd.), a liquid feed rate of 1 kg / An azacalixarene derivative A6 dispersion was prepared by 5 passes under the conditions of hr, disk peripheral speed 6 m / s, and 80% by volume of 0.5 mm zirconia beads. The average dispersion diameter of the azacalixarene derivative A6 was 101 nm.

<Manufacture of toner h>
A toner h was produced in the same manner as in Example 1 except that instead of the azacalixarene derivative A1 in the example 1, the azacalixarene derivative A6 having an average dispersion diameter of 101 nm was used.

[Comparative Example 1]
<Manufacture of toner i>
A toner i was produced in the same manner as in Example 1 except that TN-105 (zirconium salicylate complex structure) manufactured by Hodogaya Chemical Co., Ltd. was used instead of the azacalixarene derivative A1.

[Comparative Example 2]
<Manufacture of toner j>
A toner j was prepared in the same manner as in Example 1 except that E-84 (zinc salicylate complex structure) manufactured by Orient Chemical Industries, Ltd. was used instead of the azacalixarene derivative A1.

[Comparative Example 3]
<Manufacture of toner k>
In Example 1, toner k was prepared in the same manner as in Example 1 except that E-89 (calixarene derivative structure linked by a methylene group) manufactured by Orient Chemical Industries was used instead of the azacalixarene derivative A1. Produced.

  Table 2 shows the physical properties of the toners obtained in Examples 1 to 8 and Comparative Examples 1 to 3. The evaluation method of physical properties is as follows.

(Volume average particle diameter and volume average particle diameter / number average particle diameter)
The volume average particle diameter (Dv) and the volume average particle diameter / number average particle diameter (Dv / Dn) were measured with a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.).

(Roundness)
0.1 mL to 0.5 mL of 10% by mass surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku) is added to a 100 mL glass beaker, and 0.1 g to 0.5 g of each toner is added. Stir with a microspatel and then add 80 ml of ion-exchanged water. The obtained dispersion is subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). Using the flow type particle image analyzer (“FPIA-2100”; manufactured by Sysmex Corporation), the dispersion was measured at a density of 5,000 to 15,000 / μL, and the shape and distribution of the toner were measured.

(Common logarithm LogR of electrical resistivity R)
The common logarithm value LogR of the electrical resistivity R of the toner was measured by first preparing a measurement sample in which 3 g of toner was molded into a pellet of about 2 mm thickness, and using this as a SE-70 type solid electrode (Ando Electric ( LogR when a 1 kHz alternating current is applied between the electrodes, TR-10C type dielectric loss measuring device, WBG-9 oscillator, BDA-9 equilibrium point detector (all are Ando Electric) Measured by a measuring instrument composed of (manufactured by Co., Ltd.), and thereby the LogR of the toner was determined.

[Creation of carrier]
Next, a specific example of manufacturing the carrier used for the actual toner evaluation will be described. The carrier used in the present invention is not limited to these examples.
-Career-
Acrylic resin solution (solid content 50% by weight) 21.0 parts by weight Guanamine solution (solid content 70% by weight) 6.4 parts by weight Alumina particles [0.3 μm, specific resistance 10 ¹⁴ (Ω · cm)] 7.6 weights Part 65.0 parts by weight of silicone resin solution [solid content 23 mass% (SR2410: manufactured by Toray Dow Corning Silicone)]
Aminosilane 1.0 part by weight [solid content 100% by mass (SH6020: manufactured by Toray Dow Corning Silicone)]
Toluene 60 parts by weight Butyl cellosolve 60 parts by weight The carrier raw material was dispersed with a homomixer for 10 minutes to obtain a coating film forming solution of an acrylic resin and a silicone resin containing alumina particles. Firing ferrite powder [(MgO) _1.8 (MnO) _49.5 (Fe ₂ O ₃ ) _48.0 : average particle size; 25 μm] as the core material so that the coating film forming solution has a film thickness of 0.15 μm on the surface of the core material The coated ferrite powder was obtained by applying and drying with a Spira coater (Okada Seiko Co., Ltd.). The obtained coated ferrite powder was fired in an electric furnace at 150 ° C. for 1 hour. After cooling, the ferrite powder bulk was crushed using a sieve having an aperture of 106 μm to obtain a carrier. The measurement of the binder resin film thickness was performed by observing the cross section of the carrier with a transmission electron microscope so that the coating film covering the carrier surface could be observed. Thus, carrier A having a weight average particle diameter of 35 μm was obtained.

