JP2007293043A - Toner for electrostatic charge image development, method for manufacturing toner for electrostatic charge image development, electrostatic charge image developer and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development that stabilizes developing and transfer processes with lapse of time while maintaining high transfer efficiency/high picture quality by toner base particles which are nearly spherical and that stably gives an image with high picture quality without causing contamination in a machine due to desorption of an external additive. <P>SOLUTION: The toner for electrostatic charge image development comprises toner base particles for electrostatic charge image development containing a colorant and a toner binder resin obtained by polycondensation reaction of polycarboxylic acid and polyol, and an external additive, and the toner is characterized in that: 50 mol% to 100 mol% of the polycarboxylic acid comprises a specified compound; the toner base particles have an average particle size of 3 μm to 9 μm; the shape factor SF1 of the toner base particles ranges from 100 to 145; the external additive contains particles having an average particle size of 80 nm to 200nm by the coating rate of 10% to 40%; and the total coating rate by the external additive ranges from 80% to 100%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an electrostatic image developing toner capable of obtaining a high-quality image over a long period of time by suppressing in-machine contamination of a charging member and the like, a manufacturing method thereof, an electrostatic image developer, and an image forming method.

  In electrophotography, an electrostatic latent image formed on a latent image carrier (photoconductor) is developed with a toner containing a colorant, and the resulting toner image is transferred onto a transfer member, which is then heated. The latent image carrier is cleaned to form an electrostatic latent image again. The dry developer used in such an electrophotographic method includes a one-component developer that uses a toner in which a colorant and the like are blended in a binder resin, and a two-component developer in which a carrier is mixed with the toner. Broadly divided. In a one-component developer, magnetic powder is used, and the magnetic one-component developer is transported to a developing carrier (photoreceptor) by magnetic force and developed. It can be classified as a non-magnetic one-component developer to be developed. Since the latter half of the 1980s, the market for electrophotography has been strongly demanded for miniaturization and high functionality with the key to digitization, and in particular, high-quality prints close to high-quality printing and silver halide photography are desired for full color image quality.

Digitization processing is indispensable as a means for achieving high image quality, and the effect of digitization related to such image quality is that complex image processing can be performed at high speed. This makes it possible to control characters and photographic images separately, and the reproducibility of both qualities is greatly improved compared to analog technology. In particular, for photographic images, gradation correction and color correction are possible, and this is advantageous over analog in terms of gradation characteristics, definition, sharpness, color reproduction, and graininess. However, on the other hand, it is necessary to faithfully form a latent image created by an optical system for image output, and as a toner, the particle size is increasingly reduced, and the activity aimed at faithful reproduction is accelerated. However, it is difficult to stably obtain high image quality simply by reducing the particle size of the toner, and improvement of basic characteristics in development, transfer, and fixing characteristics is more important.
In particular, color images are formed by superimposing three or four color toners. Therefore, if any one of these toners exhibits different characteristics from the initial stage in terms of development, transfer, and fixing, or performance different from other colors, the color reproducibility is deteriorated, or the image quality is deteriorated such as deterioration of graininess and uneven color. It will be a thing. In order to maintain a stable high-quality image over time as in the initial stage, it is important how to stably control the characteristics of each toner. In fact, it has been reported that the toner is agitated in the developing machine, and the change in the fine structure of the toner surface easily occurs and the transferability is greatly changed (see Patent Document 1).

In order to improve fluidity, chargeability, and transferability, it has been proposed to make the toner shape close to a spherical shape (see Patent Document 2). However, by making the toner spherical, the following problems are likely to occur. That is, the developing machine is provided with a transport amount control plate for controlling the developer transport amount to be constant, and the transport amount can be controlled by changing the distance between the mag roll and the transport amount control plate. However, when a spherical toner is used, the fluidity as a developer increases, and at the same time, it hardens and the bulk density increases. As a result, there is a phenomenon in which developer accumulation occurs in the conveyance regulation region and the conveyance amount becomes unstable.
By controlling the surface roughness on the mag roll and reducing the gap between the control plate and the mag roll, it is possible to improve the transport amount, but the packing performance due to the developer pool becomes stronger and the stress applied to the toner accordingly. Become stronger. As a result, it has been confirmed that a fine structure change on the toner surface, in particular, embedding or peeling of the external additive easily occurs, resulting in a problem that the development and transferability are greatly changed from the initial stage.

  In order to improve these, it has been reported that spherical toner and non-spherical toner can be combined to suppress packing properties and achieve high image quality (see Patent Document 3). However, these are effective in suppressing packing properties, but non-spherical toner tends to remain as a transfer residue, and high transfer efficiency cannot be achieved. In the case of performing simultaneous development recovery, since the non-spherical toner that is the transfer residue is recovered, the ratio of the non-spherical toner increases, which causes a problem of further decreasing the transfer efficiency.

In addition, in order to improve the developability, transferability, and cleaning properties of the spherical toner, two types of inorganic fine particles having different particle sizes of particles having an average particle size of 5 nm to less than 20 nm and particles having an average particle size of 20 nm to 40 nm And adding a specific amount is disclosed (see Patent Document 4). These can initially obtain high developability, transferability, and cleaning properties, but since the force applied to the toner over time cannot be reduced, external additives can easily be buried or peeled off, Development and transferability are greatly changed from the initial stage.
Further, the detachment of the external additive does not stop in the developing machine but is scattered everywhere in the machine. In particular, when an external additive adheres to an optical lens or polygon mirror, a fine electrostatic charge image cannot be drawn. In addition, when scattered or adhered to a charging roll or the like, fine charging leakage occurs from the portion where the external additive is adhered, causing potential unevenness of the photoreceptor, and it is impossible to obtain a fine image. In particular, when a material having a lower resistance than that of a resin, such as inorganic fine particles, is used as an external additive, even a very small amount of adhesion causes a significant charging leak.

  On the other hand, it is disclosed that it is effective to use inorganic particles having a large particle size in order to suppress the burying of the external additive in the toner against such stress (see Patent Documents 5 to 7). . However, since the specific gravity of inorganic particles is large in all cases, if the external additive particles are made large, peeling of the external additive is unavoidable due to the stirring stress in the developing machine. In addition, since the inorganic particles do not exhibit a perfect spherical shape, it is difficult to control the spike of the external additive to be constant when it is deposited on the toner surface. This causes variations in the micro-surface convex shape that functions as a spacer, and stress is selectively applied to the convex portion, so that burying or peeling of the external additive is further accelerated, which is not sufficient.

  In addition, a technique of adding 50 to 200 nm organic particles to a toner in order to effectively develop a spacer function is disclosed (see Patent Document 8). By using organic particles, it is possible to effectively exhibit a spacer function in the initial stage. However, although the organic particles are less likely to be buried or peeled off with respect to stress over time, it is difficult to stably develop a high spacer function because the organic particles themselves are deformed. Further, it is conceivable to obtain a spacer effect by adding a large amount of organic particles to the toner surface or using organic particles having a large particle diameter, but in this case, the characteristics of the organic particles are greatly reflected. That is, the influence on the powder characteristics such as fluidity inhibition and thermal aggregation deterioration of the inorganic particle-added toner, and the organic particles themselves have a charge imparting ability, and the degree of control freedom from the viewpoint of charging is reduced. This will affect the charging and development.

On the other hand, not only the physical properties and structure of the external additive, but also the toner surface structure varies greatly depending on how it is externally added to the toner surface, and its characteristics are also different. In particular, the toner surface structure is largely changed by the external addition method for the toner having a nearly spherical shape. In the case of irregular shaped toner, once the external additive enters the concave part of the toner surface, the external additive is difficult to move even if the blending is continued, and since the fluidity is poor, it takes a share due to contact between the toners, Although it is easy to increase the adhesion strength between the toner and the external additive at the same position of the external additive, in the case of a nearly spherical toner, since the toner surface has no recess, the external additive on the toner surface is easy to move. In addition, since the fluidity is good, it is difficult to increase the share due to contact between the toners, and it is difficult to increase the adhesion strength between the toner and the external additive. In particular, when the particle size of the external additive is increased, the tendency becomes remarkable.
Therefore, as a method of attaching an external additive to the wet process toner, a method of adhering to the toner surface using a hybridizer (manufactured by Nara Machinery Co., Ltd.) has been proposed (see Patent Document 9). Certainly, it becomes possible to strongly fix the external additive to the toner surface, but conversely, the embedding is large, the function as a spacer is weakened, and the transfer performance is deteriorated.

Recently, there is a high demand for colorization, especially on-demand printing, and a method for forming a multicolor image on a transfer belt for high-speed copying and transferring the multicolor image to an image fixing material at a time and fixing it. Has been reported (see Patent Document 10). If the process of transferring from the photoreceptor to the transfer belt is the primary transfer, and the process of transferring from the transfer belt to the transfer body is the secondary transfer, the transfer is repeated twice, and a technique for improving the transfer efficiency becomes more and more important.
In particular, in the case of secondary transfer, a multicolor image is transferred at a time, and the transfer material (for example, in the case of paper, its thickness, surface property, etc.) changes variously. Therefore, it is necessary to control the transfer property extremely high.

By the way, a vinyl polymer has been widely used as a binder resin for toner, and a high molecular weight polymer has been proposed to obtain non-offset properties. Since the coalescence has a high softening point, it is necessary to set the temperature of the heat roller high in order to obtain a fixed image having excellent glossiness, which goes against energy saving. In addition, a toner using a vinyl polymer is easily affected by a plasticized plasticizer of vinyl chloride, and the toner itself is plasticized by being in contact with the plasticizer, and becomes sticky and plasticized. There is a problem of contamination of vinyl chloride products (hereinafter referred to as vinyl chloride resistance).
In contrast, polyester resins are excellent in vinyl chloride resistance, can be manufactured relatively easily with low molecular weight, and polyester resins are more in comparison to toners that contain vinyl polymers as binder resins. Polyester is energy-saving because it has excellent wettability to a support such as a transfer paper when melted, and has the advantage that it can be sufficiently fixed at a lower temperature than a vinyl polymer having almost the same softening point. It is often used as a binder resin for toner.

Japanese Patent Laid-Open No. 10-312089 Japanese Patent Laid-Open No. 62-184469 JP-A-6-308759 Japanese Patent Laid-Open No. 3-100161 JP-A-7-28276 JP-A-9-319134 Japanese Patent Laid-Open No. 10-312089 JP-A-6-266152 Japanese Patent Laid-Open No. 5-34971 JP-A-8-115007

  Accordingly, an object of the present invention is to solve the conventional problems and achieve the following object. That is, the object of the present invention is to maintain high transfer efficiency and high image quality with toner base particles that are nearly spherical, to stabilize the development and transfer processes over time, and to prevent internal contamination due to desorption of external additives. It is an object to provide an electrostatic image developing toner and an electrostatic image developer capable of stably obtaining a high-quality image without being generated. Another object of the present invention is to provide a method for producing the electrostatic image developing toner and an image forming method using the electrostatic charge developing toner or the electrostatic image developer.

