JP2005107387A - Toner and method for manufacturing the same, crystalline polyester resin dispersion and method for manufacturing the same, developer, toner-containing vessel, process cartridge, image forming apparatus and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a crystalline polyester resin dispersion which reconciles hot storage resistance with low-temperature fixability and is suitable for use in manufacture of toner capable of forming a high density and high sharpness image. <P>SOLUTION: The crystalline polyester resin dispersion is manufactured by a method including a step of preparing a melt-kneaded material by melt-kneading a crystalline polyester resin and a binder resin, a step of preparing a particle-containing material by forming crystalline polyester resin particles by cooling the melt-kneaded material, and a step of preparing a dispersion of the crystalline polyester resin particles by partly dissolving the particle-containing material in a solvent. A method for manufacturing the toner includes an adhesive base forming step in which an active-hydrogen-containing compound, a polymer capable of reacting with the active-hydrogen-containing compound, and the crystalline polyester resin dispersion are dispersed in an aqueous medium and reacted to obtain a toner while forming an adhesive base. A toner manufactured by the manufacturing method preferably has a softening temperature (Ts) of ≥50°C and a flowage beginning temperature (Tfb) of ≥60°C. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a toner suitably used in electrophotographic methods, electrostatic recording methods, electrostatic printing methods, and the like, and a production method thereof, and a crystalline polyester resin dispersion suitably used in the production of the toner and a production method thereof And a developer using the toner, a container containing toner, a process cartridge, an image forming apparatus, and an image forming method.

Image formation by electrophotography generally forms an electrostatic image on a photoreceptor (electrostatic image carrier), and develops the electrostatic image with a developer containing toner to form a visible image (toner image). Then, the visible image is transferred to a recording medium such as paper and fixed to obtain a fixed image (see Patent Documents 1 and 2, etc.). The toner used in the electrophotographic method is required to have general properties such as anti-aggregation, storage, fluidity, transferability, fixability, and storage stability during storage or transportation.
Recently, with the spread and development of color copying machines, color printers, and the like, attempts have been made to improve image quality by improving the toner for image formation by electrophotography. To increase the image quality, it is effective to reduce the diameter and spheroid of the toner. However, when the diameter of the toner is decreased, the transferability and fixability are reduced. On the other hand, when the toner is spheroidized, the cleaning ability is reduced. (Refer to the column of the prior art in Patent Document 3).

In addition to higher image quality, higher speeds have been studied, and in order to cope with higher speeds, quick fixability is required, particularly good fixability under low temperature conditions (low temperature fixability). Sex) is required. However, when the improvement of the low-temperature fixability is attempted, there is a problem that the thermal stability of the toner is lowered.
In order to improve the low-temperature fixability of the toner, it is conceivable to use a crystalline polyester resin as an adhesive substrate. In this case, a dispersion of the crystalline polyester resin is used in the toner production process. Since the crystalline polyester resin is synthesized in a lump by a condensation polymerization reaction, it is difficult to obtain a dispersion during the polymerization reaction as in the case of a vinyl thermoplastic resin synthesized by an addition polymerization reaction. It is necessary to prepare a dispersion of the crystalline polyester thus prepared after the condensation polymerization reaction. As a method for preparing a dispersion of the crystalline polyester resin, for example, a method using a phase separation solvent exhibiting the characteristics of a solvent or a non-solvent according to temperature is known (see Patent Document 4). However, in the case of this method, only a dispersion containing coarse particles having a dispersed particle diameter of several tens of μm can be obtained, and a volume average particle diameter of 2 μm or less can be obtained. There is a problem that can not be.

  Accordingly, a toner having excellent properties such as anti-aggregation property, charging property, fluidity, transferability, fixability, etc., good heat storage stability and low-temperature fixability, an efficient production method thereof, and the toner The related technology used has not yet been provided.

US Pat. No. 2,297,691 Japanese Patent Publication No.43-24748 JP 9-258474 A JP-A-8-176310

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention has sharp melt properties, has both heat-resistant storage stability and low-temperature fixability, is excellent in offset resistance, charging properties, charging stability, cleaning properties, etc., and is soiled even in various environments. Capable of forming a high-quality image with high image density without causing filming or filming, and an efficient manufacturing method thereof, and a crystalline polyester dispersion suitable for manufacturing the toner and its efficient Another object of the present invention is to provide a manufacturing method, a developer using the toner, a container containing toner, a process cartridge, an image forming apparatus, and an image forming method.

ただし、前記構造式（１）中、Ｒ^１及びＲ^２は、互いに同一であってもよいし、異なっていてもよく、水素原子又は炭化水素基を表す。Ｒ^３は、二価炭化水素基を表す。ｍは、１以上の整数を表す。ｎは、重合度を表す。
＜４＞ 結晶性ポリエステル樹脂が、赤外線吸収（ＩＲ）スペクトルにおける９６５±１０ｃｍ^−１及び９９０±１０ｃｍ^−１のいずれかの範囲にオレフィンのδｃｈ（面外変角振動）に基づく吸収を有する前記＜１＞から＜３＞のいずれかに記載の結晶性ポリエステル樹脂分散液の製造方法である。
＜５＞ 結晶性ポリエステル樹脂の融解温度Ｔｍ（℃）が、ＤＳＣ吸熱ピーク温度で５０〜１５０℃である前記＜１＞から＜４＞のいずれかに記載の結晶性ポリエステル樹脂分散液の製造方法である。
＜６＞ 結晶性ポリエステル樹脂における重量平均分子量（Ｍｗ）が１,０００〜３０,０００であり、数平均分子量（Ｍｎ）が５００〜６,０００であり、かつ分子量分布（Ｍｗ／Ｍｎ）が２〜８である前記＜１＞から＜５＞のいずれかに記載の結晶性ポリエステル樹脂分散液の製造方法である。
＜７＞ 結着樹脂が、ポリエステル樹脂、ポリオール樹脂、ポリスチレン樹脂及びポリスチレンアクリル樹脂から選択される少なくとも１種である前記＜１＞から＜６＞のいずれかに記載の結晶性ポリエステル樹脂分散液の製造方法である。
＜８＞ 溶融混練物における結晶性ポリエステル樹脂の固形分濃度が、結着樹脂に対し１〜５０質量％である前記＜１＞から＜７＞のいずれかに記載の結晶性ポリエステル樹脂分散液の製造方法である。
＜９＞ 溶融混練の温度Ｔｓ（℃）が、結晶性ポリエステル樹脂の融解温度をＴｍ（℃）とした時、次式、Ｔｍ≦Ｔｓ≦（Ｔｍ＋５０℃）、の関係を満たす前記＜１＞から＜８＞のいずれかに記載の結晶性ポリエステル樹脂分散液の製造方法である。
＜１０＞ 溶剤が、結晶性ポリエステル樹脂の融解温度をＴｍ（℃）とした時、（Ｔｍ−４０）未満の温度（℃）では該ポリエステル樹脂を溶解不能であり、（Ｔｍ−４０）以上の温度（℃）では該ポリエステル樹脂を溶解可能である前記＜１＞から＜９＞のいずれかに記載の結晶性ポリエステル樹脂分散液の製造方法である。
＜１１＞ 前記＜１＞から＜１０＞のいずれかに記載の結晶性ポリエステル樹脂分散液の製造方法により製造されることを特徴とする結晶性ポリエステル樹脂分散液である。
＜１２＞ 結晶性ポリエステル樹脂粒子の体積平均粒径が、０．２〜２μｍである前記＜１１＞に記載の結晶性ポリエステル樹脂分散液である。
＜１３＞ 活性水素基含有化合物と、該活性水素基含有化合物と反応可能な重合体と、前記＜１１＞から＜１２＞のいずれかに記載の結晶性ポリエステル樹脂分散液とを、水系媒体中で分散させかつ反応させて接着性基材を生成させつつトナーを得る接着性基材生成工程を少なくとも含むことを特徴とするトナーの製造方法である。
＜１４＞ 前記＜１３＞に記載のトナーの製造方法により製造されることを特徴とするトナーである。
＜１５＞ 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重合体を反応させて水系媒体中で接着性基材を生成しつつ粒子状に得られ、結晶性ポリエステル樹脂粒子を含む前記＜１４＞に記載のトナーである。
＜１６＞ 軟化温度（Ｔｓ）が５０℃以上であり、かつ流出開始温度（Ｔｆｂ）が６０℃以上である前記＜１４＞から＜１５＞のいずれかに記載のトナーである。
＜１７＞ 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重合体を反応させて水系媒体中で接着性基材を生成しつつ粒子状に得られ、結晶性ポリエステル樹脂粒子を含み、軟化温度（Ｔｓ）が５０℃以上であり、かつ流出開始温度（Ｔｆｂ）が６０℃以上であることを特徴とするトナーである。
＜１８＞ 前記＜１４＞から＜１７＞のいずれかに記載のトナーを含むことを特徴とする現像剤である。
＜１９＞ 前記＜１４＞から＜１７＞のいずれかに記載のトナーを容器中に収容してなることを特徴とするトナー入り容器である。 Means for solving the problems are as follows. That is,
<1> A melt-kneaded material preparation step for preparing a melt-kneaded material by melt-kneading a crystalline polyester resin and a binder resin, cooling the melt-kneaded material to form crystalline polyester resin particles, and containing particles A particle-containing material preparation step for preparing a product, and a particle dispersion preparation step for preparing a dispersion of the crystalline polyester resin particles by partially dissolving the particle-containing material with a solvent. It is a manufacturing method of a polyester resin dispersion.
<2> The method for producing a crystalline polyester resin dispersion according to <1>, wherein the crystalline polyester resin dispersion is used for producing a toner.
<3> The method for producing a crystalline polyester resin dispersion according to any one of <1> to <2>, wherein the crystalline polyester resin includes a structure represented by the following structural formula (1).

However, in the structural formula (1), R ¹ and R ² may be the same as or different from each other, and represent a hydrogen atom or a hydrocarbon group. R ³ represents a divalent hydrocarbon group. m represents an integer of 1 or more. n represents the degree of polymerization.
<4> Crystalline polyester resin, wherein having an absorption based on the infrared absorption of the olefin to one of a range of 965 ± 10 cm ^-1 and 990 ± 10 cm ^-1 in (IR) spectrum? Ch (out-of-plane deformation vibration) < It is a manufacturing method of the crystalline polyester resin dispersion liquid in any one of <1> to <3>.
<5> The method for producing a crystalline polyester resin dispersion according to any one of <1> to <4>, wherein the melting temperature Tm (° C.) of the crystalline polyester resin is 50 to 150 ° C. as a DSC endothermic peak temperature. It is.
<6> The crystalline polyester resin has a weight average molecular weight (Mw) of 1,000 to 30,000, a number average molecular weight (Mn) of 500 to 6,000, and a molecular weight distribution (Mw / Mn) of 2. It is a manufacturing method of the crystalline polyester resin dispersion in any one of said <1> to <5> which is -8.
<7> The crystalline polyester resin dispersion according to any one of <1> to <6>, wherein the binder resin is at least one selected from a polyester resin, a polyol resin, a polystyrene resin, and a polystyrene acrylic resin. It is a manufacturing method.
<8> The crystalline polyester resin dispersion according to any one of <1> to <7>, wherein the solid content concentration of the crystalline polyester resin in the melt-kneaded product is 1 to 50% by mass with respect to the binder resin. It is a manufacturing method.
<9> From the above <1>, the melt-kneading temperature Ts (° C.) satisfies the relationship of the following formula: Tm ≦ Ts ≦ (Tm + 50 ° C.) when the melting temperature of the crystalline polyester resin is Tm (° C.). <8> A method for producing a crystalline polyester resin dispersion according to any one of the above.
<10> When the melting temperature of the crystalline polyester resin is Tm (° C.), the solvent cannot dissolve the polyester resin at a temperature (° C.) lower than (Tm-40), and is not lower than (Tm-40). The method for producing a crystalline polyester resin dispersion according to any one of <1> to <9>, wherein the polyester resin can be dissolved at a temperature (° C.).
<11> A crystalline polyester resin dispersion produced by the method for producing a crystalline polyester resin dispersion according to any one of <1> to <10>.
<12> The crystalline polyester resin dispersion according to <11>, wherein the crystalline polyester resin particles have a volume average particle size of 0.2 to 2 μm.
<13> An active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and the crystalline polyester resin dispersion according to any one of <11> to <12>, in an aqueous medium A method for producing a toner, comprising at least an adhesive base material production step of obtaining a toner while producing an adhesive base material by dispersing and reacting with the above.
<14> A toner produced by the method for producing a toner according to <13>.
<15> An active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted to form an adhesive base material in an aqueous medium, and are obtained in the form of particles, including crystalline polyester resin particles The toner according to <14>.
<16> The toner according to any one of <14> to <15>, wherein the softening temperature (Ts) is 50 ° C. or higher and the outflow start temperature (Tfb) is 60 ° C. or higher.
<17> An active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted to produce an adhesive base material in an aqueous medium, and are obtained in the form of particles, including crystalline polyester resin particles The toner has a softening temperature (Ts) of 50 ° C. or higher and an outflow start temperature (Tfb) of 60 ° C. or higher.
<18> A developer comprising the toner according to any one of <14> to <17>.
<19> A toner-containing container, wherein the toner according to any one of <14> to <17> is contained in a container.