[Preparation of two-component developer]
Two-component development using toners a to k and carrier A, with 7 parts by mass of toner per 100 parts by mass of carrier uniformly mixed and charged using a type of tumbler mixer in which the container rolls and stirs. Agents a to f were prepared.

[Evaluation of toner]
(durability)
A solid pattern of A4 size and toner adhesion amount 0.6 mg / cm ² for each developer, using an evaluation machine that was modified from Fuji Xerox DocuColor 8000 Digital Press and tuned so that the linear speed and transfer time could be adjusted. As a test image, a running test of 100,000 sheets was performed in a normal temperature and normal humidity environment (temperature 25 ° C., humidity 40%). A part of the developer was sampled after the initial run and 100,000 sheets running, the charge amount was measured by the blow-off method, and the durability was evaluated by comparing the initial value and the charge amount of the toner after the running test. Table 2 shows the charge amount values and evaluation results after the initial run and 100,000 running tests. The initial value is measured in the same manner as in the toner charge amount measuring method in the present invention.
Evaluation criteria are
◎ ・ ・ ・ Change in charge amount less than 3 μc / g ○ ・ ・ ・ Change in charge amount from 3 μc / g to less than 5 μc / g Δ ・ ・ ・ Change in charge amount from 5 μc / g to less than 10 μc / g The change in charge amount was 10 μc / g or more.

(Charging environment stability)
Using a Ricoh digital full-color copier, imgioColor 2800, a 100,000 sheets image chart having a 7% image area was run in a single color mode. The charge stability was evaluated by sampling a part of the developer at the initial stage and after running 100,000 sheets and measuring the charge amount by the blow-off method. The high-temperature and high-humidity environment charge stability evaluation was performed in an environment of a temperature of 40 ° C. and a humidity of 90%, and the low-temperature and low-humidity environment charge stability evaluation was performed in an environment of a temperature of 10 ° C. and a humidity of 15%. The evaluation results are shown in Table 2.
Evaluation criteria are
◎ ・ ・ ・ Change in charge amount less than 3 μc / g ○ ・ ・ ・ Change in charge amount from 3 μc / g to less than 5 μc / g Δ ・ ・ ・ Change in charge amount from 5 μc / g to less than 10 μc / g The change in charge amount was 10 μc / g or more.

(Granulation property)
The volume average particle diameter (Dv) and the volume average particle diameter / number average particle diameter (Dv / Dn) of the toners a to s are measured with a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.). It was evaluated whether it could be close to 5.2 ± 0.3 μm and Dv / Dn could be obtained. The results are shown in Table 2.
The evaluation criteria for Dv are:
A: 5.2 ± 0.3 μm less than ± 0.1 μm B: 5.2 ± 0.3 μm ± 0.1 μm or more and less than 0.3 μm Δ: 5.2 ± 0.3 μm ± 0.3 μm or more 0 Less than 5 μm ×: It was set to ± 0.5 μm or more of 5.2 ± 0.3 μm.
The evaluation criteria for Dv / Dn are:
A: Less than 1.15 B: 1.15 or more and less than 1.17 Δ: 1.18 or more and less than 1.25 ×: 1.25 or more.

(Azaalix allene derivative dispersion diameter)
1 g of each toner is immersed in 100 g of chloroform for 10 hours, and an azacalixarene derivative dispersion liquid is added at 5,500 rpm (9,545 g) with a centrifuge (H-9R manufactured by Kokusan Co., Ltd., LN angle rotor). Centrifuged. Particles of an azacalixarene derivative were present in the centrifuged supernatant, and the particle size of the particles was measured using “LA-920” (manufactured by Horiba Seisakusho). In the measurement of LA-920, analysis was performed using an application dedicated to LA-920 (Ver3.32) (manufactured by Horiba Seisakusho). The results are shown in Table 2.

  From Table 2, it can be seen that the toners of Examples 1 to 8 are excellent in granulation properties, durability, environmental stability and granulation properties. On the other hand, TN-105 used in Comparative Example 1 (Toner i) has a zirconium salicylate complex structure and exhibits a high charge imparting effect in the pulverized toner, but the granulating property is remarkably poor, and the surface of the toner The property is also very bad. Further, E-84 used in Comparative Example 2 (toner j) has a zinc salicylate complex structure and exhibits a high charge imparting effect in the pulverized toner, but the granulating property is remarkably poor and the toner is formed. It can be seen that Comparative Examples 1 and 2 are inferior in durability, environmental stability and granulation properties as compared with the toners of Examples 1 to 8. Further, E-89 used in Comparative Example 3 (toner k) has a normal calixarene derivative structure connected by methylene groups, and shows a high charge-imparting effect even in a polymerization toner. The connected calixarene derivatives generally show a higher charge imparting effect. From these facts, by adding an azacalixarene derivative in the dissolution or dispersion preparation step A, it is possible to provide a toner having excellent chargeability, charge rise, durability, and environmental stability of the toner. I understand.