As a result of intensive studies to achieve the above object, the present inventors have found that the above problems can be solved by the means described in <1>, <3>, <4> and <5>. The present invention has been completed. It is described below together with <2> which is a preferred embodiment.
<1> An electrostatic charge image developing toner comprising an electrostatic charge image developing toner mother particle containing a binder resin for a toner and a colorant obtained by a polycondensation reaction of a polycarboxylic acid and a polyol, and an external additive, 50 mol% or more and 100 mol% or less of the polycarboxylic acid is composed of a compound represented by the formula (1) and / or the formula (2), and the average particle diameter of the toner base particles is 3 μm or more and 9 μm or less. The shape factor SF1 of the particles is 100 or more and 145 or less, and particles having an average particle diameter of 80 nm or more and 200 nm or less are included as the external additive in a coverage of 10% or more and 40% or less, and the total coverage by the external additive is 80% or more and 100 %, An electrostatic charge image developing toner,
R ¹ OOCA ¹ _m B ¹ _n A ¹ _l COOR ^{1 ′} (1)
(A ¹ : methylene group, B ¹ : aromatic hydrocarbon group, R ¹ , R ^{1 ′} : hydrogen atom or monovalent hydrocarbon group, 1 ≦ m + l ≦ 12, 1 ≦ n ≦ 3)
R ² OOCA ² _p B ² _q A ² _r COOR ^{2 ′} (2)
(A ² : methylene group, B ² : alicyclic hydrocarbon group, R ² , R ^{2 ′} : hydrogen atom or monovalent hydrocarbon group, 0 ≦ p ≦ 6, 0 ≦ r ≦ 6, 1 ≦ q ≦ 3)
<2> The electrostatic charge image developing toner according to <1>, wherein 50 mol% or more and 100 mol% or less of the polyol is composed of the compound represented by formula (3),
HOX _h Y _j X _k OH (3)
(X: alkylene oxide group, Y: bisphenol skeleton group, 1 ≦ h + k ≦ 10, 1 ≦ j ≦ 3)
<3> a step of aggregating the binder resin particles and the colorant particles in a dispersion containing at least the binder resin particles and the colorant particles to obtain aggregated particles, and a step of heating and aggregating the aggregated particles Containing the electrostatic image developing toner according to <1> or <2>,
<4> An electrostatic charge image developer comprising the electrostatic charge image developing toner and carrier according to <1> or <2>,
<5> A latent image forming step of forming an electrostatic latent image on the surface of the latent image holding member, and developing the electrostatic latent image formed on the surface of the latent image holding member with toner or an electrostatic charge image developer to form a toner image. An image forming method comprising: a developing step for forming; a transferring step for transferring the toner image formed on the surface of the latent image holding member to the surface of the recording member; and a fixing step for fixing the toner image transferred on the surface of the recording member An image forming method using the electrostatic image developing toner according to <1> or <2> as the toner, or the electrostatic image developer according to <4> as the developer. .

  According to the present invention, while maintaining high transfer efficiency and high image quality with toner base particles that are nearly spherical, the development and transfer processes are stabilized over time, and internal contamination due to desorption of external additives occurs. Therefore, it is possible to provide an electrostatic image developing toner and an electrostatic image developer capable of stably obtaining a high-quality image. Furthermore, the present invention can provide a method for producing the electrostatic image developing toner and an image forming method using the electrostatic image developing toner or the electrostatic image developer.

-Electrostatic image developing toner-
The electrostatic image developing toner of the present invention (in the present invention, the “electrostatic image developing toner” is also simply referred to as “toner”) is a binder resin for toner and coloration obtained by polycondensation reaction of polycarboxylic acid and polyol. An electrostatic charge image developing toner mother particle containing an agent and an external additive, wherein 50 mol% or more and 100 mol% or less of the polycarboxylic acid is represented by formula (1) and / or formula (2) The toner base particles have an average particle diameter of 3 μm or more and 9 μm or less, the toner base particles have a shape factor SF1 of 100 or more and 145 or less, and an average particle diameter of 80 nm as the external additive. It is characterized by containing particles having a particle size of 200 nm or less and a coverage of 10% or more and 40% or less, and a total coverage of the external additive of 80% or more and 100% or less.
R ¹ OOCA ¹ _m B ¹ _n A ¹ _l COOR ^{1 ′} (1)
(A ¹ : methylene group, B ¹ : aromatic hydrocarbon group, R ¹ , R ^{1 ′} : hydrogen atom or monovalent hydrocarbon group, 1 ≦ m + l ≦ 12, 1 ≦ n ≦ 3)
R ² OOCA ² _p B ² _q A ² _r COOR ^{2 ′} (2)
(A ² : methylene group, B ² : alicyclic hydrocarbon group, R ² , R ^{2 ′} : hydrogen atom or monovalent hydrocarbon group, 0 ≦ p ≦ 6, 0 ≦ r ≦ 6, 1 ≦ q ≦ 3)
Moreover, it is preferable that 50 mol% or more and 100 mol% or less of this polyol consists of a compound represented by Formula (3).
HOX _h Y _j X _k OH (3)
(X: alkylene oxide group, Y: bisphenol skeleton group, 1 ≦ h + k ≦ 10, 1 ≦ j ≦ 3)
That is, the electrostatic image developing toner of the present invention is an electrostatic image developing toner in which an external additive is externally added to at least toner base particles. The toner base particles include at least a binder resin and a colorant. The average particle diameter of the toner base particles is 3 to 9 μm, and the shape factor SF1 of the toner base particles is 100 to 145. The binder resin includes a toner binder resin obtained by a polycondensation reaction of a polycarboxylic acid and a polyol.

As described above, in order to achieve high transfer efficiency, it is preferable to make the toner base particles close to a sphere, but when considering the transfer efficiency over time, high transfer efficiency can be achieved simply by bringing the toner close to a sphere. I can't. By using toner base particles that are nearly spherical, the inorganic particles added to the surface of the toner base particles are uniformly attached, so that the adhesion force of the toner base particles can be reduced. On the other hand, since the inorganic particles on the surface are buried or detached over time, the function for reducing the adhesive force of the toner base particles is lowered, so that it is considered that the transfer efficiency over time and further the developability are lowered. .
In particular, since the toner base particles close to a sphere have no concave portions on the surface, the inorganic particles on the surface are easy to move, so that they are easily detached from the toner base particles, and are easily embedded when stressed.

For this reason, it is important that the external additive is uniformly attached to the surface of the toner base particles so that it is difficult to be buried and not detached with time. In order to prevent simple separation, the external additive may be firmly attached to the surface of the toner base particles. However, the external additive is embedded in the toner surface, and the spacer effect between the toner and the photosensitive member or transfer belt. Will decrease.
In addition, the detachment of the external additive is also largely due to variations in the strength of the external additive attached to the toner surface. That is, even if most of the external additives adhere to the toner surface with such strength that they do not desorb, if some of the remaining external additives have low adhesion, some of the external additives are desorbed. End up. As a result, the external additive is detached by stirring the developing machine and the like, and the charging member, the lens of the optical system and the polygon mirror are contaminated, and a fine latent image cannot be obtained.

Therefore, the present inventors consider that the variation in the adhesion strength of the external additive to the toner surface is caused by the variation in the hardness of the surface of the toner base particles, and this is the result of constituting most of the toner base particles. It was thought that this occurs due to the extremely fine compositional uneven distribution of the resin. In other words, the present invention has been completed because it is considered that variation in adhesion between the external additive and the toner base particles can be suppressed by reducing the compositional uneven distribution of the binder resin for toner.
This uneven distribution of the binder resin for toner is considered to be due to variations in the structure and molecular weight of the polymerized resin due to variations in reactivity in the polymerization process of the resin.

  A metal polycondensation catalyst is generally used for the production of polyester by polycondensation reaction. In a polycondensation reaction using a metal polycondensation catalyst, an intermediate is formed between the catalyst and the monomer during the reaction, thereby improving the reactivity and promoting the ester synthesis reaction. However, since the catalyst activity and dehydration efficiency decrease at low temperatures, polycondensation tends not to proceed, and the molecular weight and degree of polymerization often do not increase. Therefore, in the polycondensation reaction of polyester using a metal polycondensation catalyst, a high polymerization reaction temperature is required, and it is difficult to achieve energy saving. In particular, this tendency is remarkable in a monomer having a cyclic structure which is a non-crystalline polyester raw material.

  Amorphous polyester has high hardness at room temperature, and thus has high fluidity, and has properties that are very suitable for toners in terms of offset suppression, low-temperature fixability, image quality, and the like. Crystalline polyester mainly composed of linear monomers has sharp melt properties due to crystallinity and has great merit for low-temperature fixability, but has the disadvantage of being inferior in powder flowability and image strength, It is considered that the non-crystalline polyester is more suitable for the characteristics as the main component of the binder resin.

  The inventors of the present invention have a large difference in reactivity between the cyclic monomer composing the non-crystalline polyester and the linear monomer composing the crystalline polyester because of the difference in reactivity derived from the structure. I guessed. Cyclic monomers tend to be more restricted in molecular movement than linear monomers, especially at low temperatures, due to their hard structure with limited rotational movement. In particular, a monomer having an aromatic ring tends to form a resonance structure between the aromatic ring and the polycondensation reactive functional group, which causes the reaction intermediate to be resonantly stabilized, causing delocalization of electrons, and May interfere with the progress of the condensation reaction. By proceeding the reaction without hindering the progress of the polycondensation reaction, it is possible to obtain a binder resin for toner having no uneven composition. Therefore, by fully understanding this mechanism and designing a highly reactive monomer for non-crystalline polyester that reacts even at low temperatures, it is possible to obtain a binder resin with little compositional unevenness, and thus adhesion of external additives. It is thought that the variation in the state can be suppressed, which leads to the solution of this problem.

Further, the particle diameter of the external additive to be added and the coverage thereof are also important. At least one external additive must exhibit a so-called spacer effect as a transfer aid in the transfer process. For this purpose, the average particle diameter is 80 nm to 200 nm, and the coverage is 10 to 40%. Therefore, the electrostatic image developing toner of the present invention has particles having an average particle diameter of 80 nm to 200 nm as an external additive at least in a coverage of 10 to 40%.
When the average particle diameter of the external additive is smaller than 80 nm, a sufficient spacer effect cannot be obtained, and the number of points where the toner base particles directly come into contact with the photoreceptor or the transfer member without using the external additive. As a result, the intermolecular force between the two increases, the non-electrostatic adhesion increases, and transfer becomes difficult. On the other hand, when it is larger than 200 nm, the spacer effect is sufficient, but the intermolecular force is sufficiently small if there is a space up to 200 nm, and it is not necessary to expand it further. Therefore, it is this external additive having a size of 80 to 200 nm that actually functions as a transfer aid. In addition, when external energy exceeding 200 nm is applied to the surface of the toner base particles so as not to be detached, the toner base particles themselves are easily distorted or deformed. In addition, when an external additive smaller than 80 nm is used in combination as a fluidizing agent, the adhesion strength to the toner base particles becomes too strong, and sufficient fluidity cannot be given to the toner.
The external additive as a transfer aid preferably has an average particle size of 80 to 160 nm, and more preferably 80 to 140 nm.

Next, in the present invention, the coverage of the external additive having an average particle size of 80 to 400 nm is 10 to 40%. If the coverage is less than 10%, the external additive existing between the photoreceptor and the toner base particles is present. The amount of the agent (transfer aid) is small, and the toner base particles are in direct contact with the photoreceptor, so that the spacer effect cannot be exhibited. On the other hand, when the coverage is more than 40%, the gap for adding the external additive as a fluidizing agent is not present on the toner surface, and it becomes difficult to impart sufficient fluidity to the toner.
By the way, the external additive (transfer auxiliary agent) as the spacer effect exhibits a better function when the external additive is buried over time, such as by stirring the developing machine. That is, the reason why the external additive of 80 to 200 nm is added at a coverage of 10% or more is to maintain the transfer efficiency over time. Conversely, in the initial stage, the total coverage of the external additive is more important than the particle diameter of the external additive.

In the present invention, the total coverage of the external additive is 80 to 100%. If the total coverage is less than 80%, good initial transfer characteristics cannot be obtained. If the total coverage exceeds 100%, the toner base particles are coated with one or more layers of external additives, and free external additives are present. This causes desorption of the external additive.
The present toner external additive has a functional separation design, and it is preferable to use not only a transfer aid but also a fluidizing agent as an external additive in order to obtain a good toner characteristic comprehensively. For this reason, 80 to 200 nm external additives as transfer assistants have a coverage of 10 to 40%, and a fluidizing agent is used in combination so that the total coverage is 80 to 100%. This is preferable because the problems of the present invention can be solved.

(Toner mother particles)
In the present invention, the toner base particles contain at least a binder resin and a release agent. The average particle diameter of the toner base particles is 3 to 9 μm, and the shape factor of the toner base particles is 100 to 145. Details will be described below.

[Binder resin]
In the present invention, the binder resin used for the electrostatic charge image developing toner is a binder resin obtained by a polycondensation reaction of a polycarboxylic acid and a polyol, and 50 mol% or more and 100 mol% or less of the polycarboxylic acid is represented by the formula It consists of a compound represented by (1) and / or Formula (2). Moreover, it is preferable that 50 mol% or more and 100 mol% or less of this polyol consists of a compound represented by Formula (3).
R ¹ OOCA ¹ _m B ¹ _n A ¹ _l COOR ^{1 ′} (1)
(A ¹ : methylene group, B ¹ : aromatic hydrocarbon group, R ¹ , R ^{1 ′} : hydrogen atom or monovalent hydrocarbon group, 1 ≦ m + l ≦ 12, 1 ≦ n ≦ 3)
R ² OOCA ² _p B ² _q A ² _r COOR ^{2 ′} (2)
(A ² : methylene group, B ² : alicyclic hydrocarbon group, R ² , R ^{2 ′} : hydrogen atom or monovalent hydrocarbon group, 0 ≦ p ≦ 6, 0 ≦ r ≦ 6, 1 ≦ q ≦ 3)
HOX _h Y _j X _k OH (3)
(X: alkylene oxide group, Y: bisphenol skeleton group, 1 ≦ h + k ≦ 10, 1 ≦ j ≦ 3)
In the present invention, the polyester resin obtained by polycondensation is preferably an amorphous polyester resin.