The method for producing a crystalline polyester resin dispersion according to the present invention comprises a melt-kneaded material preparation step in which a crystalline polyester resin and a binder resin are melt-kneaded to prepare a melt-kneaded product, the melt-kneaded product is cooled, A particle-containing material preparing step of forming a crystalline polyester resin particle to prepare a particle-containing material, and a particle dispersion preparing step of preparing the crystalline polyester resin particle dispersion by partially dissolving the particle-containing material with a solvent, including. In the method for producing the crystalline polyester resin dispersion, in the melt kneaded material preparing step, the crystalline polyester resin and the binder resin are melt kneaded to prepare a melt kneaded material. In the particle-containing material preparation step, the melt-kneaded product is cooled to form crystalline polyester resin particles to prepare a particle-containing material. In the particle dispersion preparation step, the particle-containing material is partially dissolved with a solvent to prepare a dispersion of the crystalline polyester resin particles. That is, in the melt-kneaded product, the crystalline polyester resin particles are dispersed in the binder resin, and the binder resin is dissolved in the solvent. As a result, the crystalline polyester resin particles A dispersion in which is dispersed is prepared.
In the method for producing a crystalline polyester resin dispersion according to the present invention, the molecular weight distribution of the crystalline polyester resin indicates that log (M) is abscissa and G (according to GPC of soluble part of o-dichlorobenzene). In the molecular weight distribution diagram in which the weight represents% (%), the peak position is in the range of 3.5 to 4.0, and the half width of the peak is 1.5 or less, the crystalline polyester resin is a diol compound and An embodiment synthesized by a polycondensation reaction with a dicarboxylic acid compound, an embodiment in which the diol compound is selected from 1,4-butanediol, 1,6-hexanediol and derivatives thereof, and an embodiment in which the binder resin is a polyester resin An embodiment in which the glass transition temperature (Tg) of the binder resin is 30 to 80 ° C., an embodiment in which the weight average molecular weight (Mw) of the binder resin is 2,000 to 90,000, and melt mixing A mode in which the cooling rate in cooling the kneaded product is 0.1 to 10 ° C./min, a mode in which the solvent is at least one selected from toluene, ethyl acetate, methyl ethyl ketone, and tetrahydrofuran, and partial dissolution of the melt-kneaded product by the solvent A mode in which the melting temperature of the crystalline polyester resin is (Tm) and the temperature is (Tm-40) to (Tm-30) (° C.) is preferable.

  The crystalline polyester resin dispersion of the present invention is produced by the method for producing a crystalline polyester resin dispersion of the present invention. When a toner is produced using the crystalline polyester resin dispersion, crystalline polyester resin particles are taken into the resulting toner. The crystalline polyester resin particles have crystallinity and exhibit good heat storage stability immediately before the melting start temperature, while exhibiting a sharp viscosity decrease (sharp melt property) above the melting start temperature. The toner containing the conductive polyester resin particles can achieve both heat-resistant storage stability and low-temperature fixability.

  In the toner production method of the present invention, an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and the crystalline polyester resin dispersion are dispersed and reacted in an aqueous medium. It includes at least an adhesive substrate generation step for obtaining a toner while generating an adhesive substrate. In the method for producing a toner of the present invention, in the adhesive base material production step, an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and the crystalline polyester resin dispersion are: Dispersed and reacted in an aqueous medium to produce an adhesive substrate and a toner is obtained. According to the method for producing a toner of the present invention, the obtained toner exhibits good heat-resistant storage stability immediately before the melting start temperature, while exhibiting a sharp viscosity decrease (sharp melt property) above the melting start temperature. Polyester resin particles can be highly dispersed. As a result, it is possible to achieve both heat-resistant storage stability and low-temperature fixability, and is excellent in offset resistance, chargeability, charging stability, cleaning properties, etc., without causing soiling or filming in various environments, A toner capable of forming a high-quality image with high image density and high sharpness is efficiently produced.

  One toner of the present invention is manufactured by the toner manufacturing method. In the toner, crystalline polyester resin particles exhibiting good heat-preserving storage immediately before the melting start temperature, but exhibiting a sharp viscosity decrease (sharp melt property) above the melting start temperature are dispersed. As a result, the toner has both heat-resistant storage stability and low-temperature fixability, and is excellent in offset resistance, chargeability, charge stability, cleaning properties, etc., and can be used for soiling and filming in various environments. A high-quality image with high image density and high sharpness can be formed without the occurrence. Since the toner includes the adhesive base obtained by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an aqueous medium, the toner has anti-aggregation property, chargeability, and fluidity. Excellent properties such as transferability and fixability.

Another toner of the present invention is obtained in the form of particles while producing an adhesive substrate in an aqueous medium by reacting an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound. Polyester resin particles are included, the softening temperature (Ts) is 50 ° C. or higher, and the outflow start temperature (Tfb) is 60 ° C. or higher. In the toner, crystalline polyester resin particles exhibiting good heat-preserving storage immediately before the melting start temperature, but exhibiting a sharp viscosity decrease (sharp melt property) above the melting start temperature are dispersed. As a result, the toner has both heat-resistant storage stability and low-temperature fixability, and is excellent in offset resistance, chargeability, charge stability, cleaning properties, etc., and can be used for soiling and filming in various environments. A high-quality image with high image density and high sharpness can be formed without the occurrence. Further, since the toner includes the adhesive base material obtained by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an aqueous medium, the aggregation resistance, charging property, Excellent properties such as fluidity, transferability and fixability.
In the toner, an embodiment in which the toner binder includes a polyester resin, an embodiment in which the polyester resin includes a urea-modified polyester resin, an embodiment including at least one selected from a colorant, a release agent, and a charge control agent, a volume average A mode in which the particle size is 3 to 8 μm and the ratio of the volume average particle size to the number average particle size (volume average particle size / number average particle size) is 1.00 to 1.25, and the average circularity is 0 Preferred is an aspect of 900 to 0.995, an aspect of at least one selected from cyan toner, magenta toner, yellow toner and black toner.

The developer of the present invention contains the toner of the present invention. For this reason, when an image is formed by electrophotography using the developer, a high-quality image with a high image density and a high sharpness can be formed without causing stains or filming even under low temperature conditions.
In the developer of the present invention, an embodiment that is either a one-component developer or a two-component developer is preferable.

  The toner-containing container of the present invention contains the toner of the present invention in a container. For this reason, when image formation is performed by electrophotography using the toner contained in the toner-containing container, a high-quality image with high image density and high sharpness is produced without causing scumming or filming even under low temperature conditions. Is formed.

  The process cartridge of the present invention comprises an electrostatic latent image carrier, and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner of the present invention to form a visible image. At least. The process cartridge is attachable to and detachable from the image forming apparatus, is excellent in convenience, and uses the toner of the present invention. Therefore, the process cartridge does not cause scumming or filming even under low temperature conditions and has a high image density. A sharp high quality image can be formed.

  The image forming apparatus of the present invention includes an electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image of the present invention. The image forming apparatus includes at least a developing unit that forms a visible image by developing with toner, a transfer unit that transfers the visible image to a recording medium, and a fixing unit that fixes the transferred image transferred to the recording medium. In the image forming apparatus, the electrostatic latent image forming unit forms an electrostatic latent image on the electrostatic latent image carrier. The developing means develops the electrostatic latent image using the toner of the present invention to form a visible image. The transfer means transfers the visible image to a recording medium. The fixing unit fixes the transferred image transferred to the recording medium. As a result, a high-quality image with high image density and high sharpness can be formed without causing soiling or filming even under low temperature conditions.

  The image forming method of the present invention comprises an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and developing the electrostatic latent image with the toner of the present invention to make visible. It includes at least a developing step for forming an image, a transfer step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium. In the image forming apparatus, an electrostatic latent image is formed on the electrostatic latent image carrier in the electrostatic latent image forming step. In the developing step, the electrostatic latent image is developed using the toner of the present invention to form a visible image. In the transfer step, the visible image is transferred to a recording medium. In the fixing step, the transferred image transferred to the recording medium is fixed. As a result, a high-quality image with high image density and high sharpness can be formed without causing soiling or filming even under low temperature conditions.

  According to the present invention, conventional problems can be solved, it has sharp melt properties, has both heat-resistant storage stability and low-temperature fixability, and is excellent in offset resistance, charging properties, charging stability, cleaning properties, etc. , A toner capable of forming a high-quality image with high image density and high sharpness without causing scumming or filming under various environments, an efficient manufacturing method thereof, and suitable for manufacturing the toner A crystalline polyester dispersion and an efficient production method thereof, a developer using the toner, a container containing toner, a process cartridge, an image forming apparatus, and an image forming method can be provided.

(Crystalline polyester resin dispersion and method for producing the same)
The crystalline polyester resin dispersion of the present invention is produced by the method for producing a crystalline polyester resin dispersion of the present invention.
The method for producing a crystalline polyester resin dispersion of the present invention includes a melt-kneaded product preparation step, a particle-containing material preparation step, and a particle dispersion preparation step, and further includes other steps as necessary.
Hereinafter, the details of the crystalline polyester resin dispersion of the present invention will be clarified through the description of the method for producing the crystalline polyester resin dispersion of the present invention.

-Melt-kneaded preparation process-
The melt-kneaded material preparing step is a step of preparing a melt-kneaded material by melt-kneading the crystalline polyester resin and the binder resin.

As solid content density | concentration of the said crystalline polyester resin in the said melt kneaded material, 1-50 mass% is preferable with respect to the said binder resin, 5-45 mass% is more preferable, 10-40 mass% is more preferable.
When the solid content concentration of the crystalline polyester resin is less than 1% by mass, the particle size becomes small, but it may be compatible with the binder resin or the productivity may be reduced, and exceeds 50% by mass. In addition, the particle size in the melt-kneaded product becomes large, and it may be difficult to prepare a crystalline polyester resin dispersion having a small particle size.

There is no restriction | limiting in particular as temperature Ts (degreeC) in the case of the said melt-kneading, According to the objective, it can select suitably, For example, when the melting temperature of the said crystalline polyester resin is set to Tm (degreeC), It is preferable to satisfy the formula, Tm ≦ Ts ≦ (Tm + 50 ° C.), and it is more preferable to satisfy the following formula, Tm ≦ Ts ≦ (Tm + 30 ° C.).
If the temperature Ts (° C.) during the melt kneading is less than Tm ° C., the melt kneading time may become long or the melt kneading itself may be difficult. If it exceeds (Tm + 50 ° C.), the production energy , And the subsequent cooling efficiency may deteriorate.

There is no restriction | limiting in particular as the method of the said melt kneading | mixing, It can select suitably from a well-known method, It can carry out using a well-known kneading apparatus etc. Examples of the kneading apparatus include a batch type two roll, a Banbury mixer, a continuous type twin screw extruder, a continuous type single screw kneader, and the like.
Commercially available products of the continuous twin screw extruder include, for example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type twin screw extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by KCK, Ikekai Tekko Co., Ltd. Examples thereof include a PCM type twin screw extruder and a KEX type twin screw extruder manufactured by Kurimoto Iron Works. As a commercial item of the continuous uniaxial kneader, for example, Bush Co. Kneader may be mentioned.

--- Crystalline polyester resin--
There is no restriction | limiting in particular as said crystalline polyester resin, Although it can select suitably according to the objective, For example, what is represented by following Structural formula (1) is mentioned suitably.

In the structural formula (1), m represents an integer of 1 or more, and preferably 1 to 3. n represents a polymerization degree and represents an integer of 1 or more.
In the structural formula (1), R ¹ and R ² may be the same as or different from each other, and represent a hydrogen atom or a hydrocarbon group.
There is no restriction | limiting in particular as said hydrocarbon group, According to the objective, it can select suitably, For example, an alkyl group, an alkenyl group, an aryl group, etc. are mentioned. These may be further substituted with a substituent.
As the alkyl group, those having 1 to 10 carbon atoms are preferable, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, n-hexyl group, Examples include isohexyl group, n-heptyl group, n-octyl group, isooctyl group, n-decyl group, isodecyl group and the like. As said alkenyl group, a C2-C10 thing is more preferable, For example, a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group, an octenyl group etc. are mentioned. As said aryl group, a C6-C24 thing is more preferable, For example, a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a styryl group, a mesityl group, a cinnamyl group, a phenethyl group, a benzhydryl group etc. are mentioned.

In the structural formula (1), R ³ represents a divalent hydrocarbon group, preferably having 1 to 10 carbon atoms. For example, — (CH ₂ ) _p — (where p represents 1 to 10). .), And the like. Among _{these, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2 -, - CH 2 C (CH 3) H-, etc. are particularly preferable.

About crystallinity, molecular structure, etc. of the crystalline polyester resin, NMR measurement, differential scanning calorimeter (DSC) measurement, X-ray diffraction measurement, GC / MS measurement, LC / MS measurement, infrared absorption (IR) spectrum measurement, Etc. can be confirmed.
For example, in the infrared absorption (IR) spectrum, it is preferable to have absorption based on δch (out-of-plane variable angular vibration) of olefin in the range of 965 ± 10 cm ⁻¹ and 990 ± 10 cm ^−1. What is shown can be evaluated as crystalline.

  The molecular weight distribution of the crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably sharp, and the lower the molecular weight, the better the low-temperature fixability. In a molecular weight distribution chart in which the horizontal axis represents log (M) and the vertical axis represents mass%, the peak position is 3.5 to 4 by gel permeation chromatography (GPC) of soluble components of orthodichlorobenzene. It is preferably in the range of 0.0 and the half width of the peak is 1.5 or less.

There is no restriction | limiting in particular as a weight average molecular weight (Mw) of the said crystalline polyester resin, According to the objective, it can select suitably, For example, 1,000-30,000 are preferable, 1,200-20,000 Is more preferable.
When the weight average molecular weight is less than 1,000, the low-temperature fixability may be deteriorated, and when it exceeds 30,000, the sharp melt property may be deteriorated.
There is no restriction | limiting in particular as a number average molecular weight (Mn) of the said crystalline polyester resin, According to the objective, it can select suitably, For example, 500-6,000 are preferable and 700-5,500 are more preferable.
When the number average molecular weight is less than 500, the low-temperature fixability may be deteriorated, and when it exceeds 6,000, the sharp melt property may be deteriorated.
The molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is not particularly limited and can be appropriately selected according to the purpose. 2-8 are preferable.
When the molecular weight distribution (Mw / Mn) is less than 2, production may be difficult and costly. When it exceeds 8, the sharp melt property may be deteriorated.

The melting temperature (Tm) of the pre-crystalline polyester resin (sometimes referred to as “F _1/2 temperature”) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a differential scanning calorimeter (DSC) The DSC endothermic peak temperature in the DSC curve obtained by measurement is preferably 50 to 150 ° C, more preferably 60 to 130 ° C.
When the melting temperature (Tm) is less than 50 ° C., the heat-resistant storage stability is deteriorated, and blocking may easily occur at the temperature inside the developing device. When the melting temperature (Tm) exceeds 150 ° C., the lower limit fixing temperature is increased. Therefore, low temperature fixability may not be obtained.

There is no restriction | limiting in particular as an acid value of the said crystalline polyester resin, According to the objective, it can select suitably, For example, 5 mgKOH / g or more is preferable and 10 mgKOH / g or more is more preferable. In addition, from a viewpoint of improving hot offset property, 45 mgKOH / g or less is preferable.
If the acid value is less than 5 mg KOH / g, the affinity between paper and resin and the desired low-temperature fixability may not be achieved.
The acid value of the crystalline polyester resin can be measured, for example, by dissolving in 1,1,1,3,3,3-hexafluoro-2-propanol and titrating.