(About FIGS. 1-8)
DESCRIPTION OF SYMBOLS 1 Toner 2 Base particle 3 External additive 500 Roller type charging device 501 Charging roller 502 Core metal 503 Conductive rubber layer 504 Power source 505 Photoconductor 510 Brush type charging device 511 Fur brush roller 512 Core metal 513 Brush part 514 Power source 515 Photoconductor 521 Brush roller 523 Brush portion 524 Power source 525 Photoconductor 600 Developer 601 Development sleeve 602 Power source 603 Development unit 604 Photoconductor 605 Toner 710 Heating roller 720 Fixing roller 721 Core metal 722 Elastic member 730 Endless belt-like fixing belt 731 Base 732 Heating layer 731 Intermediate layer 734 Release layer 740 Pressure roller 741 Core metal 742 Elastic member 760 Induction heating means 761 Excitation coil 762 Coil guide plate 763 Excitation coil core 764 Excitation coil core support member 770 Recording material 800 Process cartridge 801 Photoconductor 802 Charging means 803 Developing means 804 Developer 805 Developing means 806 Cleaning means

(About Figure 9)
DESCRIPTION OF SYMBOLS 100 Image forming apparatus 120Bk, 120C, 120M, 120Y Image writing part 130Bk, 130C, 130M, 130Y Image forming part 140 Paper feeding part 160 Registration roller 200Bk, 200C, 200M, 200Y Developing device 210Bk, 210C, 210M, 210Y 215Bk, 215C, 215M, 215Y Charging device 220 Intermediate transfer belt 230Bk, 230C, 230M, 230Y Primary transfer device 250Bk, 250C, 250M, 250Y Toner transfer pipe 261 Intermediate transfer member cleaning device 262 Intermediate transfer member cleaning device 300Bk, 300C, 300M, 300Y Cleaning device (about Fig. 10)
DESCRIPTION OF SYMBOLS 10 Y, 10C, 10M, 10K Photoconductor 14 1st support roller 15 2nd support roller 16 3rd support roller 17 Intermediate transfer body cleaning apparatus 18 Image forming means 21 Exposure means 22 Secondary transfer means 23 Roller 24 2 Next transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 49 Registration roller 50 Intermediate transfer body 51 Manual feed tray 53 Paper feed Path 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Separation roller 62 Primary transfer device 100 Image forming device 110 Copier main body 120 Tandem image forming device 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separation roller 146 Paper feed path 47 conveying rollers 148 feed path 200 feeder table 300 Scanner 400 automatic document feeder

Japanese Patent No. 3640918 Japanese Patent Laid-Open No. 06-250439 Japanese Patent Publication No.55-42752 JP-A-61-69073 JP 61-221756 A JP-A-9-124659 JP-A-57-111541 JP 62-94856 A Japanese Patent Publication No. 7-31421 Japanese Examined Patent Publication No. 7-104620 Japanese Patent No. 2568675

Claims (16)

A toner comprising at least a binder resin and an azacalixarene derivative, wherein the azacalixarene derivative is a compound represented by the following general formula (I):