  In the present invention, the polycondensation reaction is performed by an esterification reaction (dehydration reaction) of a polycarboxylic acid and a polyol, or an ester exchange reaction between a polycarboxylic acid polyalkyl ester and a polyol. Although any reaction can be used as the polycondensation reaction, a polycondensation reaction using a polycarboxylic acid and a polyol and accompanied by a dehydration reaction is preferable.

50 mol% or more and 100 mol% or less of the polycarboxylic acid used for this invention consists of a compound (dicarboxylic acid) represented by Formula (1) and / or Formula (2). In the present invention, the term “carboxylic acid” includes esterified products and acid anhydrides.
R ¹ OOCA ¹ _m B ¹ _n A ¹ _l COOR ^{1 ′} (1)
(A ¹ : methylene group, B ¹ : aromatic hydrocarbon group, R ¹ , R ^{1 ′} : hydrogen atom or monovalent hydrocarbon group, 1 ≦ m + l ≦ 12, 1 ≦ n ≦ 3)
R ² OOCA ² _p B ² _q A ² _r COOR ^{2 ′} (2)
(A ² : methylene group, B ² : alicyclic hydrocarbon group, R ² , R ^{2 ′} : hydrogen atom or monovalent hydrocarbon group, 0 ≦ p ≦ 6, 0 ≦ r ≦ 6, 1 ≦ q ≦ 3)
Here, the monovalent hydrocarbon group represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydrocarbon group, or a heterocyclic group, and these groups may have an arbitrary substituent. . R ¹ , R ^{1 ′} , R ² and R ^{2 ′} are preferably a hydrogen atom or a lower alkyl group, more preferably a hydrogen atom, a methyl group or an ethyl group, and most preferably a hydrogen atom.
Moreover, the aromatic hydrocarbon group in Formula (1) and the alicyclic hydrocarbon group in Formula (2) may be substituted.

<Dicarboxylic acid represented by Formula (1)>
The dicarboxylic acid represented by the formula (1) has at least one aromatic hydrocarbon group B ¹ , but its structure is not particularly limited. Examples of the aromatic hydrocarbon group B ¹ include benzene, naphthalene, acenaphthylene, fluorene, anthracene, phenanthrene, tetracene, fluoranthene, pyrene, benzofluorene, benzophenanthrene, chrysene, triphenylene, benzopyrene, perylene, anthrene, benzonaphthacene. , Benzochrysene, pentacene, pentaphen, coronene skeleton and the like, but are not limited thereto. Further, a substituent may be further added to these structures.

The number of aromatic hydrocarbon groups B ¹ contained in the dicarboxylic acid represented by the formula (1) is 1 or more and 3 or less. If it is less than 1, the non-crystallinity of the produced polyester is lost, and if it has more than 3 aromatic hydrocarbon groups, it is difficult to synthesize such a dicarboxylic acid. Not only the efficiency is lowered, but also the melting point and viscosity of the dicarboxylic acid represented by the formula (1) are increased, and the reactivity is decreased due to the size and bulkiness of the dicarboxylic acid.

  When the dicarboxylic acid represented by the formula (1) includes a plurality of aromatic hydrocarbon groups, the aromatic hydrocarbon groups may be directly bonded to each other, and other saturated aliphatic hydrocarbon groups, etc. A structure having a skeleton of Examples of the former include a biphenyl skeleton, and examples of the latter include, but are not limited to, a bisphenol A skeleton, a benzophenone, and a diphenylethene skeleton.

A group suitable as the aromatic hydrocarbon group B ¹ has a structure in which the main skeleton has C6 to C18 carbon atoms. The number of carbon atoms of the main skeleton does not include the number of carbon atoms contained in the functional group bonded to the main skeleton. Examples include benzene, naphthalene, acenaphthylene, fluorene, anthracene, phenanthrene, tetracene, fluoranthene, pyrene, benzofluorene, benzophenanthrene, chrysene, triphenylene, bisphenol A skeleton and the like. Among these, particularly preferred skeletons include benzene, naphthalene, anthracene, and phenanthrene. Most preferably, a benzene or naphthalene structure is used.
It is preferable that the main skeleton has 6 or more carbon atoms because the production of the monomer is easy. Moreover, it is preferable that the carbon number of the main skeleton is 18 or less because the size of the monomer molecule is appropriate and the reactivity is not lowered due to the limitation of molecular motion. Furthermore, the ratio of the reactive functional group in the monomer molecule is appropriate, which is preferable because the reactivity does not decrease.

The dicarboxylic acid represented by the formula (1) contains at least one methylene group A ¹ . The methylene group may be linear or branched, and for example, a methylene chain, a branched methylene chain, a substituted methylene chain and the like can be used. In the case of a branched methylene chain, the structure of the branched portion is not limited, and may have an unsaturated bond, a further branch, a cyclic structure, or the like.
The number of methylene groups A ¹ is at least 1 and not more than 12 as the total m + 1 in the molecule. Preferably, m + 1 is 2 or more and 6 or less, and m and l are more preferably the same number. When m + 1 is 0, that is, when the dicarboxylic acid represented by the formula (1) does not have a methylene group, the aromatic hydrocarbon and the carboxyl groups at both ends are directly bonded. In this case, the reaction intermediate formed by the catalyst and the dicarboxylic acid represented by the formula (1) is resonance-stabilized and the reactivity is lowered. In addition, when m + 1 is larger than 12, the straight chain portion is too large with respect to the dicarboxylic acid represented by the formula (1), so that the produced polymer has crystallinity characteristics, or the glass transition temperature Tg is May decrease.

The bonding site between the methylene group A ¹ or carboxyl group and the aromatic hydrocarbon group B ¹ is not particularly limited, and may be any of o-position, m-position, and p-position.
Examples of the dicarboxylic acid represented by the formula (1) include 1,4-phenylenediacetic acid, 1,4-phenylenedipropionic acid, 1,3-phenylenediacetic acid, 1,3-phenylenedipropionic acid, 1,2 -Phenylenediacetic acid, 1,2-phenylenedipropionic acid and the like can be mentioned, but are not limited thereto. Preferred are 1,4-phenylene dipropionic acid, 1,3-phenylene dipropionic acid, 1,4-phenylene diacetic acid, and 1,3-phenylene diacetic acid. Examples thereof include 4-phenylene diacetate and 1,3-phenylene diacetate.

  Various functional groups may be added to any of the structures of the dicarboxylic acid represented by the formula (1). The carboxylic acid group that is a polycondensation reactive functional group may be an acid anhydride, an acid ester, or an acid chloride. However, since an intermediate between an acid ester compound and a proton is easily stabilized and tends to suppress reactivity, a carboxylic acid, a carboxylic acid anhydride, or a carboxylic acid chloride is preferably used.

<Dicarboxylic acid represented by formula (2)>
Dicarboxylic acid represented by formula (2) contains an alicyclic hydrocarbon group B ^2. There is no particular limitation on the alicyclic hydrocarbon structure, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, Examples thereof include, but are not limited to, cyclooctene, adamantane, diamantane, triamantane, tetramantane, iron, twistin, norbornene skeleton, and the like. Moreover, a substituent may be added to these substances. In view of the stability of the structure, the size and bulkiness of the molecule, cyclobutane, cyclopentane, cyclohexane, norbornene, adamantane and the like are preferable.
The number of alicyclic hydrocarbon groups contained in this monomer is at least 1 and no more than 3. When it is less than 1, the non-crystallinity of the produced polyester is lost, and when it has more than 3 alicyclic hydrocarbon groups, the melting point of the dicarboxylic acid represented by the formula (2) is increased. The reactivity decreases depending on the size and bulkiness of the molecule.
In the case of including a plurality of alicyclic hydrocarbon groups, either a structure in which alicyclic hydrocarbon groups are directly bonded to each other or a structure having a skeleton such as other saturated aliphatic hydrocarbons can be used. Examples of the former include a dicyclohexyl skeleton and the like, and examples of the latter include a hydrogenated bisphenol A skeleton, but are not limited thereto.

  A suitable alicyclic hydrocarbon group is a C3-C12 substance. The number of carbon atoms of the main skeleton does not include the number of carbon atoms contained in the functional group bonded to the main skeleton. For example, a substance having a cyclopropane, cyclobutane, cyclopentane, cyclohexane, adamantane, norbornene skeleton, or the like can be given. Among these, preferred examples of the skeleton include cyclobutane, cyclopentane, cyclohexane, norbornene, and adamantane. Particularly suitable skeletons include cyclobutane, cyclohexane, and cyclohexene structures.

The dicarboxylic acid represented by the formula (2) may have a methylene group A ² in its structure. The methylene group may be linear or branched, and for example, a methylene chain, a branched methylene chain, a substituted methylene chain and the like can be used. In the case of a branched methylene chain, the structure of the branched portion is not limited, and may have an unsaturated bond, a further branch, a cyclic structure, or the like.
Methylene group A ² number, p, r is 6 or less, respectively. When either or both of p and r are larger than 6, since the linear portion is too large for the dicarboxylic acid represented by the formula (2), the produced polymer has crystalline characteristics, The glass transition temperature Tg may decrease.

The bonding site between the methylene group A ² or carboxyl group and the alicyclic hydrocarbon group B ² is not particularly limited, and may be any of o-position, m-position, and p-position.
Examples of the dicarboxylic acid represented by the formula (2) include 1,1-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,1-cyclopentenedicarboxylic acid, Examples include cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexenedicarboxylic acid, norbornene-2,3-dicarboxylic acid, and adamantanedicarboxylic acid. It is not limited. Among these, a substance having a cyclobutane, cyclopentane, or cyclohexane skeleton is preferably used, and 1,3-cyclohexanedicarboxylic acid or 1,4-cyclohexanedicarboxylic acid is particularly preferable.
The dicarboxylic acid represented by the formula (2) may have various functional groups added to any of its structures. The carboxylic acid group that is a polycondensation reactive functional group may be an acid anhydride, an acid ester, or an acid chloride. However, since an intermediate between an acid ester compound and a proton is easily stabilized and tends to suppress reactivity, a carboxylic acid, a carboxylic acid anhydride, or a carboxylic acid chloride is preferably used.

In this invention, 50 mol% or more and 100 mol% or less of compounds (dicarboxylic acid) represented by said Formula (1) and / or Formula (2) are included with respect to the whole polycarboxylic acid component. The compound represented by the above formula (1) and the compound represented by the formula (2) can be used alone or in combination.
When the ratio of the compound represented by the formula (1) and / or the formula (2) is less than 50 mol%, the reactivity in the low-temperature polycondensation cannot be sufficiently exhibited, the molecular weight does not increase, and the degree of polymerization is low. The polyester may be low, or many residual polycondensation components may be mixed. As a result, the fluidity of the powder may deteriorate, for example, the binder resin may become sticky at room temperature, or viscoelasticity and glass transition temperature suitable for the binder resin for toner may not be obtained. Preferably, the compound represented by the above formula (1) and / or formula (2) is contained in an amount of 60 to 100 mol%, and the compound represented by the above formula (1) and / or formula (2) is contained in an amount of 80 to 100 mol%. It is more preferable.