There is no restriction | limiting in particular as a hydroxyl value of the said crystalline polyester resin, According to the objective, it can select suitably, For example, 0-50 mgKOH / g is preferable and 5-50 mgKOH / g is more preferable.
If the hydroxyl value exceeds 50 mgKOH / g, it may be impossible to achieve a predetermined low-temperature fixability and good charging characteristics.
The hydroxyl value of the crystalline polyester resin can be measured, for example, by dissolving and titrating in 1,1,1,3,3,3-hexafluoro-2-propanol.

  The crystalline polyester resin can be synthesized, for example, by subjecting an alcohol component and an acid component to a polycondensation reaction.

There is no restriction | limiting in particular as said alcohol component, According to the objective, it can select suitably, For example, a diol compound etc. are mentioned suitably.
As said diol compound, C2-C8 is preferable, for example, and 2-6 are more preferable, for example, 1, 4- butanediol, ethylene glycol, 1, 2- propylene glycol, 1, 3- propylene glycol, 1 , 6-hexanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, and derivatives thereof. These can be used individually by 1 type and can use 2 or more types together. Among these, 1,4-butanediol and 1,6-hexanediol are preferable.
As the usage-amount of the said diol compound, 80 mol% or more is preferable in the said alcohol component, and 85-100 mol% is more preferable. If the content of the diol compound in the alcohol component is less than 80 mol%, the production efficiency may deteriorate.

The acid component is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include carboxylic acids having a carbon double bond, dicarboxylic acid compounds, and polyvalent carboxylic acid compounds. Of these, dicarboxylic acid compounds are preferred.
Examples of the dicarboxylic acid compound include those having 2 to 8 carbon atoms, and more preferably those having 2 to 6 carbon atoms, such as oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, and glutaconic acid. Succinic acid, adipic acid, anhydrides of these acids, alkyl esters having 1 to 3 carbon atoms, and the like. These may be used individually by 1 type and may use 2 or more types together. Of these, fumaric acid is preferred.
As the usage-amount of the said dicarboxylic acid compound, 80 mol% or more is preferable in an acid component, and 85-100 mol% is more preferable. If the content of the dicarboxylic acid compound in the acid component is less than 80 mol%, the production efficiency may deteriorate.
Examples of the polyvalent carboxylic acid compound include trimellitic acid, pyromellitic acid, acid anhydrides thereof, alkyl esters having 1 to 3 carbon atoms of these acids, and the like.

There is no restriction | limiting in particular as said polycondensation reaction, According to the objective, it can select suitably, For example, it is made to react at 120-230 degreeC using an esterification catalyst, a polymerization inhibitor, etc. in inert gas atmosphere. This can be done.
When the polycondensation reaction is performed, a divalent monomer is reacted for the purpose of charging all monomers at once or reducing low molecular weight components for the purpose of improving the strength of the resulting crystalline polyester resin. Then, for the purpose of promoting the reaction by adding a trivalent or higher monomer, the reaction system is depressurized in the latter half of the polycondensation reaction, and the crystallinity and softening point of the crystalline polyester resin are determined. For the purpose of control, during the polycondensation reaction, a trihydric or higher polyhydric alcohol such as glycerin is added as the alcohol component, and a trihydric or higher polyvalent carboxylic acid such as trimellitic anhydride is added as the acid component. Non-linear polyester may be obtained or the like.

  Here, it is as follows when an example of the manufacturing method of the said crystalline polyester resin is shown. That is, for example, 1,5-butanediol, fumaric acid, trimellitic anhydride, and hydroquinone are charged into a 5-liter four-necked flask equipped with a nitrogen introducing tube, a dehydrating tube, a stirrer, and a thermocouple, After reacting at 5 ° C. for 5 hours, the temperature was raised to 200 ° C. and reacted for 1 hour. Next, a crystalline polyester resin can be synthesized by reacting under pressure of 8.3 kPa for 1 hour.

--Binder resin--
The binder resin is not particularly limited and can be appropriately selected from known binder resins in the toner. Examples thereof include polyester resins, polyol resins, polystyrene resins, polystyrene acrylic resins, and the like. . These may be used individually by 1 type and may use 2 or more types together. Among these, when the main component of the adhesive base material in the toner is a polyester resin, the polyester resin is preferable in terms of compatibility at the time of fixing, and it is used for low-temperature fixability and a full-color image forming apparatus. A polyester resin is preferable also in terms of improving glossiness in some cases.

There is no restriction | limiting in particular as glass transition temperature (Tg) of the said binder resin, According to the objective, it can select suitably, For example, 30-80 degreeC is preferable and 40-65 degreeC is more preferable.
When the glass transition temperature (Tg) is less than 30 ° C, the heat-resistant storage stability may be deteriorated, and when it exceeds 80 ° C, the low-temperature fixability may be deteriorated.

There is no restriction | limiting in particular as a weight average molecular weight (Mw) of the said binder resin, According to the objective, it can select suitably, For example, 2,000-90,000 are preferable and 2,500-30,000 are preferable. More preferred.
When the weight average molecular weight is less than 2,000, heat-resistant storage stability may be deteriorated, and when it exceeds 90,000, low-temperature fixability may be deteriorated.

-Particle content preparation process-
The particle-containing material preparation step is a step of cooling the melt-kneaded material to form crystalline polyester resin particles to prepare a particle-containing material.
There is no restriction | limiting in particular as a cooling rate in the case of cooling of the said melt-kneaded material, According to the objective, it can select suitably, For example, 0.1-10 degreeC / min is preferable, 0.1-8 degreeC / min. Minute is more preferable, and 0.1 to 5 ° C./minute is particularly preferable.
When the cooling rate is less than 0.1 ° C./min, the production efficiency may deteriorate, and when it exceeds 10 ° C./min, much production energy may be consumed.
The cooling can be performed using a known cooling device or the like. In the present invention, after the cooling, coarse pulverization may be performed using, for example, a hammer mill, a rotoplex or the like.

The crystalline polyester resin particles can be formed in the molten mixture by the cooling, but the particle size of the crystalline polyester resin particles is not particularly limited and may be appropriately selected depending on the purpose. For example, the volume average particle size is preferably 0.2 μm to 2 μm.
When the volume average particle size of the crystalline polyester resin particles is less than 0.2 μm, the low-temperature fixability may be deteriorated, and when it exceeds 2 μm, it may not be contained in the toner.

-Particle dispersion preparation process-
The particle dispersion preparation step is a step of preparing a dispersion of the crystalline polyester resin particles by partially dissolving the particle-containing material with a solvent.
The solvent is not particularly limited and may be appropriately selected depending on the intended purpose.For example, an organic solvent is preferably used, but at a high temperature, the crystalline polyester resin is completely dissolved to form a transparent uniform solution. Preferably, it is insoluble or hardly soluble in the crystalline polyester resin at low temperatures and forms an opaque heterogeneous solution. When the melting temperature of the crystalline polyester resin is (Tm), (Tm-40 It is more preferable that the crystalline polyester resin cannot be dissolved at a temperature (° C.) lower than), and that the crystalline polyester resin can be dissolved at a temperature (° C.) equal to or higher than (Tm-40).
There is no restriction | limiting in particular as said organic solvent, According to the objective, it can select suitably, For example, toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran etc. are mentioned, for example. Among these, toluene, ethyl acetate, methyl ethyl ketone, and tetrahydrofuran are preferable. These may be used individually by 1 type and may use 2 or more types together.

The temperature at the time of partial dissolution differs depending on the type of solvent used and the like, and cannot be specified unconditionally. For example, when the melting temperature of the crystalline polyester resin is (Tm), A temperature (° C.) of (Tm-40) to (Tm-30) is preferable, and a temperature (° C.) of (Tm-40) to (Tm-35) is more preferable.
When the temperature at the time of partial dissolution is a temperature (° C.) lower than (Tm-40), the dissolution portion at normal temperature may increase, and the temperature (° C.) exceeds (Tm-30). In manufacturing, a lot of energy may be required.

There is no restriction | limiting in particular as the usage-amount of the said solvent, According to the objective, it can select suitably, For example, 30-900 mass parts is preferable with respect to 100 mass parts of said melt-kneaded materials, 40-400 mass parts is More preferred.
When the amount used is less than 30 parts by mass, the clay of the dispersion liquid may be high, and when it exceeds 900 parts by mass, the production efficiency may be deteriorated or the cost may be increased.

  Here, it is as follows when an example of the manufacturing method of the crystalline polyester resin dispersion liquid of this invention is shown. That is, after the crystalline polyester resin and the polyester resin as the binder resin are sufficiently mixed with a blender, the mixture is melt-kneaded using a twin screw extruder having a cooling function, and then 0.1 to 10 ° C / A melt-kneaded product (master batch) is prepared by cooling to a cooling rate of 1 minute. A particle dispersion containing crystalline polyester resin particles having a volume average particle size of 0.2 μm to 2 μm can be prepared by partially dissolving the obtained melt-kneaded product in ethyl acetate as the organic solvent. .

There is no restriction | limiting in particular as a volume average particle diameter of the said crystalline polyester resin particle contained in the said particle dispersion liquid, Although it can select suitably according to the objective, For example, 0.2-2 micrometers is preferable.
When the volume average particle size is less than 0.2 μm, the low-temperature fixability may be deteriorated. When the volume average particle size is more than 2 μm, the volume average particle size is too large and may be unsuitable for toner use.

Since the crystalline polyester resin particles contained in the particle dispersion have crystallinity, when used for the toner, the crystalline polyester resin particles exhibit good heat storage stability until just before the melting start temperature, while melting starts. Above the temperature, the viscosity is drastically decreased, sharp meltability can be imparted to the toner, a toner having both good heat storage stability and low-temperature fixability can be obtained, and the release width of the toner (Difference between the minimum fixing temperature and the hot offset occurrence temperature) can be improved, and a toner exhibiting good fixability can be obtained.
The crystalline polyester resin particle dispersion of the present invention produced by the method for producing a crystalline polyester resin dispersion of the present invention can be used in various fields. It can be particularly preferably used.

(toner)
As the toner of the present invention, (1) a first form produced by the toner production method of the present invention described later, (2) an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted. The toner binder is produced in an aqueous medium and obtained in the form of particles, including crystalline polyester resin particles, the softening temperature (Ts) is 50 ° C. or higher, and the outflow start temperature (Tfb) is 60 ° C. or higher. A certain second form is particularly preferred.
In the case of the first embodiment, an embodiment including the adhesive base material and the crystalline polyester resin particles described above, the softening temperature (Ts) is 50 ° C. or higher, and the outflow start temperature (Tfb) is 60 ° C. or higher. It is preferable that it is at least 1 selected from the aspect etc. which are. In the case of the second embodiment, an embodiment manufactured by the toner manufacturing method of the present invention described later is preferable.

  The toner of the present invention further contains other components such as a colorant, a release agent, resin fine particles, and a charge control agent, if necessary, in addition to the adhesive base and the crystalline polyester resin particles described above.

-Adhesive substrate-
The adhesive substrate is obtained by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium, and is obtained in the form of particles. Other binders appropriately selected from binder resins may be included.

The weight average molecular weight of the adhesive substrate is not particularly limited and may be appropriately selected depending on the purpose. For example, 1,000 or more is preferable, and 2,000 to 10,000,000 is more preferable. 3,000 to 1,000,000 is particularly preferred.
When the weight average molecular weight is less than 1,000, the hot offset resistance may be deteriorated.

There is no restriction | limiting in particular as glass transition temperature (Tg) of the said adhesive base material, According to the objective, it can select suitably, For example, 30-70 degreeC is preferable and 40-65 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 addition, the storage elastic modulus (TG ′) of the adhesive base material is preferably higher than the viscosity (Tη) of the adhesive base material from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability. Specifically, the difference ΔT (TG′−Tη) between the storage elastic modulus (TG ′) and the viscosity temperature (Tη) is preferably 0 to 100 ° C., more preferably 10 to 90 ° C. Preferably, it is 20-80 degreeC.

  In the present invention, the physical properties of the adhesive base contained in the toner are directly related to physical properties such as the flow characteristics of the toner, and the weight average molecular weight, the glass transition temperature ( Tg), the storage elastic modulus (TG ′), the difference ΔT (TG′−Tη) between the storage elastic modulus (TG ′) and the viscosity temperature (Tη), and the like, are the physical properties of the toner as they are. it can.

There is no restriction | limiting in particular as a specific example of the said adhesive base material, According to the objective, it can select suitably, A polyester-type resin etc. are mentioned especially suitably.
There is no restriction | limiting in particular as said polyester resin, According to the objective, it can select suitably, For example, a urea modified polyester resin etc. are mentioned especially suitably.
The urea-modified polyester resin comprises an amine (B) as the 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. It is obtained by reacting in a medium.
The urea-modified polyester resin may contain a urethane bond in addition to the urea bond.

  Preferable specific examples of the urea-modified polyester resin include the following (1) to (10), that is, (1) a polyester pre-reacted polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate. A mixture of a polymer urealated with isophorone diamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid, and (2) a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid A mixture of a polyester prepolymer reacted with diisocyanate and uread with isophoronediamine, a bicondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (3) bisphenol A ethylene oxide 2 mol A polyester prepolymer obtained by reacting an adduct / bisphenol A propylene oxide 2 mol adduct and a polycondensate of terephthalic acid with isophorone diisocyanate, and urethanized with isophorone diamine, and bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene. Mixture of oxide 2 mol adduct and polycondensate of terephthalic acid, (4) Bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate were reacted with isophorone diisocyanate. A mixture of a polyester prepolymer uread with isophoronediamine, a bisphenol A propylene oxide 2-mole adduct and a polycondensate of terephthalic acid, (5) bisphenol A A polyester prepolymer obtained by reacting a polycondensate of tylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate and uread with hexamethylenediamine, and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid (6) Polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide with 2 mol of bisphenol A and isophorone diisocyanate with urea and hexamethylenediamine and 2 mol of bisphenol A ethylene oxide. Product / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate, (7) bisphenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate A mixture of a polyester prepolymer reacted with socyanate with urethanized with ethylenediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (8) bisphenol A ethylene oxide 2 mol adduct and isophthalic acid (9) Bisphenol A ethylene, a mixture of a polyester prepolymer obtained by reacting a polycondensate of bisphenol with diphenylmethane diisocyanate and uread with hexamethylene diamine, a bicondensate of bisphenol A ethylene oxide and a polycondensate of isophthalic acid, Polyester prepolymer obtained by reacting polycondensate of oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride with diphenylmethane diisocyanate Mixture of uremer with hexamethylenediamine and bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid polycondensate, (10) bisphenol A ethylene oxide 2-mole addition And a mixture of a polyester prepolymer obtained by reacting a polycondensate of isophthalic acid and toluene diisocyanate with urea diisocyanate with hexamethylenediamine, a bicondensate of bisphenol A ethylene oxide and a polycondensate of isophthalic acid, etc. Preferably mentioned.