However, in the said general formula (I), m and n are integers, respectively, and m + n is 4-8. R ₁ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a — (CH ₂ ) _q COOR ₁₀ (R ₁₀ represents a hydrogen atom or a lower alkyl group, and q represents an integer of 1 to 3). . R ₂ is a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 12 carbon atoms, an aralkyl group, —NO ₂ , —NH ₂ , —N (R ₇ ) ₂ (R ₇ is a lower alkyl group) ), —SO ₃ R ₈ (R ₈ is a hydrogen atom), a phenyl group, an alkoxy group, or —Si (CH ₃ ) ₃ . R ₃ and R ₄ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, —NH ₂ , —N (R ₉ ) ₂ (R ₉ is a lower alkyl group). R ₁₁ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or — (CH ₂ ) _p COOR ₂₀ (R ₂₀ represents a hydrogen atom or a lower alkyl group, and p represents an integer of 1 to 3). . R ₁₂ is a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 12 carbon atoms, an aralkyl group, —NO ₂ , —NH ₂ , —N (R ₁₇ ) ₂ (R ₁₇ is a lower alkyl group) ), —SO ₃ R ₁₈ (R ₁₈ is a hydrogen atom), a phenyl group, an alkoxy group, or —Si (CH ₃ ) ₃ . R ₁₃ and R ₁₄ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, —NH ₂ , or —N (R ₁₉ ) ₂ (R ₁₉ is a lower alkyl group).   Dissolving or dispersing liquid preparation step A in which the toner is prepared by dissolving or dispersing a toner material containing at least a binder resin and an azacalixarene derivative in an organic solvent to prepare a dissolved or dispersed liquid of the toner material, and the toner An emulsification or dispersion preparation step B for preparing an emulsification or dispersion by adding a material dissolution or dispersion into an aqueous medium and emulsifying or dispersing it, and an organic solvent removal step for removing the organic solvent from the emulsification or dispersion The toner according to claim 1, wherein the toner is produced by a toner production method including C.   In the emulsification or dispersion preparation step B, the toner material solution or dispersion is added to an aqueous medium containing anionic resin fine particles having an average particle size of 5 nm to 50 nm and an anionic surfactant to emulsify or disperse. The toner according to claim 2, wherein an emulsified or dispersed liquid is prepared.   4. The toner according to claim 2, wherein an average dispersion diameter of the azacalixarene derivative in a toner material dissolved or dispersed in the dispersion is 10 nm to 500 nm.   The toner according to claim 1, wherein the binder resin is a polyester resin.   The toner according to claim 2, wherein the toner material includes an active hydrogen group-containing compound and a modified polyester resin capable of reacting with the active hydrogen group-containing compound.   The toner according to any one of claims 1 to 6, wherein the content of the azacalixarene derivative in the toner is 0.01% by mass to 5.0% by mass.   The toner according to claim 1, wherein the toner has a charge amount of −80 μC / g to −10 μC / g.   The toner according to claim 1, wherein a common logarithmic value LogR of the electric resistivity R (Ωcm) of the toner is 10.9 LogΩcm to 11.4 LogΩcm.   The toner according to claim 1, wherein the toner has a volume average particle diameter / number average particle diameter (Dv / Dn) of 1.05 to 1.25.   The toner according to claim 1, wherein the toner has an average circularity of 0.950 to 0.990.   A charging step of charging the electrophotographic photosensitive member with a charging unit; an exposure step of forming an electrostatic latent image on the charged electrophotographic photosensitive member with an exposing unit; and a toner obtained by developing the electrostatic latent image with toner A developing process for forming an image, a primary transfer process for transferring the toner image onto an intermediate transfer member by a primary transfer unit, and a toner image transferred on the intermediate transfer member is transferred onto a recording medium by a secondary transfer unit. A secondary transfer step, a fixing step of fixing the toner image transferred onto the recording medium onto the recording medium, and a surface of the electrophotographic photosensitive member on which the toner image is transferred onto the intermediate transfer member by the primary transfer unit. And a cleaning step for cleaning the transfer residual toner adhering thereto, wherein the toner in the developing step is the toner according to claim 1. Color image forming method.   In the secondary transfer step, the linear velocity of transfer of the toner image to the recording material is 300 mm / sec to 1000 mm / sec, and the transfer time at the nip portion of the secondary transfer means is 0.5 msec to 20 msec. The full-color image forming method according to claim 12.   14. The full-color image forming method according to claim 12, wherein a tandem type electrophotographic image forming process is employed.   An electrophotographic photosensitive member; a charging unit that charges the electrophotographic photosensitive member; an exposure unit that forms an electrostatic latent image on the charged electrophotographic photosensitive member; and a static image formed on the electrophotographic photosensitive member. Developing means for converting an electrostatic latent image into a toner image with toner; transfer means for transferring a toner image formed on the electrophotographic photosensitive member onto a recording material with or without an intermediate transfer member; and the recording material Fixing means for fixing the toner image transferred thereon onto a recording material by a heat and pressure fixing member, and attaching the toner image to the surface of the electrophotographic photosensitive member after being transferred onto the intermediate transfer member or recording material by the transfer means. An image forming apparatus comprising: a cleaning unit that cleans the transfer residual toner that is being transferred, wherein the toner is the toner according to claim 1.   A process cartridge having at least an electrophotographic photosensitive member and a developing unit that uses a toner as an electrostatic latent image formed on the electrophotographic photosensitive member, and is detachable from the image forming apparatus main body. A process cartridge, wherein the toner is the toner according to claim 1.

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