<Diol represented by Formula (3)>
In the electrostatic image developing toner of the present invention, the binder resin is a binder resin obtained by a polycondensation reaction of a polycarboxylic acid and a polyol, and 50 mol% or more and 100 mol% or less of the polyol is represented by the formula (3). It is preferable to consist of a compound (diol).
HOX _h Y _j X _k OH (3)
(X: alkylene oxide group, Y: bisphenol skeleton group, 1 ≦ h + k ≦ 10, 1 ≦ j ≦ 3)
The diol represented by the above formula (3) includes at least one bisphenol skeleton group Y. The bisphenol skeleton is not particularly limited as long as it is a skeleton composed of two phenol groups. Examples thereof include bisphenol A, bisphenol C, bisphenol E, bisphenol F, bisphenol M, bisphenol P, bisphenol S, and bisphenol Z. Yes, but not limited to this. Examples of the skeleton that can be preferably used include bisphenol A, bisphenol C, bisphenol E, bisphenol F, bisphenol M, bisphenol P, bisphenol S, and bisphenol Z, and more preferably bisphenol A, bisphenol E, and bisphenol F. is there.
The number j of the bisphenol skeleton is 1 or more and 3 or less. When the diol represented by the formula (3) does not have a bisphenol skeleton, the produced polyester may have the characteristics of a crystalline polyester and is not suitable for the purpose. On the other hand, when it contains more than 3, it is difficult to produce such a diol, which is not practical from the viewpoint of efficiency and cost, but also has a large and bulky molecule. The reactivity becomes low due to an increase in the temperature.

In the present invention, the diol represented by the formula (3) has at least one alkylene oxide group. Examples of the alkylene oxide group include, but are not limited to, an ethylene oxide group, a propylene oxide group, and butylene oxide. Preferred are ethylene oxide and propylene oxide, and particularly preferred is ethylene oxide.
The number of alkylene oxide groups h + k is 1 or more and 10 or less in one molecule. When the number of alkylene oxides is less than 1, that is, when no alkylene oxide group is added, the electrons are delocalized by resonance stabilization between the hydroxyl group and the aromatic ring in the bisphenol skeleton, and the diol represented by the formula (3) Nucleophilic attack on carboxylic acid is weakened, and molecular weight extension and polymerization degree are suppressed. On the other hand, when more than 10 alkylene oxide groups are added, the linear portion in the diol represented by the formula (3) becomes too long, and the produced polyester has a crystalline property. The number of reactive functional groups in the diol represented by (3) decreases, and the reaction probability decreases.
The same number of h and k is preferable for promoting an even reaction. Further, the number of alkylene oxide groups h + k is preferably 6 or less, and more preferably, the number of alkylene oxide groups h, k is 2 or 1 respectively. Moreover, when it has 2 or more alkylene oxide groups, it can also have 2 or more types of alkylene oxide groups in 1 molecule.

  Examples of the diol represented by the formula (3) include bisphenol A ethylene oxide adduct (h + k is 1 to 10), bisphenol A propylene oxide adduct (h + k is 1 to 10), ethylene oxide propylene oxide adduct (h + k is 2). -10), bisphenol Z ethylene oxide adduct (h + k is 1 to 10), bisphenol Z propylene oxide adduct (h + k is 1 to 10), bisphenol S ethylene oxide adduct (h + k is 1 to 10), bisphenol S Propylene oxide adduct (h + k is 1 to 10), bisphenol F ethylene oxide adduct (h + k is 1 to 10), bisphenol F propylene oxide adduct (h + k is 1 to 10), bisphenol E ethylene oxide adduct (h + k is 1) -10) Bisphenol E propylene oxide adduct (h + k is 1 to 10), bisphenol C ethylene oxide adduct (h + k is 1 to 10), bisphenol C propylene oxide adduct (h + k is 1 to 10), bisphenol M ethylene oxide adduct ( h + k is 1-10), bisphenol M propylene oxide adduct (h + k is 1-10), bisphenol P ethylene oxide adduct (h + k is 1-10), bisphenol P propylene oxide adduct (h + k is 1-10), etc. However, it is not limited to these. Particularly preferred are bisphenol A ethylene oxide 1-mole adduct (h and k each 1), bisphenol A ethylene oxide 2-mole adduct (h and k each 2), bisphenol A propylene oxide 1-mole adduct (h and k each 1), bisphenol A ethylene oxide 1 mol propylene oxide 2 mol adduct, bisphenol E ethylene oxide 1 mol adduct (1 each of h, k), bisphenol E propylene oxide 1 mol adduct (1 each of h, k), bisphenol Examples thereof include 1 mol adduct of F ethylene oxide (1 each of h and k) and 1 mol adduct of bisphenol F propylene oxide (1 each of h and k).

  In this invention, it is preferable that 50 mol% or more and 100 mol% or less of diol represented by Formula (3) are contained in a polyol. When the content is within the above range, the reactivity in low-temperature polycondensation is sufficient, the molecular weight is increased, and a polyester having a high degree of polymerization is preferred. Further, it is preferable because the residual polycondensation component is not mixed and the binder resin is not sticky at room temperature and the fluidity of the powder is not deteriorated. More preferably, the diol represented by the above formula (3) is contained in an amount of 60 to 100 mol%, and the diol represented by the above formula (3) is further preferably contained in an amount of 80 to 100 mol%.

<Catalyst>
In the present invention, it is preferable to use a catalyst in the polycondensation reaction of the polycarboxylic acid and the polyol.
In the present invention, among these, it is preferable to use a Bronsted acid catalyst. Examples of Bronsted acid catalysts include, for example, alkylbenzene sulfonic acids such as dodecylbenzene sulfonic acid, isopropyl benzene sulfonic acid, and camphor sulfonic acid, alkyl sulfonic acid, alkyl disulfonic acid, alkyl phenol sulfonic acid, alkyl naphthalene sulfonic acid, Higher fatty acid sulfates such as alkyl tetralin sulfonic acid, alkyl allyl sulfonic acid, petroleum sulfonic acid, alkyl benzimidazole sulfonic acid, higher alcohol ether sulfonic acid, alkyl diphenyl sulfonic acid, monobutyl phenyl phenol sulfuric acid, dibutyl phenyl phenol sulfuric acid, dodecyl sulfuric acid Higher alcohol sulfate, higher alcohol ether sulfate, higher fatty acid amide alkylol sulfate, higher fatty acid amide ester Killed sulfate ester, naphthenyl alcohol sulfate, sulfated fat, sulfosuccinate ester, various fatty acids, sulfonated higher fatty acid, higher alkyl phosphate ester, resin acid, resin acid alcohol sulfate, naphthenic acid, niobic acid, and all of these Although the salt compound of these can be used, it is not limited to this. Moreover, these catalysts may have a functional group in the structure. A plurality of these catalysts may be combined as necessary. Examples of the Bronsted acid catalyst preferably used include dodecylbenzenesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and camphorsulfonic acid.

Other polycondensation catalysts generally used can be used together with the above catalyst or alone. Specific examples include metal catalysts, hydrolase type catalysts, and basic catalysts.
Examples of the metal catalyst include, but are not limited to, the following. For example, an organic tin compound, an organic titanium compound, an organic tin halide compound, and a rare earth-containing catalyst can be mentioned.
Specific examples of the rare earth-containing catalyst include scandium (Sc), yttrium (Y), and lanthanoid elements such as lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), and europium. (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), etc. are effective. is there. Of these, alkylbenzene sulfonates, alkyl sulfate esters, and those having a triflate structure are particularly effective. Examples of the triflate include X (OSO ₂ CF ₃ ) _{3 in} the structural formula. Here, X is a rare earth element, and among these, X is preferably scandium (Sc), yttrium (Y), ytterbium (Yb), samarium (Sm), or the like.
The lanthanoid triflate is described in detail in the Journal of Synthetic Organic Chemistry, Vol. 53, No. 5, p44-54).

When a metal catalyst is used as the catalyst, the metal content derived from the catalyst in the resulting binder resin is preferably 100 ppm or less, more preferably 75 ppm or less, and even more preferably 50 ppm or less. . Therefore, it is preferable not to use a metal catalyst or to use a very small amount even when a metal catalyst is used.
The metal content in the binder resin can be measured by fluorescent X-ray analysis. Specifically, the contents of tin, titanium, and rare earth metal are measured with fluorescent X-rays to obtain the metal content derived from the catalyst.

The hydrolase type catalyst is not particularly limited as long as it catalyzes an ester synthesis reaction. Examples of the hydrolase in the present invention include EC (enzyme number) 3.1 group such as carboxyesterase, lipase, phospholipase, acetylesterase, pectinesterase, cholesterol esterase, tannase, monoacylglycerol lipase, lactonase, lipoprotein lipase and the like. (See Maruo and Tamiya's "Enzyme Handbook" Asakura Shoten, (1982), etc.) Hydrolase enzymes classified into EC 3.2 group that act on glycosyl compounds such as esterases, glucosidases, galactosidases, glucuronidases, xylosidases EC that acts on peptide bonds such as hydrolase, aminopeptidase, chymotrypsin, trypsin, plasmin, subtilisin, etc. classified into EC 3.3 group such as epoxide hydrase Hydrolase classified .4 group, mention may be made of hydrolytic enzymes such as classified into EC3.7 group such as furo retinoic hydrolase.
Among the above esterases, enzymes that hydrolyze glycerol esters to liberate fatty acids are called lipases, but lipases are highly stable in organic solvents, catalyze ester synthesis reactions in high yields, and are available at a lower price. There are advantages such as what you can do. Therefore, in the present invention, it is desirable to use lipase from the viewpoint of yield and cost.
Lipases of various origins can be used, but preferable examples include Pseudomonas genus, Alcaligenes genus, Achromobacter genus, Candida genus, Aspergillus genus, Rhizopus Examples include lipases obtained from microorganisms such as (Rhizopus) genus and Mucor genus, lipases obtained from plant seeds, lipases obtained from animal tissues, pancreatin, and steapsin. Of these, it is desirable to use lipases derived from microorganisms of the genus Pseudomonas, Candida, and Aspergillus.

Examples of the basic catalyst include, but are not limited to, general organic basic compounds, nitrogen-containing basic compounds, and tetraalkyl or arylphosphonium hydroxides such as tetrabutylphosphonium hydroxide. Examples of the organic base compound include ammonium hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and examples of the nitrogen-containing basic compound include amines such as triethylamine and dibenzylmethylamine, pyridine, methylpyridine, methoxypyridine, Alkali metals such as quinoline and imidazole, alkali metals such as sodium, potassium, lithium and cesium and alkaline earth metals such as calcium, magnesium and barium, hydrides, amides, alkalis, alkaline earth metals and acids And salts with carbonates, phosphates, borates, carboxylates and phenolic hydroxyl groups.
Moreover, a compound with an alcoholic hydroxyl group, a chelate compound with acetylacetone, and the like can be exemplified, but the invention is not limited thereto.

  As a total addition amount of a catalyst, it can add 1 type or multiple in the ratio of 0.1-10,000 ppm with respect to a polycondensation component.

In the present invention, the polyester resin is preferably obtained by a polycondensation reaction at a temperature lower than the conventional reaction temperature. The reaction temperature is preferably 70 ° C or higher and 150 ° C or lower. More preferably, it is 80 degreeC or more and 140 degrees C or less.
It is preferable that the reaction temperature is 70 ° C. or higher, because no decrease in reactivity due to a decrease in monomer solubility and catalyst activity occurs, and an increase in molecular weight is not suppressed. Moreover, since it can manufacture with low energy as reaction temperature is 150 degrees C or less, it is preferable. Moreover, since coloring of resin, decomposition | disassembly of produced | generated polyester, etc. do not arise, it is preferable.

  This polycondensation reaction can be carried out by a general polycondensation method such as bulk polymerization, emulsion polymerization, suspension polymerization, or other underwater polymerization, solution polymerization, interfacial polymerization, etc., but bulk polymerization is preferably used. Although the reaction can be performed under atmospheric pressure, general conditions such as reduced pressure and nitrogen flow can be used for the purpose of increasing the molecular weight of the obtained polyester molecule.

In the present invention, the binder resin for toner preferably has a glass transition temperature of 30 ° C. or higher and 75 ° C. or lower from the viewpoint of fixability and image formability. A glass transition temperature of 30 ° C. or higher is preferable because the fluidity of the toner powder at normal temperature is good. A glass transition temperature of 75 ° C. or lower is preferable because sufficient melting can be obtained and a satisfactory minimum fixing temperature can be obtained.
The glass transition temperature is more preferably 35 to 70 ° C, still more preferably 45 to 65 ° C. The glass transition temperature can be controlled by the molecular weight of the binder resin, the monomer composition of the binder resin, the addition of a crosslinking agent, and the like.
Moreover, a glass transition point can be measured by the method prescribed | regulated to ASTMD3418-82, and is measured with a differential scanning calorimeter (DSC).