-Active hydrogen group-containing compound-
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, or the like when a polymer capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in the aqueous medium.
The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected depending on the purpose. For example, the polymer capable of reacting with the active hydrogen group-containing compound is In the case of the isocyanate group-containing polyester prepolymer (A), the amines (B) can be increased in molecular weight by a reaction such as an elongation reaction or a crosslinking reaction with the isocyanate group-containing polyester prepolymer (A). Is preferred.
There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

The amines (B) are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), and amino mercaptan. (B4), amino acid (B5), and those obtained by blocking the amino groups of B1 to B5 (B6).
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) are particularly 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 the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the block (B6) obtained by blocking the amino group of B1 to B5 include ketimines obtained from any of the amines (B1) to (B5) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Compounds, oxazolyzone compounds, and the like.

  In addition, a reaction terminator can be used 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. Use of the reaction terminator is preferable in that the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), or those obtained by blocking these (ketimine compounds).

As a mixing ratio of the amines (B) and the isocyanate group-containing polyester prepolymer (A), the isocyanate group [NCO] in the isocyanate group-containing prepolymer (A) and the amines (B) The mixing equivalent ratio ([NCO] / [NHx]) of the amino group [NHx] is preferably 1/2 to 2/1, more preferably 1.5 / 1 to 1 / 1.5. The ratio is preferably 1.2 / 1 to 1 / 1.2, particularly preferably.
When the isocyanate group [NCO] is less than 1, the molecular weight of the urea-modified polyester may be low. When the isocyanate group [NCO] exceeds 2, the molecular weight of the urea-modified polyester resin is low and hot offset resistance deteriorates. Sometimes.

--Polymer capable of reacting with active hydrogen group-containing compound--
The polymer capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes 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. It can be appropriately selected from known resins and the like, and examples thereof include polyol resins, polyacrylic resins, polyester resins, epoxy resins, and derivative resins thereof.
These may be used individually by 1 type and may use 2 or more types together. Among these, a polyester resin is particularly preferable because it has a sharp molecular weight distribution and good melt properties.

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 chloride group, and the like.
These may be contained singly or in combination of two or more. Among these, an isocyanate group is particularly 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 fixability even in the absence of a release oil application mechanism to a fixing heating medium. It is particularly preferable that it is a urea bond-forming group-containing polyester resin (RMPE) because it can be secured.
As said urea bond production | generation group, an isocyanate group etc. are mentioned, for example. When the urea bond-forming group in the urea bond-forming group-containing polyester resin (RMPE) is the isocyanate group, the isocyanate group-containing polyester prepolymer (A) and the like are particularly preferable as the polyester resin (RMPE). It is done.

  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), And those obtained by reacting the 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, the diol (DIO) alone or a mixture of the diol (DIO) and a small amount of the 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, 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, and alkylene oxide adducts of bisphenols, alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. 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 PA, phenol novolak, cresol novolak, and the like. Examples of the alkylene oxide adducts of trihydric or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide to the trihydric or higher polyphenols.

  The mixture mass ratio (DIO: TO) of the diol (DIO) and the trivalent or higher polyol (TO) in the mixture of the diol (DIO) and the trivalent or higher polyol (TO) is 100: 0.01-10 are preferable and 100: 0.01-1 are 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 tricarboxylic or higher 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 DIC and a small amount of trivalent or higher polycarboxylic acid (TC) is preferable.
Examples of the dicarboxylic acid include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, aromatic dicarboxylic acid, and the like.
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 (TO) 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.

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

  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] to the carboxyl group [COOH] in the polycarboxylic acid (PC) is usually preferably 2/1 to 1/1. More preferably, it is 0.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1.
Even if the equivalent ratio ([OH] / [COOH]) exceeds 2/1 or less than 1/1, the molecular weight distribution of the resulting polyester resin is lowered, and the desired polyester resin is obtained. It may not be possible.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyol (PO), Although it can select suitably according to the objective, For example, 0.5-40 mass% is preferable. 1-30 mass% is more preferable, and 2-20 mass% is especially 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), Although it can select suitably according to the objective, For example, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurate And those blocked with phenol derivatives, oximes, caprolactams, 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 and triisocyanatocycloalkyl-isocyanurate.
These can be used alone or in combination of two or more.

As a mixing ratio when the polyisocyanate (PIC) and the active hydrogen group-containing polyester resin (for example, a hydroxyl group-containing polyester resin) are reacted, the isocyanate group [NCO] in the polyisocyanate (PIC) and the hydroxyl group-containing component are used. The mixing equivalent ratio ([NCO] / [OH]) with the hydroxyl group [OH] in the polyester resin is usually preferably 5/1 to 1/1, and preferably 4/1 to 1.2 / 1. More preferably, it is particularly preferably 2.5 / 1 to 1.5 / 1.
When the isocyanate group [NCO] exceeds 5, the low-temperature fixability may deteriorate, and when it is less than 1, the low-temperature fixability may deteriorate.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, 0.5-40 mass% is Preferably, 1-30 mass% is more preferable, and 2-20 mass% is still more 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 in one molecule of the isocyanate group-containing polyester prepolymer (A) is preferably 1 or more, more preferably 2 to 3, and more preferably 2.01 to 2.5.
When the average number of the isocyanate groups is less than 1, the molecular weight of the polyester resin (RMPE) modified with the urea bond-forming group is lowered, and the hot offset resistance may be deteriorated.

--- Aqueous medium--
There is no restriction | limiting in particular as said aqueous medium, It can select suitably from well-known things, For example, water, the mixture with the solvent miscible with this water, etc. are mentioned.
The solvent miscible with water is not particularly limited as long as it is miscible with water, and examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, lower ketones, and ethyl acetate.
Examples of the alcohol include methanol, isopropanol, ethylene glycol and the like. Examples of the cell solves include methyl cell solve. Examples of the lower ketones include acetone and methyl ethyl ketone.

-Crystalline polyester resin particles-
The crystalline polyester resin particles are as described above, and examples include those contained in the crystalline polyester resin dispersion of the present invention.
There is no restriction | limiting in particular as content in the said toner of the said crystalline polyester resin particle, According to the objective, it can select suitably, For example, 0.1-30 mass% is preferable as a solid content density | concentration. 5-25 mass% is more preferable.
When the content is less than 0.1% by mass, the low-temperature fixability may not be effective, and when it exceeds 30% by mass, the fixing temperature range may be narrowed.

In the present invention, the toner includes the above-described crystalline polyester resin dispersion of the present invention in which the crystalline polyester resin particles are contained in addition to the above-mentioned adhesive base material and the crystalline polyester resin particles. The binder resin contained therein may also be included.
In this case, the binder resin is as described above. Among them, a polyester resin is preferable, and an unmodified polyester resin is more preferable. When the toner contains the unmodified polyester resin, it is advantageous in that low-temperature fixability and glossiness are improved.

  The unmodified polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the same as the urea bond-forming group-containing polyester resin, that is, polyol (PO) and polycarboxylic acid ( PC)) and the like. The unmodified polyester resin is partially compatible with the urea bond-forming group-containing polyester resin (RMPE), that is, has a similar structure compatible with each other. It is preferable in terms of hot offset.

The weight average molecular weight of the unmodified polyester resin is preferably 1000 to 30000, more preferably 1500 to 10000, and particularly preferably 2000 to 8000, as measured by GPC (gel permeation chromatography). When the weight average molecular weight is less than 1000, the heat-resistant storage stability may be deteriorated, and when it exceeds 10,000, the low-temperature fixability may be deteriorated.
The hydroxyl value of the unmodified polyester resin is preferably 5 or more, more preferably 10 to 120, still more preferably 20 to 80. If the hydroxyl value is less than 5, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin is preferably 1 to 30, and more preferably 5 to 20. Generally, it becomes easy to be negatively charged by giving the toner an acid value.

When the unmodified polyester resin is contained in the toner, the mixing mass ratio (RMPE / PE) of the urea bond-forming group-containing polyester resin (RMPE) and the unmodified polyester resin (PE) is 5/95. -70/30 are preferable, 5 / 95-60 / 40 are more preferable, 7 / 93-50 / 50 are still more preferable, and 7 / 93-25 / 75 are especially preferable.
When the mixing mass ratio of the unmodified polyester resin (PE) exceeds 95, the hot offset resistance deteriorates, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. Low temperature fixability may deteriorate.

  The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, colorants, mold release agents, resin fine particles, charge control agents, inorganic fine particles, fluidity improvers, and cleaning properties are improved. Agents, magnetic materials, metal soaps, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, it is preferable to include at least one selected from the colorant, the release agent, and the charge control agent.

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 Zhu, Cadmium Red, Cadmium Mercury Red, Antimony Zhu, Permanent Red 4R Parared, Faisered, 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, Pigment 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 Oil Red, 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, Chrome oxide, pyridian, emerald green, pigment green B, naphthol green B, green gold, a Cid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon, and the like.
These may be used individually by 1 type and may use 2 or more types together.

The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 15% by weight, and more preferably 3 to 10% by weight.
When the content is less than 1% by mass, a desired coloring degree may not be obtained, and when it exceeds 15% by mass, an unnecessarily high coloring degree may be obtained.

The colorant can also be used as a master batch combined with a resin.
The resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include styrene or a substituted polymer thereof, a styrene copolymer, polymethyl methacrylate, polybutyl methacrylate, and polyvinyl chloride. Polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic 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 An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

  The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. This flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant 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.

There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes etc. are mentioned suitably.
Examples of the waxes include carbonyl group-containing waxes, polyolefin waxes, and long-chain hydrocarbons. These may be used individually by 1 type and may use 2 or more types together. Among these, a carbonyl group-containing wax is preferable.
Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, dialkyl ketones, and the like. Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, and 1,18-octadecane. Examples thereof include diol distearate. Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate. Examples of the polyalkanoic acid amide include dibehenyl amide. Examples of the polyalkylamide include trimellitic acid tristearylamide. Examples of the dialkyl ketone include distearyl ketone. Of these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferred.
Examples of the polyolefin wax include polyethylene wax and polypropylene wax.
Examples of the long chain hydrocarbon include paraffin wax and sazol wax.

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, 40-160 degreeC is preferable, 50-120 degreeC is more preferable, 60-90 degreeC is especially preferable.
When the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability, and when it exceeds 160 ° C., cold offset may easily occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 to 1000 cps, more preferably 10 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 effect of improving hot offset resistance and low-temperature fixability may not be obtained, and if it exceeds 1000 cps, the effect of improving hot offset resistance and low-temperature fixability is obtained. It may disappear.

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, 0-40 mass% is preferable and 3-30 mass% is more preferable.
When the content exceeds 40% by mass, the low-temperature fixability may be hindered or the image quality may be deteriorated (the glossiness is too high).

The resin fine particles are generally added for the purpose of controlling the toner shape (average circularity, particle size distribution, etc.). The resin fine particles adhere to or bind to the surface of the toner when the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen-containing compound are dispersed in the aqueous medium to form toner particles. Etc.
The resin fine particle is not particularly limited as long as it is a resin capable of forming an aqueous dispersion in the aqueous medium, can be appropriately selected from known resins, and may be a thermoplastic resin, It may be a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, And polycarbonate resin. These may be used individually by 1 type and may use 2 or more types together. Among these, a vinyl resin, a polyurethane resin, an epoxy resin, a polyester resin, and a mixture thereof are preferable because an aqueous dispersion of fine spherical resin particles is easily obtained.
The vinyl resin is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer, and specific examples include styrene- (meth) acrylic ester resin, styrene-butadiene copolymer, (meth) acrylic acid- Examples include acrylic ester polymers, styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, styrene- (meth) acrylic acid copolymers, and the like.

  The glass transition temperature (Tg) of the resin fine particles is preferably 40 to 100 ° C. The weight average molecular weight of the resin fine particles is preferably 9,000 to 200,000. When the Tg is less than 40 ° C. and / or the weight average molecular weight is less than 9,000 in the resin fine particles, the storage stability of the toner deteriorates, and blocking may occur during storage and in the developing machine. When the Tg exceeds 100 ° C. and / or the weight average molecular weight exceeds 200,000, the resin fine particles may inhibit the adhesion to the fixing paper, and the minimum fixing temperature may increase.

The content of the resin fine particles in the toner is preferably 0.5 to 5.0% by mass, and more preferably 0.5 to 4.0% by mass.
When the content is less than 0.5% by mass, the storability of the toner deteriorates, and blocking may occur during storage and in the developing machine. When the content exceeds 5.0% by mass, The resin fine particles inhibit the exudation of the wax, and the wax releasability effect cannot be obtained, resulting in an offset.

The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, a colorless or nearly white material may be used. Preferably, for example, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxyamines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten Examples thereof include a single substance or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, and a metal salt of a salicylic acid derivative. These may be used individually by 1 type and may use 2 or more types together.
Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, phenolic condensate E-89 (above, manufactured by Orient Chemical Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), fourth Copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR which is a boron complex -147 (manufactured by Nippon Carlit), quinacridone, azo pigment, other sulfonic acid groups, carbo Sill group, polymer compounds having a functional group such as quaternary ammonium salts, and the like.
The charge control agent may be melted and kneaded with the master batch and then dissolved or dispersed, or may be added together with each component of the toner when directly dissolving or dispersing in the organic solvent, or The toner particles may be fixed on the toner surface after production.

  The content of the charge control agent in the toner varies depending on the type of the adhesive base material, the presence or absence of additives, the dispersion method, and the like, and cannot be defined generally. 0.1-10 mass parts is preferable with respect to part, and 0.2-5 mass parts is more preferable. When the content is less than 0.1 parts by mass, the charge amount of the toner is too low, which may cause toner scattering and background staining. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too high. The effect of the main charge control agent is diminished, and the electrostatic attraction force with the developing roller is increased, leading to a decrease in developer fluidity and a decrease in image density.

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.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. The specific surface area of the inorganic fine particles by BET method is preferably 20 to 500 m ² / g.
The content of the inorganic fine particles in the toner is preferably 0.01 to 5.0% by mass, and more preferably 0.01 to 2.0% by mass.

The fluidity improver means a material that can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, Examples thereof include a silane coupling agent having a fluoroalkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil.
The cleaning improver is added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium. For example, a fatty acid metal salt such as zinc stearate, calcium stearate, stearic acid, Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as methyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.
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. are mentioned. Among these, white is preferable in terms of color tone.

  The shape, size, etc. of the toner of the present invention are not particularly limited and can be appropriately selected according to the purpose. However, the following thermal characteristics, image density, average circularity are as follows. Preferably, the ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter).

The thermal characteristics are also called flow tester characteristics, and are evaluated as, for example, a softening temperature (Ts), an outflow start temperature (Tfb), a 1/2 method softening point (T1 / 2), and the like.
These thermal characteristics can be measured by an appropriately selected method. For example, the thermal characteristics can be obtained from a flow curve measured using an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation).
There is no restriction | limiting in particular as said softening temperature (Ts), According to the objective, it can select suitably, For example, 50 degreeC or more is preferable and 80-120 degreeC is more preferable. When the softening temperature (Ts) is less than 50 ° C., at least one of heat resistant storage stability and low temperature storage stability may deteriorate.
There is no restriction | limiting in particular as said outflow start temperature (Tfb), According to the objective, it can select suitably, For example, 60 degreeC or more is preferable and 70-150 degreeC is more preferable. If the outflow start temperature (Tfb) is less than 60 ° C., at least one of heat resistant storage stability and low temperature storage stability may deteriorate.
The 1/2 method softening point (T1 / 2) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 60 ° C. or higher is preferable, and 80 to 170 ° C. is more preferable. If the 1/2 method softening point (T1 / 2) is less than 60 ° C., at least one of heat resistant storage stability and low temperature storage stability may be deteriorated.

The image density is preferably 1.90 or more, more preferably 2.00 or more, and particularly preferably 2.10 or more, as measured by a spectrometer (X-Light, 938 Spectrodensitometer). preferable.
If the image density is less than 1.90, the image density may be low and high image quality may not be obtained.
The image density is, for example, an image of 1.00 ± 0.05 mg / cm on the copy paper (TYPE 6000 <70W>; manufactured by Ricoh Co., Ltd.) using imagio Neo 450 (manufactured by Ricoh Co., Ltd.). ² solid images were formed at a fixing roller surface temperature of 160 ± 2 ° C., and the image density at any six locations in the obtained solid images was measured with a spectrometer (X-Light, 938 Spectrodensitometer). It can measure by using and measuring and calculating the average value.

The average circularity is a value obtained by dividing the perimeter of an equivalent circle having the same projected shape as the toner shape by the perimeter of the actual particles, and is preferably 0.900 to 0.980, for example, 0.950 to 0 .975 is more preferred. The particles having an average circularity of less than 0.94 are preferably 15% or less.
If the average circularity is less than 0.900, satisfactory transferability and a high-quality image free from dust may not be obtained. If the average circularity exceeds 0.980, image formation employing blade cleaning or the like is employed. In the system, defective cleaning occurs on the photoconductor and the transfer belt, and in the case of image formation with a high image area ratio such as a photographic image, an untransferred image is formed due to defective paper feeding, etc. The accumulated toner may become a transfer residual toner on the photoconductor, resulting in background smearing of the image, or it may contaminate the charging roller for charging the photoconductor in contact with the original charging ability. It may become impossible to demonstrate.
The average circularity is measured by, for example, an optical detection band method in which a suspension containing toner particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. For example, it can be measured using a flow type particle image analyzer FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.).

There is no restriction | limiting in particular as a volume average particle diameter of the said toner, Although it can select suitably according to the objective, For example, 3-8 micrometers is preferable.
When the volume average particle size is less than 3 μm, in the case of a two-component developer, the toner may be fused to the surface of the carrier during long-term agitation in the developing device, and the charging ability of the carrier may be reduced. In the 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 the thickness exceeds 8 μm, the resolution is high and high. It becomes difficult to obtain an image of an image quality, and when the balance of the toner in the developer is performed, the variation in the particle diameter of the toner may increase.

The ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) in the toner is preferably 1.00 to 1.25, more preferably 1.10 to 1.25.
When the ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) exceeds 1.25, the two-component developer causes the surface of the carrier to be agitated for a long period of time in the developing device. The toner may be fused and the charging ability of the carrier may be reduced. With a one-component developer, the toner filming on the developing roller and the toner is thinned, causing the toner to be fused to a member such as a blade. In addition, it is difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the variation in the toner particle diameter may increase.

  The volume average particle diameter and the ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) are, for example, a particle size measuring device “Coulter Counter TAII” manufactured by Coulter Electronics, It can be measured using a particle size measuring device “LA-920” manufactured by HORIBA, Ltd.

  The coloration of the toner of the present invention is not particularly limited and can be appropriately selected according to the purpose, and can be at least one selected from black toner, cyan toner, magenta toner and yellow toner. This toner can be obtained by appropriately selecting the type of the colorant.

  The toner of the present invention includes the adhesive base formed by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an aqueous medium. Excellent in various properties such as fluidity, transferability, fixability, and the like, and includes the crystalline polyester resin particles. Shows a decrease in viscosity (sharp melt properties). For this reason, the toner is excellent in offset resistance, chargeability, charge stability, cleanability, etc. while being able to achieve both heat-resistant storage stability and low-temperature fixability. Can produce a high-quality image with a high image density and can be used particularly favorably in the following toner-containing container, developer, process cartridge, image forming apparatus and image forming method of the present invention. .

  The toner of the present invention can be produced by a known method, but can be suitably produced by the following method for producing a toner of the present invention.

(Toner production method)
The method for producing a toner of the present invention includes at least an adhesive substrate generation step, and further includes other steps appropriately selected as necessary.

-Adhesive substrate production process-
In the adhesive base material generation step, the active hydrogen group-containing compound described above, the polymer capable of reacting with the active hydrogen group-containing compound described above, and the crystalline polyester resin dispersion described above in the aqueous medium described above. In this step, the toner is obtained while being dispersed and reacted to form the adhesive substrate.
In the adhesive substrate generation step, for example, preparation of an aqueous medium phase, preparation of an organic solvent phase, emulsification / dispersion, and others (synthesis of a polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound, Synthesis of active hydrogen group-containing compounds).

The aqueous medium phase can be prepared, for example, by dispersing the resin fine particles in the aqueous medium. There is no restriction | limiting in particular as the addition amount in this aqueous medium of this resin fine particle, According to the objective, it can select suitably, For example, 0.5-10 mass% is preferable.
The organic solvent phase is prepared by mixing the active hydrogen group-containing compound, the polymer capable of reacting with the active hydrogen group-containing compound, the crystalline polyester resin dispersion, the colorant, and the release agent in the organic solvent. In addition, toner raw materials such as the charge control agent and the unmodified polyester resin can be dissolved or dispersed.
It should be noted that components other than the polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound in the toner raw material are added when the resin fine particles are dispersed in the aqueous medium in the aqueous medium phase preparation. You may add and mix in an aqueous medium, or when adding the said organic solvent phase to the said aqueous medium phase, you may add to the said aqueous medium phase with this organic solvent phase.

The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner raw material, and can be appropriately selected according to the purpose, and has a boiling point of less than 150 ° C. in terms of ease of removal. For example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Examples thereof include methyl ethyl ketone and methyl isobutyl ketone. Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are 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 the usage-amount of the said organic solvent, According to the objective, it can select suitably, For example, 40-300 mass parts is preferable with respect to 100 mass parts of said toner raw materials, and 60-140 mass parts is. More preferably, 80-120 mass parts is still more preferable.

The emulsification / dispersion can be performed by emulsifying / dispersing the previously prepared organic solvent phase in the previously prepared aqueous medium phase. In the emulsification / dispersion, when the active hydrogen group-containing compound, the polymer capable of reacting with the active hydrogen group-containing compound, and the crystalline polyester resin dispersion are subjected to an elongation reaction or a cross-linking reaction, the adhesive group The material is generated.
The adhesive substrate (for example, the urea-modified polyester resin) includes, for example, (1) a polymer that can react with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)). The organic solvent phase is emulsified and dispersed in the aqueous medium phase together with the active hydrogen group-containing compound (for example, the amines (B)) to form a dispersion, and both are extended in the aqueous medium phase. Or (2) the organic solvent phase is emulsified and dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance to form a dispersion, and the aqueous medium It may be produced by extending or cross-linking both in the phase, or (3) the organic solvent phase is added and mixed in the aqueous medium and then the active hydrogen group-containing The compound was added to form a dispersion, it may be generated by elongation reaction or crosslinking reaction from particle interfaces in the aqueous medium phase. In the case of (3), a modified polyester resin is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided in the toner particles.

  The emulsification / dispersion causes the active hydrogen group-containing compound, the polymer capable of reacting with the active hydrogen group-containing compound, and the crystalline polyester resin dispersion to undergo an extension reaction or a cross-linking reaction to form the adhesive substrate. There are no particular restrictions on the reaction conditions for the reaction, and it may be appropriately selected according to the combination of the polymer capable of reacting with the active hydrogen group-containing compound, the active hydrogen group-containing compound, and the crystalline polyester resin dispersion. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours, and the reaction temperature is preferably 0 to 150 ° C, more preferably 40 to 98 ° C.

In the aqueous medium phase, as a method for stably forming the dispersion containing a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), for example, In an aqueous medium phase, a polymer capable of reacting with the active hydrogen group-containing compound dissolved or dispersed in the organic solvent (for example, the isocyanate group-containing polyester prepolymer (A)), the crystalline polyester resin dispersion, Examples include a method in which the toner raw materials such as the colorant, the release agent, the charge control agent, and the unmodified polyester resin are added and dispersed by shearing force.
The dispersion is not particularly limited as a method thereof, and can be appropriately selected using a known disperser. Examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, and a friction type. Examples thereof include a disperser, a high-pressure jet disperser, and an ultrasonic disperser. Among these, a high-speed shearing disperser is preferable in that the particle size of the dispersion can be controlled to 2 to 20 μm.
When the high-speed shearing disperser is used, conditions such as the rotation speed, dispersion time, and dispersion temperature are not particularly limited and can be appropriately selected according to the purpose. For example, the rotation speed is 1000 -30000 rpm is preferable, 5000-20000 rpm is more preferable, the dispersion time is preferably 0.1-5 minutes in the case of a batch system, and the dispersion temperature is preferably 0-150 ° C. under pressure, -98 degreeC is more preferable. The dispersion temperature is generally easier when the temperature is higher.

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

In the emulsification / dispersion, it is preferable to use a dispersant as necessary from the viewpoint of sharpening the particle size distribution and performing stable dispersion.
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a poorly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters and the like, and those having a fluoroalkyl group are preferable. 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- [omega-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [omega-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxy Ethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate and the like. Examples of commercially available surfactants having a fluoroalkyl group include 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 (large) Nihon Ink Co., Ltd.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); Manufactured) and the like.

  Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of the amine salt type surfactant include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Among the cationic surfactants, aliphatic quaternary ammonium such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt, etc. Salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like. Commercially available products of the cationic surfactant include, for example, Surflon S-121 (manufactured by Asahi Glass Co., Ltd.); Florard FC-135 (manufactured by Sumitomo 3M Co.); Unidyne DS-202 (manufactured by Daikin Industries Ltd.), MegaFuck F-150 F-824 (manufactured by Dainippon Ink Co., Ltd.); Xtop EF-132 (manufactured by Tochem Products); Footgent F-300 (manufactured by Neos).

Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.
Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine and the like.

Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing a hydroxyl group, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and a compound containing a carboxyl group, amides Examples thereof include homopolymers or copolymers such as compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, and celluloses.
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, glycerol monoacrylate Glycerin monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide and the like. Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of the esters of vinyl alcohol and a compound containing 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, or 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.

In the emulsification / dispersion, a dispersion stabilizer can be used as necessary.
Examples of the dispersion stabilizer include acids that are soluble in acids and alkalis such as calcium phosphate salts.
When the dispersion stabilizer is used, the calcium phosphate salt can be removed from the fine particles by a method of dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water or a method of decomposing with an enzyme.

  In the emulsification / dispersion, a catalyst for the elongation reaction or the crosslinking reaction can be used. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

  The organic solvent is removed from the emulsified slurry obtained in the emulsification / dispersion. The organic solvent is removed by (1) a method in which the entire reaction system is gradually heated to completely evaporate and remove the organic solvent in the droplets, and (2) the emulsion dispersion is sprayed in a dry atmosphere. And a method in which the water-insoluble organic solvent in the droplets is completely removed to form toner fine particles, and the aqueous dispersant is removed by evaporation.

  When the organic solvent is removed, toner particles are formed. The toner particles can be washed, dried, etc., and then classified as desired. The classification can be performed, for example, by removing fine particle portions by a cyclone, a decanter, centrifugation, or the like in a liquid, and the classification operation may be performed after obtaining a powder after drying. Unnecessary fine particles or coarse particles obtained by the classification can be used in the adhesive base material production step.

Thus, the obtained toner particles are mixed with particles of the colorant, release agent, charge control agent, etc., and further, a mechanical impact force is applied to the release agent from the surface of the toner particles. And the like can be prevented from being detached.
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 etc. are 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 is lowered, and a hybridization system (Nara Machinery Co., Ltd.) Product), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.

Here, a preferred specific example of the toner production method of the present invention is shown below.
-Adhesive substrate production process-
-Preparation of aqueous medium phase (aqueous phase)-
In a reaction vessel equipped with a stirrer and a thermometer, water, sodium salt of ethylene oxide methacrylate adduct sulfate, styrene, methacrylic acid, and ammonium persulfate were charged and stirred for 15 minutes at 400 rpm. An emulsion of is obtained. The emulsion is heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, a 1% by mass ammonium persulfate aqueous solution is added to the reaction solution and aged at 75 ° C. for 5 hours to obtain a vinyl resin ( An aqueous dispersion of a styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer) (hereinafter abbreviated as “fine particle dispersion”) is prepared. Thereafter, water, the fine particle dispersion, a 48.5 mass% aqueous solution of sodium dodecyl diphenyl ether disulfonate, and ethyl acetate are mixed and stirred to prepare a milky white liquid (hereinafter abbreviated as “aqueous phase”).