The weight average molecular weight suitable for the non-crystalline binder resin produced in the present invention to be suitable for toner is in the range of 5,000 to 50,000, more preferably 7,000 to 35,000. . A weight average molecular weight of 5,000 or more is preferable because powder flowability at normal temperature is good and toner blocking does not occur. Furthermore, the cohesive force as a binder resin for toner is good, and the hot offset property is not lowered, which is preferable. A weight average molecular weight of 50,000 or less is preferable because a good hot offset property and a good minimum fixing temperature can be obtained. Further, the time and temperature required for polycondensation are appropriate, and the production efficiency is good, which is preferable.
The weight average molecular weight can be measured by, for example, gel permeation chromatography (GPC).

In the present invention, the amorphous polyester can be polycondensed together with polycondensation components other than those described above as long as the characteristics thereof are not impaired.
As the polycarboxylic acid, a polyvalent carboxylic acid containing two or more carboxyl groups in one molecule can be used. Among these, a divalent carboxylic acid is a compound containing two carboxyl groups in one molecule. For example, oxalic acid, succinic acid, itaconic acid, glutaconic acid, glutaric acid, maleic acid, adipic acid, β-methyl Adipic acid, speric acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, malic acid, citric acid, hexahydroterephthalic acid, Malonic acid, pimelic acid, tartaric acid, mucous acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, biphenyl-p, p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, Naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarbo Acid, anthracene dicarboxylic acid, n- dodecyl succinic acid, n- dodecenylsuccinic acid, iso-dodecyl succinic acid, iso-dodecenyl succinic acid, n- octyl succinic acid, and n- octenyl succinate and the like. Examples of the polyvalent carboxylic acid other than the divalent carboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid.
Moreover, although these acid anhydrides or acid chlorides and acid esterified compounds can be mentioned, it is not limited thereto.

  As the polyol (polyhydric alcohol), a polyol containing two or more hydroxyl groups in one molecule can be used. Among these, a divalent polyol (diol) is a compound containing two hydroxyl groups in one molecule. For example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, butenediol, neopentyl glycol, pentane. Glycol, hexane glycol, cyclohexanediol, cyclohexanedimethanol, octanediol, nonanediol, decanediol, dodecanediol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenols other than the bisphenols mentioned above, hydrogen Examples thereof include added bisphenols. Examples of polyols other than divalent polyols include glycerin, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, and tetraethylol benzoguanamine.

  The content of these polycarboxylic acid monomers is less than 50 mol% of the polycarboxylic acid which is a polycondensation component. More preferably, it is 40 mol% or less, More preferably, it is 20 mol% or less. Moreover, it is preferable that content of said polyol is less than 50 mol% of the polyol which is a polycondensation component, More preferably, it is 40 mol% or less, More preferably, it is 20 mol% or less.

In the present invention, the polycondensation step may include a polycarboxylic acid and a polyol, which are the aforementioned polycondensation components, and a polymerization reaction between a prepolymer prepared in advance. The prepolymer is not limited as long as it is a polymer that can be melted or uniformly mixed with the monomer.
Further, the binder resin of the present invention includes a homopolymer of the above-described polycondensation component, a copolymer in which two or more monomers including the above-described polymerizable component are combined, a mixture thereof, a graft polymer, one It may have partial branching or a crosslinked structure.

  In the present invention, using the binder resin for toner produced as described above, a mechanical manufacturing method such as a melt-kneading pulverization method, or a binder resin dispersion using the polyester (in the present invention, “binding” Toner base particles are manufactured by a so-called chemical manufacturing method in which a toner is manufactured from a binder resin dispersion, and an external additive is added thereto. Thus, a toner can be manufactured.

  When the toner base particles are produced by the melt kneading and pulverization method, it is preferable to stir and mix the polyester resin produced as described above with other toner base particle raw materials in advance using a Henschel mixer, a supermixer or the like before melt kneading. . At this time, a combination of the agitator capacity, the rotation speed of the agitator, the agitation time, and the like must be selected.

Next, the toner base particles can be obtained by kneading the agitated product of the binder resin for toner and other raw material for the toner base particles in a molten state by a known method. Kneading with a single-screw or multi-screw extruder is preferable because dispersibility is improved. At this time, the number of kneading screw zones of the kneading apparatus, the cylinder temperature, the kneading speed, etc. must all be set to appropriate values and controlled. Among the control factors at the time of kneading, the number of rotations of the kneader, the number of kneading screw zones, and the cylinder temperature have a particularly great influence on the kneading state. In general, the number of rotations is preferably 300 to 1,000 rpm, and the number of kneading screw zones is kneaded better by using a multi-stage zone such as a two-stage screw rather than a single stage. The set temperature of the cylinder is preferably determined by the softening temperature of the non-crystalline polyester which is the main component of the binder resin, and is usually about −20 to + 150 ° C. than the softening temperature. A cylinder set temperature within the above range is preferable because sufficient kneading and dispersion can be obtained and aggregation does not occur. Furthermore, the kneading share is increased, sufficient dispersion can be obtained, and cooling after kneading is easy, which is preferable.
The melt-kneaded kneaded product is sufficiently cooled and then pulverized by a known method such as a mechanical pulverization method such as a ball mill, a sand mill, or a hammer mill, or an airflow pulverization method. If cooling by a conventional method is not sufficient, a cooling or freeze pulverization method can also be selected.

  In order to control the particle size distribution of the toner base particles, the toner base particles after pulverization may be classified. By eliminating particles having an inappropriate diameter by classification, there is an effect of improving the fixability and image quality of the obtained toner.

  On the other hand, in response to recent demands for high image quality, many toner chemical manufacturing methods have been adopted as technologies for reducing the diameter of toner and for low-energy manufacturing methods. In the present invention, a general production method can be used as a chemical production method of the toner using the above-described binder resin for toner, but an aggregation and coalescence method is preferable. The aggregation coalescence method is a known aggregation method in which a latex in which a binder resin is dispersed in water is produced and aggregated (aggregated) with other toner raw materials.

The method for dispersing the binder resin produced as described above in water is not particularly limited. It can be selected from known methods such as forced emulsification, self-emulsification, and phase inversion emulsification. Of these, the self-emulsification method and the phase inversion emulsification method are preferably applied in consideration of the energy required for emulsification, the particle size controllability of the obtained emulsion, stability, and the like.
The self-emulsification method and the phase inversion emulsification method are described in “Application Technology of Ultrafine Particle Polymer” (CMC Publishing). As the polar group used in the self-emulsification method, a carboxyl group, a sulfone group, and the like can be used. In the present invention, a carboxyl group is preferably used when applied to an amorphous polyester binder resin for toner.
In the present invention, the median diameter of the binder resin in the binder resin particle dispersion is preferably 1 μm or less, more preferably 10 to 500 nm, and still more preferably 80 to 500 nm.

Using the binder resin dispersion prepared as described above, so-called latex, it is possible to produce a toner in which the toner particle diameter and distribution are controlled using an aggregation method.
That is, in the present invention, a step of aggregating the binder resin particles and the colorant particles in a dispersion containing at least the binder resin particles and the colorant particles to obtain aggregated particles, and heating the aggregated particles to fuse Preferably, the electrostatic image developing toner is produced by a method for producing an electrostatic image developing toner including the step of causing the electrostatic image developing toner to be produced.
Specifically, the toner base particles are prepared by mixing the latex prepared as described above with a colorant particle dispersion and, if necessary, a release agent particle dispersion, and further adding an aggregating agent to cause heteroaggregation. The agglomerated particles having a diameter are formed, and then heated to a temperature equal to or higher than the glass transition point or the melting point of the binder resin particles to fuse and coalesce the agglomerated particles, and then washed and dried. In this manufacturing method, the shape of the toner base particles can be controlled from an indeterminate shape to a spherical shape by selecting the heating temperature condition.

  After completing the coalescence and coalescence process of aggregated particles, the desired toner base particles are obtained through an optional washing process, solid-liquid separation process, and drying process. It is desirable to perform replacement cleaning. Moreover, although there is no restriction | limiting in particular in a solid-liquid separation process, From the point of productivity, suction filtration, pressure filtration, etc. are suitable. Further, the drying process is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity.

  As a flocculant, besides a surfactant, an inorganic salt or a divalent or higher metal salt can be suitably used. In particular, when a metal salt is used, it is preferable in characteristics such as cohesion control and toner chargeability. The metal salt compound used for aggregation is obtained by dissolving a general inorganic metal compound or a polymer thereof in a resin particle dispersion, but the metal elements constituting the inorganic metal salt are a periodic table (long period table). 2A, 3A, 4A, 5A, 6A, 7A, 8, 1B, 2B, and 3B having a charge of 2 or more are preferred, and any resin that dissolves in the form of ions in the aggregated system of resin particles can be used. Good. Specific examples of preferred inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and polyaluminum chloride, polyaluminum hydroxide, calcium sulfide. And inorganic metal salt polymers. Among these, an aluminum salt and a polymer thereof are particularly preferable. In general, in order to obtain a sharper particle size distribution, even if the valence of the inorganic metal salt is more than 1, more than 2, more than 3, and the same valence, the polymerization type inorganic metal salt weight Combined is more suitable.

In the present invention, the electrostatic image developing toner base particles contain at least a binder resin and a colorant.
As the coloring component (coloring agent), any of known pigments and dyes can be used. Specifically, carbon black such as furnace black, channel black, acetylene black, thermal black, inorganic pigments such as bengara, bitumen, titanium oxide, fast yellow, disazo yellow, pyrazolone red, chelate red, brilliant carmine, para brown, etc. Azo pigments, phthalocyanine pigments such as copper phthalocyanine and metal-free phthalocyanine, and condensed polycyclic pigments such as flavantron yellow, dibromoanthrone orange, perylene red, quinacridone red and dioxazine violet. Chrome Yellow, Hansa Yellow, Benzidine Yellow, Slen Yellow, Quinoline Yellow, Permanent Orange GTR, Pyrarozone Orange, Vulcan Orange, Watch Chang Red, Permanent Red, Dupont Oil Red, Resor Red, Rhodamine B Lake, Lake Red C, Rose Bengal, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxalate, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 17, C.I. I. Pigment blue 15: 1, C.I. I. And various pigments such as CI Pigment Blue 15: 3. These may be used alone or in combination of two or more.

In addition to the above polycondensable resin particle dispersion, addition polymerization resin particle dispersions prepared by using conventionally known emulsion polymerization can be used together.
Examples of addition polymerization monomers for preparing these resin particle dispersions include styrenes such as styrene and parachlorostyrene, vinyl naphthalene, vinyl chloride, vinyl bromide, vinyl fluoride, vinyl acetate, propion. Vinyl esters such as vinyl acid, vinyl benzoate, vinyl butyrate, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-chloroethyl acrylate, Methylene aliphatic carboxylic esters such as phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide such as vinyl methyl ether, vinyl ethyl ether, vinyl Monomers having N-containing polar groups such as vinyl ethers such as ruisobutyl ether, N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone, methacrylic acid, acrylic Homopolymers and copolymers of vinyl monomers such as vinyl carboxylic acids such as acid, cinnamic acid and carboxyethyl acrylate, and various waxes can also be used.

  In the case of addition polymerization monomers, emulsion polymerization can be carried out using an ionic surfactant or the like to produce a resin particle dispersion, and in the case of other resins, it is oily and the solubility in water is compared. If it is soluble in a low solvent, the resin is dissolved in those solvents and dispersed in an aqueous medium with a disperser such as a homogenizer together with an ionic surfactant or polymer electrolyte, and then heated or decompressed. Then, the resin particle dispersion can be obtained by evaporating the solvent.

  In the present invention, if necessary, known additives can be blended in combination of one or more kinds within a range that does not affect the results of the present invention. For example, flame retardants, flame retardant aids, brighteners, waterproofing agents, water repellents, inorganic fillers (surface modifiers), mold release agents, antioxidants, plasticizers, surfactants, dispersants, lubricants, Fillers, extenders, binders, charge control agents and the like. These additives can be blended in any process for producing an electrostatic image developing toner.

  Examples of internal additives include various commonly used charge control agents such as quaternary ammonium salt compounds and nigrosine compounds as charge control agents. However, stability during production and reduction of wastewater contamination can be used. Therefore, materials that are difficult to dissolve in water are suitable.

Examples of mold release agents include low molecular weight polyolefins such as polyethylene, polypropylene and polybutene, silicones having a softening point upon heating, fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide and the like. Plant waxes such as ester wax, carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, animal waxes such as beeswax, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax , Minerals such as microcrystalline wax, Fischer-Tropsch wax, petroleum-based wax, and modified products thereof can be used.
These waxes are dispersed in water together with ionic surfactants, polymer electrolytes such as polymer acids and polymer bases, and heated with a homogenizer or pressure discharge type disperser that can be heated to the melting point or higher and subjected to strong shearing. And a dispersion of particles less than 1 micron can be made.