--Synthesis of prepolymer--
Put a bisphenol A ethylene oxide 2-mole adduct, bisphenol A propylene oxide 3-mole adduct, terephthalic acid, adipic acid, and dibutyltin oxide in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and normal pressure. After reacting at 230 ° C. for 8 hours and further reacting the reaction solution under a reduced pressure of 10 to 15 mmHg for 5 hours, trimellitic anhydride was put into the reaction vessel and reacted at 180 ° C. under normal pressure for 2 hours. Thus, a low molecular weight polyester is synthesized.
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, bisphenol A ethylene oxide 2-mole adduct, bisphenol A propylene oxide 2-mole adduct, terephthalic acid, trimellitic anhydride, and dibutyltin oxide are added. Charge and react at 230 ° C. for 8 hours under normal pressure. Subsequently, it is made to react under reduced pressure of 10-15mHg for 5 hours, and an intermediate polyester is synthesize | combined.
Next, the intermediate polyester, isophorone diisocyanate, and ethyl acetate are charged into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours to produce a prepolymer (the active hydrogen A polymer capable of reacting with the group-containing compound).

--Synthesis of ketimine (the active hydrogen group-containing compound)-
Isophoronediamine and methyl ethyl ketone are charged into a reaction vessel equipped with a stir bar and a thermometer, and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound (the active hydrogen group-containing compound).

-Preparation of master batch (MB)-
Water, carbon black as a colorant, and a polyester resin were added and mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The mixture is kneaded with two rolls at 150 ° C. for 30 minutes, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron) to prepare a master batch.

-Preparation of organic solvent phase-
In a reaction vessel equipped with a stirrer and a thermometer, the low molecular weight polyester, carnauba wax, CCA (“salicylic acid metal complex E-84”), and ethyl acetate were charged, and the temperature was raised to 80 ° C. with stirring. Hold for 5 hours, then cool to 30 ° C. over 1 hour. Next, the master batch and ethyl acetate are charged into a reaction vessel and mixed for 1 hour to obtain a raw material solution.
The obtained raw material solution was transferred to a reaction vessel, and using a bead mill (“Ultra Visco Mill”; manufactured by Imex Co., Ltd.), a liquid feed speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads were 80 The carbon black and the carnauba wax are dispersed in 3 passes under the condition of volume% filling. Next, a 65% by mass ethyl acetate solution of the low molecular weight polyester is added to the dispersion. One pass is performed in a bead mill under the same conditions as above, and the mixture is dispersed to prepare an organic solvent phase.

--Emulsification / Dispersion--
In a reaction vessel, the organic solvent phase, the prepolymer, the crystalline polyester resin dispersion of the present invention, and the ketimine compound are charged, and 5,000 rpm using a TK homomixer (manufactured by Tokushu Kika). After mixing for 1 minute, 1200 parts by mass of the aqueous phase was added to the reaction vessel, and the mixture was mixed and emulsified / dispersed at 13,000 rpm for 20 minutes using a TK homomixer to prepare an emulsified slurry. To do.
Next, the emulsified slurry is charged into a reaction vessel equipped with a stirrer and a thermometer, and the solvent is removed at 30 ° C. for 8 hours. Thereafter, the emulsified slurry is aged at 45 ° C. for 4 hours.

--- Washing and drying--
The emulsified slurry after aging is filtered under reduced pressure, ion-exchanged water is added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered. 10 mass% sodium hydroxide aqueous solution is added to the filter cake obtained here, and it mixes with a TK homomixer (30 minutes at 12,000 rpm of rotations), Then, it filters under reduced pressure. 10 mass% hydrochloric acid is added to the filter cake obtained here, and after mixing with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), the mixture is filtered. Ion exchanged water is added to the filter cake obtained here, and after mixing with a TK homomixer (at a rotation speed of 12,000 rpm for 10 minutes), filtration is performed twice to obtain a final filter cake. The final filter cake obtained here is dried for 48 hours at 45 ° C. with a circulating dryer, and sieved with a mesh having a mesh size of 75 μm to obtain toner particles.
Then, the toner of the present invention can be produced by mixing the obtained toner particles with hydrophobic silica and hydrophobic titanium oxide using a Henschel mixer.

(Developer)
The developer of the present invention contains at least the toner of the present invention, and other components such as a carrier selected as appropriate. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner of the present invention, even if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, and the filming of the toner on the developing roller or the toner is made thin. Therefore, the toner is not fused to a member such as a blade, and good and stable developability and image can be obtained even when the developing device is used (stirred) for a long time. Further, in the case of the two-component developer using the toner of the present invention, even if the balance of the toner over a long period of time is performed, the fluctuation of the toner particle diameter in the developer is small, and even in the long-term stirring in the developing device, Good and stable developability can be obtained.

  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, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, a weakly magnetized material such as a copper-zinc (Cu—Zn) -based (30 to 80 emu / g) 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 Is preferred. These may be used alone or in combination of two or more.

The particle diameter of the core material is preferably an average particle diameter (volume average particle diameter (D ₅₀ )) of 10 to 150 μm, and more preferably 40 to 100 μm.
If the average particle size (volume average particle size (D ₅₀ )) is less than 10 μm, the carrier particle distribution may increase the number of fine powders, lowering the magnetization per particle and causing carrier scattering. If the thickness exceeds 150 μm, the specific surface area may decrease and toner scattering may occur. In the case of a full color with many solid portions, reproduction of the solid portions may be particularly poor.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, fluorine And a copolymer of vinylidene fluoride and vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride and a non-fluorinated monomer, and a silicone resin. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate resin, poly Examples include acrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin. Examples of the polystyrene resin include polystyrene resin and styrene acrylic copolymer resin. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester resin include polyethylene terephthalate resin and polybutylene terephthalate resin.

  The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the application method include an immersion method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cersol butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.

The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass.
When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

  When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 to 98% by mass Is preferable, and 93-97 mass% is more preferable.

Since the developer of the present invention contains the toner of the present invention, it is excellent in offset resistance, chargeability, charge stability, cleanability, etc. while achieving both heat-resistant storage stability and low-temperature fixability. A high-quality image with high image density and high sharpness can be formed without causing soiling or filming under various environments.
The developer of the present invention can be suitably used for image formation by 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. It can be particularly suitably used for containers, process cartridges, image forming apparatuses and image forming methods.

(Toner container)
The toner-containing container of the present invention comprises the toner or the developer of the present invention contained in a container.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a container main body and a cap containing a toner etc. are mentioned suitably.
The size, shape, structure, material and the like of the container body containing toner are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably cylindrical. A spiral irregularity is formed on the peripheral surface, and the toner as the contents can be transferred to the discharge port side by rotating, and part or all of the spiral part has a bellows function, etc. Is particularly preferred.
The material of the toner-containing container body is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferably used. Among them, for example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, Preferable examples include vinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and the like.
The toner-containing container of the present invention is easy to store and transport, has excellent handleability, and is preferably used for replenishing toner by being detachably attached to the process cartridge and image forming apparatus of the present invention described later. Can do.

(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a developer to form a visible image. And at least developing means for forming the film, and other means appropriately selected as necessary.
The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.
The process cartridge of the present invention can be detachably provided in various electrophotographic apparatuses, and is preferably provided detachably in the electrophotographic apparatus of the present invention described later.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further appropriately selected as necessary. It has other means, for example, static elimination means, cleaning means, recycling means, control means and the like.
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and further other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step, Includes recycling and control processes.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the electrostatic latent image forming step can be performed by the electrostatic latent image forming means, and the developing step is the developing The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit.

-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
There are no particular restrictions on the material, shape, structure, size, etc. of the electrostatic latent image carrier (sometimes referred to as “photoconductive insulator” or “photoconductor”), and among the known ones The shape is preferably a drum shape, and examples of the material include inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors such as polysilane and phthalopolymethine. It is done. Among these, amorphous silicon or the like is preferable in terms of long life.

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to.
The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it can be developed using, for example, the toner or the developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferred examples include a developer containing at least a developer, and at least a developing device capable of contacting or non-contacting the toner or the developer with the electrostatic latent image. More preferred is a developing device.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

  The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the electrophotographic toner remaining on the electrostatic latent image carrier, and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step of recycling the electrophotographic color toner removed in the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control means is a process for controlling the respective steps, and can be suitably performed by the control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  One mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 1 includes a photosensitive drum 10 (hereinafter referred to as “photosensitive member 10”) as the electrostatic latent image carrier, a charging roller 20 as the charging unit, and exposure as the exposure unit. The apparatus 30 includes a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and for transferring (secondary transfer) a developed image (toner image) to a transfer sheet 95 as a final transfer material. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is arranged between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

  In the image forming apparatus 100 shown in FIG. 1, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 2 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 1, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and Except for the fact that the cyan developing unit 45C is disposed directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 2, the same components as those in FIG. 1 are denoted by the same reference numerals.

Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The tandem image forming apparatus shown in FIG. 3 is a tandem type color image forming apparatus. The tandem image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 3. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Yes.

  Next, formation of a full color image (color copy) using the tandem image forming apparatus will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  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 contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta and cyan is stored in each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means in the tandem image forming apparatus. ) And black, yellow, magenta and cyan toner images are formed in the respective image forming means. That is, each of the image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem image forming apparatus is photosensitive as shown in FIG. On the basis of the body 10 (the black photoreceptor 10K, the yellow photoreceptor 10Y, the magenta photoreceptor 10M, and the cyan photoreceptor 10C), the charger 60 that uniformly charges the photoreceptor, and each color image information. The photosensitive member is exposed to each color image corresponding image (L in FIG. 4), and an electrostatic latent image corresponding to each color image is formed on the photosensitive member. A developing device 61 that develops using color toner (black toner, yellow toner, magenta toner, and cyan toner) to form a toner image with each color toner, and the toner image is an intermediate transfer member. The image forming apparatus includes a transfer charger 62 for transferring the image onto 0, a photoconductor cleaning device 63, and a static eliminator 64, and each monochrome image (black image, yellow image, magenta) based on the image information of each color. Image and cyan image) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16, respectively. The black image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Is done. Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feeding roller 150 is rotated to feed out the sheets (recording paper) on the manual feed tray 51, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.
Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  In the image forming apparatus and the image forming method of the present invention, the toner of the present invention having excellent offset resistance, charging properties, charging stability, cleaning properties and the like is used while achieving both heat-resistant storage stability and low-temperature fixability. Therefore, a high-quality image with high image density and high sharpness can be formed without causing soiling or filming under various environments.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Synthesis Example 1)
-Synthesis of crystalline polyester resin-
In a 5-liter four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer and a thermocouple, 2070 g of 1,4-butanediol as an alcohol component, 2535 g of fumaric acid as an acid component, and 291 g of trimellitic anhydride In addition, 4.9 g of hydroquinone was charged and reacted at 160 ° C. for 5 hours, and then heated to 200 ° C. and reacted for 1 hour. Next, the crystalline polyester resin of Synthesis Example 1 was synthesized by reacting for 1 hour under a pressure of 8.3 kPa.

  About the obtained crystalline polyester resin of Synthesis Example 1, melting temperature (Tm), DSC endothermic peak temperature, weight average molecular weight (Mw), number average molecular weight (Mn), and δch (out-of-plane change) (Angular vibration) was measured. The results are shown in Table 1. In addition, the obtained crystalline polyester resin of Synthesis Example 1 had a DSC endothermic peak temperature of 123 ° C., a weight average molecular weight (Mw) of 2,100, and a number average molecular weight (Mn) of 710.

<Melting temperature (Tm)>
Using an elevated flow tester (“CFT-500”; manufactured by Shimadzu Corporation), measurement was performed under the following measurement conditions. The temperature at which half of the sample flows out was taken as the melting temperature (Tm).
〔Measurement condition〕
Sample: 1g
Temperature increase rate: 6 ° C./min Load: 20 kg / cm ²
Nozzle: 1mm x 1mm

<DSC endothermic peak temperature>
The temperature (° C.) at the peak of the DSC curve obtained by measurement using a differential scanning calorimeter (DSC) (manufactured by Shimadzu Corporation) was measured and used as the DSC endothermic peak temperature.

<Weight average molecular weight (Mw) and number average molecular weight (Mn)>
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured from the molecular weight distribution by gel permeation chromatography (GPC) of the soluble part of orthodichlorobenzene.

<Δch>
The absorption peak wavelength based on δch (out-of-plane variable vibration) of olefin was determined from the chart of the measured infrared absorption (IR) spectrum.

(Synthesis Examples 2 to 7)
-Synthesis of crystalline polyester resin-
In the same manner as in Synthesis Example 1, the crystalline polyester resins of Synthesis Examples 2 to 7 were synthesized. For each resin, melting temperature (Tm), DSC endothermic peak temperature, weight average molecular weight (Mw), number average molecular weight (Mn ) And δch (out-of-plane variable vibration). The results are shown in Table 1. IR charts of the obtained crystalline polyester resins of Synthesis Examples 2 to 7 are shown in FIGS.

(Example 1)
-Preparation of crystalline polyester resin dispersion-
After thoroughly mixing 1 part by mass of the crystalline polyester resin of Synthesis Example 5 and 4 parts by mass of polyester resin A (Tg = 43 ° C., Mn = 2,700, Mw = 6,000) as a binder resin Then, a melt-kneaded product is prepared by melt-kneading at 130 ° C. using a twin-screw extruder having a cooling function (manufactured by Toshiba Machine Co., Ltd.), and then cooled at a cooling rate of 1 ° C./minute to obtain crystalline polyester resin particles And a particle-containing material was prepared. Part of the obtained particle-containing material was dissolved in 5 parts by mass of ethyl acetate at 23 ° C. to prepare the particle dispersion in which crystalline polyester resin particles having a volume average particle size as shown in Table 2 were dispersed. . Thus, the crystalline polyester resin dispersion liquid of Example 1 was obtained.

(Example 2)
-Preparation of crystalline polyester resin dispersion-
1 part by mass of the crystalline polyester resin of Synthesis Example 2 and 4 parts by mass of polyester resin A as a binder resin are sufficiently mixed with a blender, and then melt-kneaded at 140 ° C. using a twin-screw extruder having a cooling function. After preparing the melt-kneaded product, it was cooled at a cooling rate of 9 ° C./min to form the crystalline polyester resin particles to prepare a particle-containing material. Part of the obtained particle-containing material was dissolved in 5 parts by mass of methyl ethyl ketone at 23 ° C. to prepare the particle dispersion in which crystalline polyester resin particles having a volume average particle diameter as shown in Table 2 were dispersed. Thus, a crystalline polyester resin dispersion of Example 2 was obtained.

(Example 3)
-Preparation of crystalline polyester resin dispersion-
1 part by mass of the crystalline polyester resin of Synthesis Example 3 and 4 parts by mass of polyester resin A as a binder resin are sufficiently mixed with a blender, and then melt-kneaded at 180 ° C. using a twin-screw extruder having a cooling function. Then, the melt-kneaded product was prepared and then cooled at a cooling rate of 5 ° C./min to form the crystalline polyester resin particles to prepare the particle-containing product. Part of the obtained particle-containing material was dissolved in 5 parts by mass of toluene at 23 ° C. to prepare the particle dispersion in which crystalline polyester resin particles having a volume average particle size as shown in Table 2 were dispersed. The crystalline polyester resin dispersion liquid of Example 3 was obtained by the above.

Example 4
-Preparation of crystalline polyester resin dispersion-
1 part by mass of the crystalline polyester resin of Synthesis Example 4 and 4 parts by mass of polyester resin A as a binder resin are sufficiently mixed with a blender, and then melt-kneaded at 130 ° C. using a twin screw extruder having a cooling function. After preparing the melt-kneaded product, it was cooled at a cooling rate of 0.3 ° C./min to form the crystalline polyester resin particles to prepare a particle-containing material. The obtained particle-containing material was partially dissolved at 23 ° C. in 5 parts by mass of tetrahydrofuran / ethyl acetate = 1/4 (molar ratio) to disperse crystalline polyester resin particles having a volume average particle size as shown in Table 2. A prepared particle dispersion was prepared. Thus, a crystalline polyester resin dispersion of Example 4 was obtained.

(Example 5)
-Preparation of crystalline polyester resin dispersion-
1 part by mass of the crystalline polyester resin of Synthesis Example 6 and 4 parts by mass of polyester resin A as a binder resin are sufficiently mixed with a blender, and then melt-kneaded at 120 ° C. using a twin-screw extruder having a cooling function. After preparing the melt-kneaded product, it was cooled at a cooling rate of 3 ° C./min to form the crystalline polyester resin particles to prepare a particle-containing material. Part of the obtained particle-containing material was dissolved in 5 parts by mass of ethyl acetate at 23 ° C. to prepare the particle dispersion in which crystalline polyester resin particles having a volume average particle diameter as shown in Table 2 were dispersed. did. The crystalline polyester resin dispersion liquid of Example 5 was obtained by the above.

(Example 6)
-Preparation of crystalline polyester resin dispersion-
1 part by mass of the crystalline polyester resin of Synthesis Example 7 and 4 parts by mass of polyester resin A as a binder resin are sufficiently mixed with a blender, and then melt-kneaded at 65 ° C. using a twin-screw extruder having a cooling function. After preparing the melt-kneaded product, it was cooled at a cooling rate of 0.2 ° C./min to form the crystalline polyester resin particles to prepare a particle-containing material. Part of the obtained particle-containing material was dissolved in 5 parts by mass of ethyl acetate at 23 ° C. to prepare the particle dispersion in which crystalline polyester resin particles having a volume average particle size as shown in Table 2 were dispersed. . Thus, a crystalline polyester resin dispersion liquid of Example 6 was obtained.

(Example 7)
-Preparation of crystalline polyester resin dispersion-
In Example 1, the crystalline polyester resin dispersion of Example 7 was obtained in the same manner as in Example 1 except that 4 parts by mass of the polyester resin A as the binder resin was changed to 1 part by mass of the polyester resin A. It was.

(Example 8)
-Preparation of crystalline polyester resin dispersion-
In Example 1, the crystalline polyester resin dispersion of Example 8 was obtained in the same manner as in Example 1 except that 4 parts by mass of the polyester resin A as the binder resin was changed to 30 parts by mass of the polyester resin A. It was.

Example 9
-Preparation of crystalline polyester resin dispersion-
In Example 1, except that the polyester resin A as the binder resin was changed to a polyester resin B (Tg = 35 ° C., Mw = 8,500, Mn = 3,500), the same as in Example 1, A crystalline polyester resin dispersion of Example 9 was obtained.

(Example 10)
-Preparation of crystalline polyester resin dispersion-
In Example 1, the same procedure as in Example 1 was carried out except that the polyester resin A as the binder resin was changed to a polyol resin (Tg = 55 ° C., Mw = 85,000, Mn = 13,200). A crystalline polyester resin dispersion of Example 10 was obtained.

(Example 11)
-Preparation of crystalline polyester resin dispersion-
In Example 1, Example 11 was carried out in the same manner as Example 1 except that the polyester resin A as the binder resin was changed to polystyrene resin (Tg = 78 ° C., Mw = 2,000, Mn = 700). A crystalline polyester resin dispersion was obtained.

(Example 12)
-Preparation of crystalline polyester resin dispersion-
In Example 1, except that the polyester resin A as the binder resin was changed to polystyrene acrylic resin (Tg = 65 ° C., Mw = 5,200, Mn = 2,000), A crystalline polyester resin dispersion of Example 12 was obtained.

(Comparative Example 1)
-Preparation of crystalline polyester resin dispersion-
In a 2 liter reaction vessel made of metal, 100 g of the crystalline polyester resin of Synthesis Example 5 and 400 g of ethyl acetate were charged, dissolved by heating at 79 ° C., and then cooled in an ice water bath at a cooling rate of 9 ° C./min. Thus, a crystalline polyester resin dispersion of Comparative Example 1 was prepared.

(Comparative Example 2)
-Preparation of crystalline polyester resin dispersion-
In a 2 liter reaction vessel made of metal, 100 g of the crystalline polyester resin of Synthesis Example 5 and 400 g of methyl ethyl ketone were charged, dissolved by heating at 80 ° C., and then cooled in an ice water bath at a cooling rate of 23 ° C./min. A crystalline polyester resin dispersion of Comparative Example 2 was prepared.

(Comparative Example 3)
-Preparation of crystalline polyester resin dispersion-
In a metal 2 liter reaction vessel, 100 g of the crystalline polyester resin of Synthesis Example 5 and 400 g of toluene are charged, heated and dissolved at 110 ° C., and then cooled in an ice-water bath at a cooling rate of 15 ° C./min. A crystalline polyester resin dispersion of Comparative Example 3 was prepared.

(Comparative Example 4)
-Preparation of crystalline polyester resin dispersion-
In a 2 liter reaction vessel made of metal, 100 g of the crystalline polyester resin of Synthesis Example 5 and 400 g of ethyl acetate were charged and dissolved by heating at 79 ° C., and then cooled in an ice-water bath at a cooling rate of 10 ° C./min. Thus, a crystalline polyester resin dispersion of Comparative Example 4 was prepared.

(Comparative Example 5)
-Preparation of crystalline polyester resin dispersion-
In a 2 liter reaction vessel made of metal, 100 g of the crystalline polyester resin of Synthesis Example 5 and 400 g of ethyl acetate were charged and dissolved by heating at 79 ° C., and then cooled in an ice-water bath at a cooling rate of 20 ° C./min. Thus, a crystalline polyester resin dispersion of Comparative Example 5 was prepared.

(Comparative Example 6)
-Preparation of crystalline polyester resin dispersion-
In a 2 liter reaction vessel made of metal, 100 g of the crystalline polyester resin of Synthesis Example 5 and 400 g of ethyl acetate were charged and dissolved by heating at 79 ° C., and then cooled in an ice water bath at a cooling rate of 17 ° C./min. Thus, a crystalline polyester resin dispersion of Comparative Example 6 was prepared.

  In addition, the volume average particle diameter of the crystalline polyester resin particles in each of the crystalline polyester resin dispersions in Examples 1 to 12 and Comparative Examples 1 to 6 was measured using a particle size measuring device “LA-920” manufactured by Horiba, Ltd. The measured results are shown in Tables 2 to 4.

(Example 13)
-Adhesive substrate production process-
-Preparation of aqueous medium phase (aqueous phase)-
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts by weight of water, 11 parts by weight of sodium salt of ethylene oxide methacrylate adduct sulfate ("Eleminol RS-30"; manufactured by Sanyo Chemical Industries), 138 parts by weight of styrene Then, 138 parts by weight of methacrylic acid and 1 part by weight of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The emulsion was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Next, 30 parts by mass of a 1% by mass ammonium persulfate aqueous solution was added to the reaction solution, and aged at 75 ° C. for 5 hours to co-polymerize vinyl resin (styrene salt of styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate). An aqueous dispersion of polymer) (hereinafter referred to as “fine particle dispersion”) was prepared.
The obtained “fine particle dispersion” had a volume average particle size of 0.14 μm as measured with a laser diffraction particle size distribution analyzer (“LA-920”; manufactured by Horiba, Ltd.). Further, a part of the obtained “fine particle dispersion” was dried to isolate the resin component. The glass transition temperature (Tg) of the resin component was 152 ° C.
Thereafter, 990 parts by weight of water, 80 parts by weight of the fine particle dispersion, 37 parts by weight of a 48.5% by weight aqueous solution of sodium dodecyldiphenyl ether disulfonate (“Eleminol MON-7”; manufactured by Sanyo Chemical Industries), and 90 parts by weight of ethyl acetate Were mixed and stirred to prepare a milky white liquid (hereinafter referred to as “aqueous phase”).

--Synthesis of low molecular weight polyester--
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 229 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 529 parts by mass of bisphenol A propylene oxide 3 mol adduct, 208 parts by mass of terephthalic acid, 46 adipic acid 46 Part by mass and 2 parts by mass of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Next, the reaction solution was reacted for 5 hours under a reduced pressure of 10 to 15 mmHg, and then 44 parts by mass of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure. Molecular polyester was synthesized.
The obtained low molecular weight polyester had a number average molecular weight (Mn) of 2,500, a weight average molecular weight (Mw) of 6,700, a glass transition temperature (Tg) of 43 ° C., and an acid value of 25.
--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 9,500, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.
Then, 410 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 pipe, a stirrer, and a nitrogen introduction pipe, and are heated at 100 ° C. for 5 hours. By reacting, a prepolymer (polymer capable of reacting with the active hydrogen group-containing compound) was synthesized.
The free isocyanate content of the obtained prepolymer was 1.53% by mass.

--Synthesis of ketimine (the active hydrogen group-containing compound)-
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts by mass of isophoronediamine and 75 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound (the active hydrogen group-containing compound).
The amine value of the obtained ketimine compound (the active hydrogen group-containing compound) was 418.

-Preparation of masterbatch (MB)-
1200 parts by weight of water, 540 parts by weight of carbon black (“Printex35”; manufactured by Dexa) as a colorant [DBP oil absorption = 42 ml / 100 mg, pH = 9.5], polyester resin (“RS801”; manufactured by Sanyo Chemical Industries) 1200 parts by mass was added and mixed with 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.

-Preparation of organic solvent phase-
In a reaction vessel in which a stir bar and a thermometer are set, 378 parts by mass of the low-molecular polyester, 110 parts by mass of carnauba wax, 22 parts by mass of CCA (“salicylic acid metal complex E-84”; manufactured by Orient Chemical Industries), and ethyl acetate 947 parts by mass were charged, and the temperature was raised to 80 ° C. with stirring, maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts by mass of the master batch and 500 parts by mass of ethyl acetate were charged into the reaction vessel and mixed for 1 hour to obtain a raw material solution.
1324 parts by mass of the obtained raw material solution was transferred to a reaction vessel, and using a bead mill (“Ultra Visco Mill”; manufactured by Imex Co., Ltd.), the liquid feeding speed was 1 kg / hr, the disk peripheral speed was 6 m / sec, and 0.5 mm zirconia. The carbon black and carnauba wax were dispersed by three passes under the condition of 80% by volume of beads. Next, 1042.3 parts by mass of a 65% by mass ethyl acetate solution of the low molecular weight polyester was added to the dispersion. One pass was performed in a bead mill under the same conditions as described above, and the mixture was dispersed to prepare an organic solvent phase.
The solid content concentration of the obtained organic solvent phase (130 ° C., 30 minutes) was 50% by mass.

--Emulsification / Dispersion--
Into a reaction vessel, 664 parts by mass of the organic solvent phase, 109.4 parts by mass of the prepolymer, 73.9 parts by mass of the crystalline polyester resin dispersion of Example 5 and 4.6 parts by mass of the ketimine compound are charged. After mixing for 1 minute at 5,000 rpm using a TK homomixer (manufactured by Tokushu Kika), 1200 parts by mass of the aqueous phase was added to the reaction vessel, and the rotational speed was 13 using a TK homomixer. The mixture was mixed for 20 minutes at 1,000 rpm, emulsified and dispersed, and an emulsified slurry was prepared.
Next, the emulsified slurry was charged into a reaction vessel equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours. Thereafter, the emulsified slurry was aged at 45 ° C. for 4 hours.

--- Washing and drying--
After 100 parts by mass of the emulsified slurry after aging was filtered under reduced pressure, 100 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered. . 100 mass parts of 10 mass% sodium hydroxide aqueous solution was added to the filter cake obtained here, it mixed with TK type homomixer (30 minutes at 12,000 rpm of rotations), and then it filtered under reduced pressure. 100 mass parts of 10 mass% hydrochloric acid was added to the filter cake obtained here, it mixed with TK type homomixer (10 minutes at 12,000 rpm), and then filtered. Add 300 parts by mass of ion-exchanged water to the filter cake obtained here, mix it with a TK homomixer (10 minutes at 12,000 rpm), and then filter twice to obtain the final filter cake. It was. The final filter cake obtained here was dried at 45 ° C. for 48 hours with a circulating drier and sieved with a mesh having an opening of 75 μm, whereby the toner of Example 13 was obtained.

(Comparative Example 7)
-Preparation of toner-
In Example 13, a toner of Comparative Example 7 was prepared in the same manner as in Example 13 except that the crystalline polyester resin dispersion liquid of Example 5 was not used.

-External additive treatment-
To 100 parts by mass of each of the obtained toners of Example 13 and Comparative Example 7, 0.7 part by mass of hydrophobic silica and 0.3 part by mass of hydrophobized titanium oxide were mixed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The external additive treatment was performed.
For each externally treated toner, the toner physical properties of volume average particle size and particle size distribution, average circularity, charge amount, and thermal characteristics (flow tester characteristics) were measured as follows. The results are shown in Table 5.