  Examples of flame retardants and flame retardant aids include, but are not limited to, bromine flame retardants that have already been widely used, antimony trioxide, magnesium hydroxide, aluminum hydroxide, and ammonium polyphosphate.

In the present invention, the average particle diameter of the toner base particles is 3 μm or more and 9 μm or less. The thickness is preferably 3 to 7.5 μm, and more preferably 4 to 6.8 μm or less.
When the average particle diameter of the toner base particles is less than 3 μm, the adhesion is insufficient and a developed image without fog cannot be obtained. On the other hand, if it exceeds 9 μm, sufficient image resolution cannot be obtained.
In the present invention, the average particle diameter of the toner base particles is a volume median diameter (D ₅₀ ). The volume median diameter (D ₅₀ ) can be measured using a laser diffraction particle size distribution measuring device or the like.

In the present invention, the toner base particles preferably have an average volume particle distribution GSDv of 1.4 or less. In particular, in the case of a chemical toner, GSDv is more preferably 1.3 or less.
GSDv draws cumulative distribution from the smaller diameter side for the volume for the particle size range (channel) divided on the basis of the particle size distribution, and the particle diameter that becomes 16% cumulative is the volume D _16v and the particle diameter that becomes 84% cumulative. It is defined as volume D _84v . Using these, the volume average particle distribution (GSDv) is calculated by the following equation.
Average volume particle distribution GSDv = ( _D84v / _D16v ) ^0.5
A GSDv of 1.4 or less is preferable because the particle diameter is uniform, good fixability is obtained, and no device failure due to poor fixing occurs. In addition, it is preferable because it does not cause in-machine contamination or developer deterioration due to toner scattering.
The average volume particle distribution GSDv can be measured by using an electric resistance type particle size distribution Zokan Fengshi Multisizer or the like.

  The toner base particles used in the present invention have a shape factor SF1 of 100 to 145, but are preferably pseudo-spherical having an SF1 of 120 to 140. The effect of adding the inorganic oxide to the pseudo-spherical shape is also superior to the case of the irregular toner base particles. That is, when the same amount of inorganic oxide is added to the toner base particles, the powder flowability of the toner of the pseudo spherical toner base particles is considerably higher than that of the amorphous toner base particles. Even if the charge amount is approximately the same, the toner of the pseudo spherical toner base particles exhibits high developability and transferability.

  SF1 is calculated as follows.

ここでＭＬは粒子の絶対最大長、Ａは粒子の投影面積である。
これらは、主に顕微鏡画像又は走査電子顕微鏡画像をルーゼックス画像解析装置によって取り込み、解析することによって数値化される。
尚、本発明において、トナー母粒子の平均粒子径、ＧＳＤｖ及び形状係数は、これに外添剤を外添した静電荷像現像トナーの平均粒子径及び形状係数によって近似することができる。

Here, ML is the absolute maximum length of the particle, and A is the projected area of the particle.
These are quantified mainly by capturing and analyzing a microscope image or a scanning electron microscope image with a Luzex image analyzer.
In the present invention, the average particle size, GSDv, and shape factor of the toner base particles can be approximated by the average particle size and shape factor of the electrostatic charge image developing toner having an external additive added thereto.

The electrostatic image developing toner of the present invention is obtained by externally adding an external additive to toner base particles.
(External additive)
In the present invention, as the external additive of the toner, particles having an average particle diameter of 80 nm or more and 200 nm or less are set to a coverage of 10 to 40%, and the total coverage including other external additives is set to 80 to 100%. If added, any external additive may be used.
There are no particular restrictions on the transfer aid having an average particle size of 80 to 200 nm, and either inorganic particles or organic resin particles can be used, but it is preferable to use inorganic particles rather than organic resin particles. Inorganic particles are preferred as the inorganic particles. The organic resin particles may be crushed by stress such as developing machine stirring, and a sufficient spacer effect may not be obtained.
Here, the average particle diameter of the external additive means a volume median diameter, and when the external additive causes aggregation, it indicates the average primary particle diameter of the particles. The average particle diameter of the external additive can be measured by a laser diffraction type particle size distribution analyzer or the like. For the external additive externally added to the toner, after calculating the area of the external additive by image analysis of the external additive on the toner surface observed with a scanning electron microscope or the like with LUSEX or the like, the equivalent calculated from the area is calculated. The average particle diameter can be calculated from the circle diameter. In that case, it is preferable to calculate by observation of 100 or more.

  These inorganic particles include silica, titanium oxide, metatitanic acid, aluminum oxide, magnesium oxide, alumina, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, chromium oxide, antimony trioxide, and oxidation. Examples of the particles include zirconium. Among these, it is preferable to use one selected from silica, titanium oxide, and metatitanic acid from the viewpoint of precise charge control of the toner to which lubricant particles and cerium oxide are added.

In particular, in an image requiring high transfer efficiency such as a full-color image, the silica has a monodisperse spherical silica having a true specific gravity of 1.3 to 1.9 and an average particle diameter of 80 to 200 nm. It is preferable that It is preferable to control the true specific gravity to 1.9 or less because peeling from the toner base particles can be suppressed. Further, it is preferable to control the true specific gravity to 1.3 or more because aggregation and dispersion can be suppressed. The true specific gravity of the monodispersed spherical silica is more preferably in the range of 1.4 to 1.8.
Since the monodispersed spherical silica is monodispersed and spherical, it is preferable because it is uniformly dispersed on the surface of the toner base particles and a stable spacer effect can be obtained. The definition of the monodispersion can be discussed in terms of a standard deviation with respect to the average particle diameter including aggregates, and the standard deviation is preferably an average particle diameter D ₅₀ × 0.22 or less. Further, the definition of sphere can be discussed by Wadell's degree of sphericity, and the degree of sphericity is preferably 0.6 or more, and more preferably 0.8 or more.
The degree of spheroidization can be obtained from the following formula using Wadell's degree of sphericity.
Degree of sphericity = (surface area of sphere having the same volume as actual particle) / (surface area of actual particle)
In the above formula, the molecule (surface area of a sphere having the same volume as the actual particle) is calculated from the average particle diameter. The denominator (actual particle surface area) is substituted for the BET specific surface area using Shimadzu powder specific surface area measuring apparatus SS-100 type.
The reason why silica is preferable is that the refractive index is around 1.5, and even if the particle size is increased, the transparency is reduced due to light scattering, particularly the haze value (light transmission index) at the time of taking an image on the OHP surface, etc. It does not affect

Moreover, it is preferable to add an additive responsible for functions such as powder flowability and charge control. Specifically, the primary particle diameter is preferably a small inorganic particle having an average particle diameter of 7 to 40 nm. The small-diameter inorganic particles are preferably small-diameter inorganic oxides.
Examples of the small-diameter inorganic oxide include silica, alumina, titanium oxide (titanium oxide, metatitanic acid, etc.), calcium carbonate, magnesium carbonate, calcium phosphate, carbon black, and the like.
In particular, the use of titanium oxide having an average particle size of 15 to 40 nm does not affect the transparency, and has good chargeability, environmental stability, fluidity, caking resistance, stable negative chargeability and image quality maintainability. Is preferable in that it is obtained.
In addition, the surface treatment of the small-diameter inorganic particles increases the dispersibility and increases the powder flowability. Specifically, as the surface treatment, hydrophobic treatment with dimethyldimethoxysilane, hexamethyldisilazane (HMDS), methyltrimethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane or the like is preferably used.

The toner of the present invention can be produced by mixing toner base particles and an external additive (external additive) with a Henschel mixer or a V blender. In addition, when the toner base particles are produced by a wet method, external addition can also be performed by a wet method.
Further, it is also preferable to mix the toner base particles and the external additive and then sieve using a sieve having an opening. At this time, the opening is preferably 25 to 106 μm, and more preferably 25 to 45 μm. This is preferable because coarse particles can be removed.

-Electrostatic image developer-
The electrostatic image developer of the present invention contains the electrostatic image developing toner of the present invention described above.
That is, the electrostatic charge image developer of the present invention (hereinafter sometimes simply referred to as “developer”) is produced by mixing the toner described above and the following carrier. The mixing ratio (weight ratio) of toner and carrier in the developer is preferably in the range of toner: carrier = 1: 99 to 20:80, and preferably in the range of 3:97 to 12:88. More preferred.
It is also preferable to mix the electrostatic image developing toner and the carrier and then sieve using a sieve having openings. At this time, the opening is preferably 53 to 430 μm, and more preferably 53 to 212 μm. This is preferable because coarse particles can be removed.

(Career)
There is no restriction | limiting in particular as a carrier which can be used for the developing agent of this invention, A well-known carrier can be used. For example, the resin coat carrier which has a resin coating layer on the core material surface can be mentioned. Further, a resin-dispersed carrier in which magnetic powder or the like is dispersed in a matrix resin may be used.
Coating resins and matrix resins used for carriers include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic. Examples include acid copolymers, styrene-methacrylic acid copolymers, straight silicone resins composed of organosiloxane bonds or modified products thereof, fluororesins, polyesters, polycarbonates, phenol resins, epoxy resins, urea resins, urethane resins, melamine resins, etc. However, it is not limited to these.
In general, the carrier preferably has an appropriate electric resistance value, and it is preferable to disperse the conductive fine powder in the resin for adjusting the resistance. Examples of the conductive fine powder include metals such as gold, silver and copper, carbon black, titanium oxide, zinc oxide, barium sulfate, aluminum borate, potassium titanate, tin oxide, and carbon black. However, it is not limited to these.
Examples of the carrier core material include magnetic metals such as iron, nickel, and cobalt, magnetic oxides such as ferrite and magnetite, and glass beads. However, in order to use the carrier for the magnetic brush method, a magnetic material is used. Preferably there is. The average particle diameter of the carrier core material is preferably in the range of 10 to 100 μm, and more preferably in the range of 25 to 50 μm.
In order to coat the surface of the core material of the carrier with a resin, a method of coating the coating resin and, if necessary, various additives with a solution for forming a coating layer dissolved in an appropriate solvent is employed. The solvent is not particularly limited and may be appropriately selected in consideration of the coating resin to be used, coating suitability, and the like.
Specific resin coating methods include a dipping method in which the powder of the carrier core material is immersed in the coating layer forming solution, a spray method in which the coating layer forming solution is sprayed on the surface of the carrier core material, and a carrier core material. Examples thereof include a fluidized bed method in which a coating layer forming solution is sprayed in a state of being suspended by flowing air, and a kneader coater method in which a carrier core material and a coating layer forming solution are mixed in a kneader coater to remove the solvent.

-Image forming method-
The image forming method of the present invention will be described in detail below. The image forming method of the present invention includes a latent image forming step of forming an electrostatic latent image on the surface of the latent image holding member, and developing the electrostatic latent image formed on the surface of the latent image holding member with toner or an electrostatic charge image developer. A developing step for forming a toner image (development image), a transfer step for transferring the toner image formed on the surface of the latent image holding member to the surface of the recording member, and a toner image transferred on the surface of the recording member. Including a fixing step for heat fixing, and further, if necessary, a cleaning step for cleaning toner remaining on the surface of the latent image carrier, wherein the electrostatic image developing toner of the present invention is used as the toner. It is characterized by. The same effect can be obtained by using the electrostatic charge image developer of the present invention instead of the toner carried on the developer carrying member.

  The latent image forming step is a step of forming an electrostatic latent image by uniformly charging the surface of the latent image carrier with a charging means and then exposing the latent image carrier with a laser optical system or an LED array. It is. Examples of the charging means include a non-contact charger such as corotron and scorotron, and a contact method in which the surface of the latent image carrier is charged by applying a voltage to a conductive member in contact with the surface of the latent image carrier. Any type of charger may be used. However, a contact charging type charger is preferable from the viewpoint that the amount of ozone generated is small, environmentally friendly, and excellent printing durability. In the contact charging type charger, the shape of the conductive member may be any of a brush shape, a blade shape, a pin electrode shape, a roller shape, and the like, but a roller-like member is preferable. The image forming method of the present invention is not subject to any particular limitation in the latent image forming process.

  The developing step is a step of bringing a developer carrying member having a developer layer containing at least toner on the surface thereof into contact with or approaching the surface of the latent image carrying member to the electrostatic latent image on the surface of the latent image carrying member. In which a toner image (developed image) is formed on the surface of the latent image carrier. The development method can be performed using a known method, but examples of the development method using a two-component developer include a cascade method and a magnetic brush method. The image forming method of the present invention is not particularly limited with respect to the developing method.

The transfer step is a step of directly transferring the toner image formed on the surface of the latent image carrier to the recording medium or transferring the image once transferred to the intermediate transfer body to the recording medium to form a transfer image. It is.
A corotron can be used as a transfer device for transferring the toner image from the latent image carrier to paper or the like. The corotron is effective as a means for uniformly charging the paper, but a high voltage of several kV must be applied and a high voltage power source is required in order to give a predetermined charge to the paper as a recording medium. Further, since ozone is generated by corona discharge, the rubber parts and the latent image carrier are deteriorated. Therefore, a conductive transfer roll made of an elastic material is pressed against the latent image carrier to transfer the toner image onto the paper. A contact transfer method is preferred. In the image forming method of the present invention, the transfer device is not particularly limited.

The cleaning step is a step of removing toner, paper dust, dust and the like adhering to the surface of the latent image carrier by bringing a blade, a brush, a roll or the like into direct contact with the surface of the latent image carrier.
The most commonly employed method is a blade cleaning method in which a rubber blade such as polyurethane is pressed against the latent image carrier. On the other hand, a magnet is fixedly arranged inside, a rotatable cylindrical non-magnetic sleeve is provided on the outer periphery thereof, and a magnetic carrier system that collects toner by carrying a magnetic carrier on the sleeve surface, or a semiconductive It is also possible to remove the toner by making the resin fiber or animal hair rotatable in the form of a roll and applying a bias having a polarity opposite to that of the toner to the roll. In the former magnetic brush system, a cleaning pretreatment corotron may be provided. In the image forming method of the present invention, the cleaning method is preferably a cleaning step having at least a blade.

  The fixing step is a step of fixing the toner image transferred to the surface of the recording medium with a fixing device. As the fixing device, a heat fixing device using a heat roll is preferably used. The heat fixing device includes a fixing roller having a heater lamp for heating inside a cylindrical metal core, a so-called release layer formed on the outer peripheral surface by a heat resistant resin film layer or a heat resistant rubber film layer, and the fixing roller. The pressure roller or pressure belt is disposed in pressure contact with the roller and has a heat-resistant elastic layer formed on the outer peripheral surface of the cylindrical metal core or the surface of the belt-like base material. The fixing process of the unfixed toner image is performed by inserting a recording material on which an unfixed toner image is formed between a fixing roller and a pressure roller or a pressure belt, and using a binder resin, an additive, and the like in the toner. Fix by heat melting. In the image forming method of the present invention, the fixing method is not particularly limited.

  In the image forming method of the present invention, when producing a full-color image, each of the plurality of latent image carriers has a developer carrier of each color, and the plurality of latent image carriers and developer carriers. Each color toner image is sequentially laminated on the same surface of the recording medium by a series of processes including a latent image forming process, a developing process, a transferring process, and a cleaning process, and the stacked full-color toners. An image forming method in which an image is thermally fixed in a fixing step is preferably used. By using the electrostatic image developer in the image forming method, stable development, transfer, and fixing performance can be obtained even in a tandem system suitable for, for example, downsizing and color speeding up.

Examples of the recording material to which the toner image is transferred include plain paper, OHP sheet, and the like used for electrophotographic copying machines and printers. In order to further improve the smoothness of the image surface after fixing, the surface of the recording medium is preferably as smooth as possible. For example, coated paper in which the surface of plain paper is coated with a resin, art paper for printing Etc. can be used suitably.
According to the image forming method using the electrostatic charge image developing toner of the present invention, while maintaining high transfer efficiency and high image quality, the development and transfer processes are stabilized over time, and the interior of the apparatus by desorption of external additives is achieved. It is possible to obtain a high-quality image with high transfer efficiency that stably obtains an image having high image quality, particularly intermediate color reproducibility and gradation, without causing contamination.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all.
-Preparation of electrostatic image developing toner-
[Production of Toner C1]
(Preparation of resin particle dispersion (1))
1,4-cyclohexanedicarboxylic acid 17.5 parts by weight Bisphenol A 1 ethylene oxide adduct 31.0 parts by weight (both end equivalent 2 mol adduct)
0.15 parts by weight of dodecylbenzenesulfonic acid The above materials were mixed, put into a reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 25 hours under a nitrogen atmosphere. As a result, a uniform transparent amorphous polyester resin was obtained. It was.
A small sample was taken and the following physical properties were measured.
Weight average molecular weight by GPC 23,000
Glass transition temperature (onset) 57 ° C

For the measurement of the molecular weight, the weight average molecular weight Mw and the number average molecular weight Mn were measured by gel permeation chromatography (GPC) under the conditions described below. At a temperature of 40 ° C., a solvent (tetrahydrofuran) is flowed at a flow rate of 1.2 ml per minute, and 3 mg of a tetrahydrofuran sample solution having a concentration of 0.2 g / 20 ml is injected as a sample weight for measurement. When measuring the molecular weight of a sample, select the measurement conditions that fall within the range in which the logarithm of the molecular weight of the calibration curve and the number of counts are linear, using several types of monodisperse polystyrene standard samples. .
In addition, the reliability of the measurement results is as follows:
Weight average molecular weight Mw = 28.8 × 10 ⁴
Number average molecular weight Mn = 13.7 × 10 ⁴
Can be confirmed.
Further, as the GPC column, TSK-GEL, GMH (manufactured by Toyo Soda Co., Ltd.) and the like satisfying the above conditions were used.
A differential scanning calorimeter (Shimadzu Corporation, DSC50) was used to measure the glass transition temperature Tg of the polyester.

  The resin was put into a three-necked flask equipped with a stirrer and a condenser, and stirring was continued while gradually adding 1N and NaOH while maintaining the temperature at 95 ° C. When 50 parts by weight of NaOH aqueous solution was added in total, the resin became a slurry. The slurry was charged into a flask adjusted to 180 parts by weight of ion-exchanged water at 85 ° C., emulsified with a homogenizer (IKA, Ultra Turrax) for 12 minutes, and then further emulsified for 12 minutes in an ultrasonic bath. The flask was cooled with water at 25 ° C. The median diameter of the obtained resin particles was measured using a laser diffraction particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.) to obtain an amorphous polyester resin particle dispersion (1) having a median diameter of 410 nm. Moreover, the solid content concentration of the resin particle dispersion (1) was 40%.

(Preparation of cyan pigment dispersion (C1))
Cyan pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., PB15: 3) 20 parts by weight Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) 2 parts by weight Ion exchange water 78 parts by weight The above components are mixed and dissolved, and homogenizer Dispersed for 5 minutes using an ultrasonic bath (manufactured by IKA, Ultra Tarrax), and a cyan pigment dispersion (C1) was obtained. )
The number average particle diameter D50n of the pigment in the dispersion was 121 nm. Thereafter, ion exchange water was added to adjust the solid content concentration of the dispersion to 15%.

(Preparation of release agent particle dispersion (W1))
30 parts by weight of polyethylene wax (Toyo Petrolite, Polywax 725, melting point 103 ° C.)
3 parts by weight of cationic surfactant (manufactured by Kao Corporation, Sanizol B50) 67 parts by weight of ion-exchanged water The above components were sufficiently dispersed while being heated to 95 ° C. with a homogenizer (manufactured by IKA, Ultra Turrax T50), and then pressure Dispersion treatment was performed using a discharge type homogenizer (Gorin homogenizer manufactured by Gorin Co., Ltd.) to prepare a release agent particle dispersion liquid (W1). The number average particle diameter D50n of the release agent particles in the obtained dispersion was 460 nm. Thereafter, ion exchange water was added to adjust the solid concentration of the dispersion to 30%.

(Preparation of resin particle dispersion A)
Styrene 460 parts by weight n-butyl acrylate 140 parts by weight Acrylic acid 12 parts by weight Dodecanethiol 9 parts by weight The above components were mixed and dissolved to prepare a solution.
On the other hand, 12 parts by weight of an anionic surfactant (manufactured by Dow Chemical Co., Ltd., Dowfax) was dissolved in 250 parts by weight of ion-exchanged water, and the solution was added and dispersed and emulsified in a flask. (Monomer emulsion A)
Furthermore, 1 part by weight of an anionic surfactant (manufactured by Dow Chemical Co., Dowfax) was dissolved in 555 parts by weight of ion-exchanged water and charged into a polymerization flask.
The polymerization flask was sealed, a reflux tube was installed, and the polymerization flask was heated to 75 ° C. with a water bath while being slowly stirred while injecting nitrogen, and held.
9 parts by weight of ammonium persulfate was dissolved in 43 parts by weight of ion-exchanged water and dropped into the polymerization flask via a metering pump over 20 minutes, and then the monomer emulsion A was added for 200 minutes through the metering pump. It was dripped over.
Thereafter, the polymerization flask was kept at 75 ° C. for 3 hours while continuing the stirring slowly to complete the polymerization.
As a result, an anionic resin particle dispersion A having a median particle diameter of 520 nm, a glass transition point of 61.0 ° C., a weight average molecular weight of 36,000, and a solid content of 42% was obtained.

(Preparation of cyan toner mother particles 1)
Resin particle dispersion (1) 120 parts by weight Resin particle dispersion A 40 parts by weight Release agent particle dispersion (W1) 33 parts by weight Cyan pigment dispersion (C1) 60 parts by weight Polyaluminum chloride 10% by weight aqueous solution 15 parts by weight (Asada Chemical Co., PAC100W)
1% nitric acid aqueous solution 3 parts by weight The above components were dispersed in a round stainless steel flask for 3 minutes at 5,000 rpm using a homogenizer (manufactured by IKA, Ultra Turrax T50). The lid is equipped with a stirring device, a thermometer and a pH meter, and a heating mantle heater is set, and the whole dispersion in the flask is appropriately adjusted to the minimum number of rotations with which the stirring is performed and stirred. The mixture was heated to 1 ° C. at 1 ° C./1 min, held at 62 ° C. for 30 minutes, and the particle size of the aggregated particles was confirmed with a Coulter counter (TA II, manufactured by Beckman Coulter). Immediately after the temperature rise was stopped, 50 parts by weight of the resin particle dispersion (1) was added and held for 30 minutes, and then an aqueous sodium hydroxide solution was added until the pH in the system reached 6.5, and then at 1 ° C./1 min. Heated to 97 ° C. After the temperature rise, an aqueous nitric acid solution was added to adjust the pH in the system to 5.0, and the aggregated particles were heated and fused by holding for 10 hours. Thereafter, the temperature in the system was lowered to 50 ° C., an aqueous sodium hydroxide solution was added to adjust the pH to 12.0, and the mixture was maintained for 10 minutes. After removing from the flask, sufficiently filtering with ion-exchanged water and washing with water, dispersed in ion-exchanged water so that the solid content becomes 10% by weight, and added with nitric acid and stirred at pH 3.0 for 10 minutes. Thereafter, the slurry obtained by sufficiently filtering and washing with water through ion-exchanged water again was freeze-dried to obtain cyan toner mother particles 1. The cyan toner base particles 1 thus obtained had an average particle diameter D ₅₀ of 6.4 μm and an average value of the shape factor SF1 of 132.