<Toner particle size>
The volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner are measured with a particle size measuring device (“Coulter Counter TAII” manufactured by Coulter Electronics Co., Ltd.) with an aperture diameter of 100 μm. From these results, (volume average particle diameter (Dv) / number average particle diameter (Dn)) was calculated.

<Average circularity>
The average circularity of the toner was measured using a flow particle image analyzer (“FPIA-2100”; manufactured by Toa Medical Electronics Co., Ltd.). Specifically, 0.1 to 0.5 ml of a surfactant (alkylbenzene sulfonate) as a dispersant was added to 100 to 150 ml of water from which impure solids had been removed in advance. Next, 0.1 to 0.5 g of each toner was added and dispersed. The obtained dispersion was dispersed for about 1 to 3 minutes with an ultrasonic disperser, and the shape and distribution of the electrostatic charge image developing toner were measured with the concentration of the dispersion set at 3000 to 10,000 / μl. The average circularity was calculated from these measurement results.

<Charge amount>
6 g of each developer was weighed, charged into a metal cylinder that could be sealed, and blown to measure the charge amount. The toner concentration was adjusted to 4.5 to 5.5% by mass.

<Thermal characteristics of toner (flow tester characteristics)>
The thermal characteristics of the toner were measured using an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation) according to the following measurement conditions. The toner flow curve by the flow tester exhibits the behavior as shown in FIGS. 5 (A) and 5 (B). From the obtained flow curve, temperatures such as Ts, Tfb, and T1 / 2 are obtained. In FIGS. 5A and 5B, Ts means a softening temperature (melting and kneading temperature). Tfb means the outflow start temperature. T1 / 2 means the melting temperature due to the 1/2 method softening point.
〔Measurement condition〕
Load: 10 kg / cm ²
Temperature increase rate: 3.0 ° C / min
Die diameter: 0.50mm
Die length: 10.0mm

-Preparation of developer-
Next, each developer of Example 13 and Comparative Example 7 was prepared in a conventional manner from 5% by mass of each toner treated with an external additive and 95% by mass of a copper-zinc ferrite carrier having an average particle diameter of 40 μm coated with a silicone resin. Was prepared.
Using the developers of Example 13 and Comparative Example 17 obtained, (a) fixing property, (b) image density, (c) background stain, (d) cleaning property, (e ) Filming property, (f) heat-resistant storage property (penetration), (g) low-temperature fixability, (h) hot offset property, and (i) comprehensive evaluation. The results are shown in Table 5. The used imaginio Neo 450 (manufactured by Ricoh Co., Ltd.) is an electrophotographic apparatus (image forming apparatus) capable of printing 45 sheets of A4 size paper per minute.

(A) Fixability Using the electrophotographic apparatus (image Neo Neo 450, manufactured by Ricoh Co., Ltd.), transfer paper of plain paper and cardboard (“Type 6200” manufactured by Ricoh Co., Ltd.) and “Copy Printing Paper <135> manufactured by NBS Ricoh Co., Ltd. )), A black solid image was adjusted so that 1.0 ± 0.1 mg / cm ² of toner was developed, and the temperature of the fixing belt was adjusted to be variable. Using the image forming apparatus in this state, a temperature at which no offset occurs in plain paper (offset non-occurrence temperature) was measured. In addition, the minimum fixing temperature for thick paper was measured. The lower limit fixing temperature was defined as the fixing lower limit temperature at which the remaining ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more.

(B) Image Density Using the electrophotographic apparatus (image Neo 450, manufactured by Ricoh Co., Ltd.), the amount of each developer adhered to copy paper (“TYPE 6000 <70W>”; manufactured by Ricoh Co., Ltd.) is 1.00. A black solid image of ± 0.05 mg / cm ² was continuously run up to 100,000 sheets, and at the start, the image density at any five locations for each color alone after 10,000 sheets and 100,000 sheets was measured with a spectrometer ( It measured using "938 Spectrodensitometer"; X-Rite company make. The image density value is shown as an average value of image densities at five locations.
Note that the higher the image density value, the higher the image density, which means that a high density image can be formed.

(C) Stain on the background Using the electrophotographic apparatus (image Neo Neo 450, manufactured by Ricoh Co., Ltd.), continuously run up to 100,000 blank images on copy paper (“TYPE 6000 <70W>”; manufactured by Ricoh Co., Ltd.). At the start, it is stopped during development after 10,000 sheets and after 100,000 sheets, the developer on the developed photoreceptor is transferred to tape, and the difference from the image density of the untransferred tape is measured with a spectrometer ( It measured using "938 Spectrodensitometer"; X-Rite company make.

(D) Cleanability Up to 100,000 black solid images using copy paper (“TYPE 6000 <70W>”; manufactured by Ricoh Co., Ltd.) using the electrophotographic apparatus (image Neo Neo 450, manufactured by Ricoh Co., Ltd.). Running continuously, at the start, transfer residual toner on the photoconductor that passed through the cleaning process after 10,000 sheets and 100,000 sheets was transferred to white paper with Scotch tape (manufactured by Sumitomo 3M Co., Ltd.), and the white paper was macbeth Measurement was made using a reflection densitometer RD514, and the evaluation was performed according to the following criteria.
〔Evaluation criteria〕
○ (Good): The difference from the blank is 0.01 or less.
X (defect): The difference with a blank is more than 0.01.

(E) Filming property Using the electrophotographic apparatus (image Neo Neo 450, manufactured by Ricoh Co., Ltd.), using a copy paper (“TYPE 6000 <70W>”; manufactured by Ricoh Co., Ltd.), 100,000 black solid images. The presence or absence of toner filming on the developing roller or the photoreceptor after continuous running was observed and evaluated according to the following criteria.
〔Evaluation criteria〕
○: Filming does not occur on the developing roller or the photoreceptor.
Δ: Streaky filming is observed on the developing roller or the photosensitive member.
X: Filming is generally observed on the developing roller or the photoreceptor.

(F) Heat-resistant storage stability (Penetration)
Each toner was filled in a 50 ml glass container and left in a constant temperature bath at 50 ° C. for 20 hours. The toner was cooled to room temperature, and the penetration was measured by a penetration test (JIS K2235-1991). The larger the penetration value, the better the heat resistance.

(G) Low-temperature fixability For the low-temperature fixability, the measured lower limit fixing temperature was evaluated according to the following criteria.
〔Evaluation criteria〕
○: The lower limit fixing temperature is 5 ° C. or lower than the conventional one.
Δ: Fixing lower limit temperature is equivalent to the conventional one.
X: The fixing lower limit temperature is 5 ° C. or more higher than before.

(H) Hot offset property The hot offset property was evaluated according to the following criteria, with the temperature of the fixing roll where the winding occurred in the fixing property evaluation as the hot offset temperature.
〔Evaluation criteria〕
○: Hot offset temperature is 5 ° C. or more higher than conventional.
Δ: Hot offset temperature is equivalent to the conventional one.
X: The hot offset temperature is 5 ° C. or more lower than conventional.

(I) Comprehensive evaluation Comprehensive evaluation was performed based on the following reference | standard from the result of all the said performance evaluations.
〔Evaluation criteria〕
○: Overall excellent.
Δ: Overall is normal.
X: Overall poor.

表５の結果から、優れた熱溶融特性を有する結晶性ポリエステル樹脂粒子を含有する実施例１３のトナーは、シャープメルト性を示し、低温定着性に優れ、印字品質が良好であり、連続印字での画質の安定性にも優れ、安定したクリーニング性を有し、感光体、現像ローラ等に対するフィルミング汚染が防止され、低温定着性にも優れており、総合評価が良好（○）であると判定された。
これに対し、比較例７のトナーは、耐熱保存性、低温定着性、クリーニング性などが劣り、総合評価が不良（×）であると判断された。

From the results of Table 5, the toner of Example 13 containing crystalline polyester resin particles having excellent heat melting characteristics exhibits sharp melt properties, excellent low-temperature fixability, good print quality, and continuous printing. Excellent image quality stability, stable cleaning, filming contamination on the photoreceptor, developing roller, etc., excellent low-temperature fixability, and good overall evaluation (○) It was judged.
On the other hand, the toner of Comparative Example 7 was inferior in heat-resistant storage stability, low-temperature fixability, cleaning properties, etc., and the overall evaluation was judged to be poor (x).

  The toner of the present invention has sharp melt properties, has both heat-resistant storage stability and low-temperature fixability, is excellent in offset resistance, chargeability, charge stability, cleaning properties, etc., and is soiled even in various environments. And suitable for forming a high-quality image with high image density and high sharpness without causing filming or the like. The crystalline polyester dispersion of the present invention is suitably used for the production of the toner of the present invention. The developer, toner-containing container, process cartridge, image forming apparatus and image forming method of the present invention using the toner of the present invention are suitably used for high-quality image formation.

FIG. 1 is a schematic explanatory view showing an example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 2 is a schematic explanatory view showing another example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 3 is a schematic explanatory view showing an example in which the image forming method of the present invention is implemented by the image forming apparatus (tandem color image forming apparatus) of the present invention. 4 is a partially enlarged schematic explanatory diagram of the image forming apparatus shown in FIG. FIG. 5A is a graph showing a flow curve of a flow tester for evaluating the thermal characteristics of the toner. FIG. 5B is a partially enlarged graph of FIG. FIG. 6 is an IR chart diagram of the crystalline polyester resin of Consistency Example 2. FIG. 7 is an IR chart of the crystalline polyester resin of Example 3 of integrity. FIG. 8 is an IR chart of the crystalline polyester resin of Example 4 of integrity. FIG. 9 is an IR chart of the crystalline polyester resin of Example 5 of integrity. FIG. 10 is an IR chart of the crystalline polyester resin of Example 6 of integrity. FIG. 11 is an IR chart of the crystalline polyester resin of Example 7 of integrity.

Explanation of symbols

10 Photoconductor (Photoconductor drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 21 exposure device 22 secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure belt 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Developer Roller 44C Developing roller 45K Black developing unit 45Y Yellow developing unit 45M Magenta developing unit 45C Cyan developing unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separating roller 53 Constant current source 55 Switching claw 56 Discharging roller 57 Discharging tray 58 Corona charger 60 Cleaning device 61 Developing device 62 Transfer charger 63 Photoconductor cleaning device 64 Static eliminator 70 Static elimination lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100 Image forming device 120 Tandem type developer 130 Document base 142 Feed roller 143 Paper bank 144 Paper feed cassette 145 Separation roller 146 Paper feed path 147 Carriage roller 148 Paper feed path 150 Copier main body 200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF)

Claims (19)

  A melt-kneaded material preparation step of preparing a melt-kneaded material by melt-kneading a crystalline polyester resin and a binder resin, and cooling the melt-kneaded material to form crystalline polyester resin particles to prepare a particle-containing material A crystalline polyester resin dispersion comprising: a particle-containing material preparation step; and a particle dispersion liquid preparation step in which the particle-containing material is partially dissolved with a solvent to prepare the crystalline polyester resin particle dispersion. Production method.   The method for producing a crystalline polyester resin dispersion according to claim 1, wherein the crystalline polyester resin dispersion is used for producing toner. The manufacturing method of the crystalline polyester resin dispersion liquid in any one of Claim 1 to 2 with which a crystalline polyester resin contains the structure represented by following Structural formula (1).

However, in the structural formula (1), R ¹ and R ² may be the same as or different from each other, and represent a hydrogen atom or a hydrocarbon group. R ³ represents a divalent hydrocarbon group. m represents an integer of 1 or more. n represents the degree of polymerization. Crystalline polyester resin is from claim 1 having an absorption based on the infrared absorption of the olefin to one of a range of 965 ± 10 cm ^-1 and 990 ± 10 cm ^-1 in (IR) spectrum? Ch (out-of-plane deformation vibration) 3 The manufacturing method of the crystalline polyester resin dispersion liquid in any one of.   5. The method for producing a crystalline polyester resin dispersion according to claim 1, wherein a melting temperature Tm (° C.) of the crystalline polyester resin is 50 to 150 ° C. as a DSC endothermic peak temperature.   The weight average molecular weight (Mw) in the crystalline polyester resin is 1,000 to 30,000, the number average molecular weight (Mn) is 500 to 6,000, and the molecular weight distribution (Mw / Mn) is 2 to 8. The manufacturing method of the crystalline polyester resin dispersion liquid in any one of Claim 1 to 5.   The method for producing a crystalline polyester resin dispersion according to any one of claims 1 to 6, wherein the binder resin is at least one selected from a polyester resin, a polyol resin, a polystyrene resin, and a polystyrene acrylic resin.   The method for producing a crystalline polyester resin dispersion according to any one of claims 1 to 7, wherein the solid content concentration of the crystalline polyester resin in the melt-kneaded product is 1 to 50 mass% with respect to the binder resin.   9. The melt kneading temperature Ts (° C.) satisfies the relationship of the following formula, Tm ≦ Ts ≦ (Tm + 50 ° C.), where the melting temperature of the crystalline polyester resin is Tm (° C.). The manufacturing method of the crystalline polyester resin dispersion liquid of description.   When the melting temperature of the crystalline polyester resin is Tm (° C.), the solvent cannot dissolve the polyester resin at a temperature (° C.) lower than (Tm-40), and the temperature (° C.) above (Tm-40). 10) The method for producing a crystalline polyester resin dispersion according to any one of claims 1 to 9, wherein the polyester resin can be dissolved.   A crystalline polyester resin dispersion produced by the method for producing a crystalline polyester resin dispersion according to claim 1.   The crystalline polyester resin dispersion according to claim 11, wherein the crystalline polyester resin particles have a volume average particle size of 0.2 to 2 μm.   An active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and the crystalline polyester resin dispersion according to claim 11 are dispersed and reacted in an aqueous medium. A method for producing toner, comprising at least an adhesive base material production step for obtaining toner while producing an adhesive base material.   A toner manufactured by the method for manufacturing a toner according to claim 13.   15. An active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted to form an adhesive base material in an aqueous medium, and are obtained in the form of particles and include crystalline polyester resin particles. The toner described in 1.   The toner according to claim 14, wherein the softening temperature (Ts) is 50 ° C. or more and the outflow start temperature (Tfb) is 60 ° C. or more.   An active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted to form an adhesive base material in an aqueous medium, and are obtained in the form of particles, including crystalline polyester resin particles, and a softening temperature. A toner having (Ts) of 50 ° C. or higher and an outflow start temperature (Tfb) of 60 ° C. or higher.   A developer comprising the toner according to claim 14.   18. A toner-containing container comprising the toner according to claim 14 contained in a container.

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