(Preparation of cyan toner (toner C1))
The obtained toner base particles 1 were blended at a peripheral speed of 30 m / s for 15 minutes using a 5 liter Henschel mixer at the following composition ratio, and then coarse particles were removed using a sieve having a mesh opening of 45 μm. C1 was produced.
Cyan toner mother particle 1 (true specific gravity 1.2) 100 parts by weight Rutile-type titanium oxide Weight part calculated to have a coverage of 40% (average particle diameter 20 nm, n-decyltrimethoxysilane treatment, true specific gravity 4. 2)
RX50 parts by weight calculated to have a coverage of 30% (Nippon Aerosil, average particle size 40 nm, true specific gravity 2.2)
Spherical silica Part by weight calculated to have a coverage of 20% (average primary particle size 140 nm, sol-gel method, hexamethyldisilazane treatment, sphericity Ψ0.90, true specific gravity: 1.7)

Here, the relationship between the coverage of the external additive and the amount added is calculated using the following formula (A).
Toner surface coverage [%] X
= (√3 / 2π) × (dt / da) × (ρt / ρa) × C × 100 (A)
da: Average particle diameter of external additive (D ₅₀ )
dt: average particle diameter of toner (D ₅₀ )
ρa: True specific gravity of external additive ρt: True specific gravity of toner C: Weight of external additive / toner weight

[Preparation of Toner C2]
(Preparation of resin particle dispersion (2))
Styrene 370 parts by weight n-butyl acrylate 30 parts by weight Acrylic acid 8 parts by weight Dodecanethiol 24 parts by weight Carbon tetrabromide 4 parts by weight The above materials were mixed and dissolved into a nonionic surfactant (Nonipol 400: Sanyo) Kasei Co., Ltd.) 6 parts by weight and anionic surfactant (Neogen SC: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 10 parts by weight are dissolved in 550 parts by weight of ion-exchanged water and emulsified and dispersed in a flask, and slowly mixed for 12 minutes. Then, 50 parts by weight of ion-exchanged water in which 4 parts by weight of ammonium persulfate was dissolved was added thereto. After carrying out nitrogen substitution, while stirring the inside of the flask, it was heated in an oil bath until the contents reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result of measuring the obtained resin by the same method as the resin dispersion 1, resin particle dispersion in which resin particles having a median diameter of 160 nm, a glass transition temperature Tg of 58 ° C., and a weight average molecular weight Mw of 12,000 are dispersed. A liquid (2) was obtained. The solid content concentration of the resin particle dispersion (2) was 42%.

(Preparation of cyan pigment dispersion (C2))
Cyan pigment (B15: 3) 60 parts by weight Nonionic surfactant (Nonipol 400: manufactured by Sanyo Kasei Co., Ltd.) 5 parts by weight Ion-exchanged water 240 parts by weight Cyan pigment dispersion liquid in which colorant (cyan pigment) particles having a number average particle diameter D50n of 250 nm are dispersed by stirring with an optimizer for 10 minutes using Lux T50 (manufactured by IKA) C2) was prepared. Thereafter, ion exchange water was added to adjust the solid concentration of the dispersion to 38%.

(Preparation of release agent particle dispersion (W2))
100 parts by weight of paraffin wax (HNP0190: Nippon Seiwa Co., Ltd., melting point 85 ° C.)
Cationic surfactant (Sanisol B50: manufactured by Kao Corporation) 5 parts by weight Ion-exchanged water 240 parts by weight The above components were mixed, heated to 95 ° C., and homogenizer (UltraTurrax T50 in a round stainless steel flask). : Dispersing agent particle dispersion (W2) in which release agent particles having a number average particle diameter D50n of 550 nm are dispersed by dispersing with a pressure discharge homogenizer for 10 minutes using IKA) Produced.

(Preparation of cyan toner mother particles 2)
Resin particle dispersion (2) 234 parts by weight Cyan pigment dispersion (C2) 30 parts by weight Release agent particle dispersion (W2) 40 parts by weight Polyaluminum hydroxide (Ahoda Chemical Co., Paho2S) 1.9 parts by weight Ion 600 parts by weight of exchanged water The above components were mixed and dispersed in a round stainless steel flask using a homogenizer (Ultra Turrax T50: manufactured by IKA), and then stirred in the oil bath for heating. Heated to 55 ° C. After holding at 55 ° C. for 40 minutes, it was confirmed that aggregated particles having an average particle diameter D ₅₀ of 5.0 μm were generated. Further, when the temperature of the heating oil bath was raised and maintained at 56 ° C. for 2.5 hours, the average particle diameter D ₅₀ of the aggregated particles was 6.2 μm. Thereafter, 34 parts by weight of the resin particle dispersion (2) was added to the dispersion containing the aggregated particles, and then the temperature of the heating oil bath was maintained at 50 ° C. for 30 minutes. After adjusting the pH of the system to 7.0 by adding a 1N sodium hydroxide solution to the dispersion containing the aggregated particles, the stainless steel flask is sealed, and the stirring is continued to 80 ° C. using a magnetic seal. Heated and held for 4 hours. After cooling, the reaction product was filtered off, washed four times with ion exchange water, and then lyophilized to produce cyan toner mother particles 2. The average particle diameter D ₅₀ of the cyan toner base particles 2 was 6.5 μm, and the average value of the shape factor SF1 was 133.

(Preparation of cyan toner (toner C2))
The obtained toner base particles 2 were blended for 15 minutes at a peripheral speed of 30 m / s using a Henschel mixer at the following composition ratio, and then coarse particles were removed using a sieve having a mesh opening of 45 μm. Produced.
Cyan toner mother particle 2 (true specific gravity 1.1) 100 parts by weight Rutile-type titanium oxide Part by weight calculated to have a coverage of 40% (average particle diameter 20 nm, n-decyltrimethoxysilane treatment, true specific gravity 4. 2)
RX50 parts by weight calculated to have a coverage of 30% (Nippon Aerosil, average particle size 40 nm, true specific gravity 2.2)
Spherical silica Part by weight calculated to have a coverage of 60% (average primary particle size 140 nm, sol-gel method, hexamethyldisilazane treatment, sphericity Ψ0.90, true specific gravity 1.7)

[Preparation of Toner C3]
(Preparation of resin particle dispersion (3))
18.0 parts by weight of phenylenediacetic acid 32.0 parts by weight of bisphenol A 1 ethylene oxide adduct (2 mol adduct in terms of both ends)
0.13 parts by weight of dodecylbenzenesulfonic acid The above materials were mixed, put into a reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 25 hours under a nitrogen atmosphere. As a result, a uniform transparent amorphous polyester resin was obtained. It was.
A small sample was taken and the following physical properties were measured.
Weight average molecular weight by GPC 16,500
Glass transition temperature (onset) 58 ° C
The resin was put into a three-necked flask equipped with a stirrer and a condenser, and stirring was continued while gradually adding 1N and NaOH while maintaining the temperature at 95 ° C. When 50 parts by weight of NaOH aqueous solution was added in total, the resin became a slurry. The slurry was put into a flask adjusted to 85 parts by weight of ion-exchanged water at 85 ° C., emulsified with a homogenizer (IKA, Ultra Turrax) for 12 minutes, and then further emulsified for 12 minutes in an ultrasonic bath. The flask was cooled with water at 25 ° C. The median diameter of the obtained resin particles was measured using a laser diffraction particle size distribution measuring apparatus (LA-920, manufactured by Horiba, Ltd.) to obtain an amorphous polyester resin particle dispersion (3) having a median diameter of 390 nm. The solid content concentration of the resin particle dispersion (3) was 40%.

(Preparation of cyan toner mother particles 3)
Resin particle dispersion (3) 120 parts by weight Resin particle dispersion A 40 parts by weight Release agent particle dispersion (W1) 33 parts by weight Cyan pigment dispersion (C1) 60 parts by weight Polyaluminum chloride 10% by weight aqueous solution 15 parts by weight (Asada Chemical Co., PAC100W)
3% by weight of 1% nitric acid aqueous solution The above components were dispersed in a round stainless steel flask for 3 minutes at 5,000 rpm using a homogenizer (manufactured by IKA, Ultra Turrax T50). The lid is equipped with a stirring device, a thermometer and a pH meter, and a heating mantle heater is set, and the whole dispersion in the flask is appropriately adjusted to the minimum number of revolutions to be stirred and stirred. The mixture was heated to 1 ° C. at 1 ° C./1 min, held at 62 ° C. for 30 minutes, and the particle size of the aggregated particles was confirmed with a Coulter counter (manufactured by Nikka Machine Co., Ltd., TA II). Immediately after the temperature rise was stopped, 50 parts by weight of the resin particle dispersion (1) was added and held for 30 minutes, and then an aqueous sodium hydroxide solution was added until the pH in the system reached 6.5, and then at 1 ° C./1 min. Heated to 97 ° C. After the temperature rise, an aqueous nitric acid solution was added to adjust the pH in the system to 5.0, and the aggregated particles were heated and fused by holding for 10 hours. Thereafter, the temperature in the system was lowered to 50 ° C., an aqueous sodium hydroxide solution was added to adjust the pH to 12.0, and the mixture was maintained for 10 minutes. Then, after removing from the flask, sufficiently filtering with ion-exchanged water and washing with water, dispersed in ion-exchanged water so that the solid content becomes 10% by weight, added with nitric acid, and stirred at pH 3.0 for 10 minutes. Thereafter, the slurry obtained by sufficiently filtering and washing with water through ion exchange water again was freeze-dried to obtain cyan toner base particles 3. The resulting cyan toner base particles 3 had an average particle diameter D ₅₀ of 6.5 μm and an average value of the shape factor SF1 of 135.

(Preparation of cyan toner (toner C3))
A cyan toner (toner C3) was produced with the same external additive composition and production conditions as the cyan toner (toner C1) except that the obtained toner base particles 3 were used.

[Production of Toner C4]
(Preparation of resin particle dispersion (4))
1,4-cyclohexanedicarboxylic acid 14.9 parts by weight Bisphenol A 2 ethylene oxide adduct 35.1 parts by weight (both end equivalent 4 mol adduct)
0.10 parts by weight of dibutyltin oxide catalyst ([CH ₃ (CH ₂ ) ₃ ] ₂ SnO, Mw 248.94)
The above materials were mixed, put into a reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours under a nitrogen atmosphere. However, polycondensation did not proceed at all. Then, when the temperature was raised to 200 ° C. and polycondensation was carried out for 25 hours, a uniform transparent amorphous polyester resin was obtained.
A small sample was taken and the following physical properties were measured.
Weight average molecular weight by GPC 23,800
Glass transition temperature (onset) 44 ° C

  The resin was put into a three-necked flask equipped with a stirrer and a condenser, and stirring was continued while gradually adding 1N and NaOH while maintaining the temperature at 95 ° C. When 50 parts by weight of NaOH aqueous solution was added in total, the resin became a slurry. The slurry was charged into a flask adjusted to 180 parts by weight of ion-exchanged water at 85 ° C., emulsified with a homogenizer (IKA, Ultra Turrax) for 12 minutes, and then further emulsified for 12 minutes in an ultrasonic bath. The flask was cooled with water at 25 ° C. The median diameter of the obtained resin particles was measured using a laser diffraction particle size distribution measuring apparatus (LA-920, manufactured by Horiba, Ltd.) to obtain a non-crystalline polyester resin particle dispersion (4) having a median diameter of 360 nm. The solid content concentration of the resin particle dispersion (4) was 41%.

(Preparation of cyan toner mother particles 4)
Resin particle dispersion (4) 117 parts by weight Resin particle dispersion A 40 parts by weight Release agent particle dispersion (W1) 33 parts by weight Cyan pigment dispersion (C1) 60 parts by weight Polyaluminum chloride 10% by weight aqueous solution 15 parts by weight (Asada Chemical Co., PAC100W)
3% by weight of 1% nitric acid aqueous solution The above components were dispersed in a round stainless steel flask for 3 minutes at 5,000 rpm using a homogenizer (manufactured by IKA, Ultra Turrax T50). The lid is equipped with a stirring device, a thermometer and a pH meter, and a heating mantle heater is set, and the whole dispersion in the flask is appropriately adjusted to the minimum number of revolutions to be stirred and stirred. The mixture was heated to 1 ° C. at 1 ° C./1 min, held at 62 ° C. for 30 minutes, and the particle size of the aggregated particles was confirmed with a Coulter counter (manufactured by Nikka Machine Co., Ltd., TA II). Immediately after the temperature rise was stopped, 50 parts by weight of the resin particle dispersion (4) was added and held for 30 minutes. Then, an aqueous sodium hydroxide solution was added until the pH in the system reached 6.5, and then at 1 ° C./1 min. Heated to 97 ° C. After the temperature rise, an aqueous nitric acid solution was added to adjust the pH in the system to 5.0, and the aggregated particles were heated and fused by holding for 10 hours. Thereafter, the temperature in the system was lowered to 50 ° C., an aqueous sodium hydroxide solution was added to adjust the pH to 12.0, and the mixture was maintained for 10 minutes. After removing from the flask, sufficiently filtering with ion-exchanged water and washing with water, dispersed in ion-exchanged water so that the solid content becomes 10% by weight, and added with nitric acid and stirred at pH 3.0 for 10 minutes. Thereafter, the slurry obtained by sufficiently filtering and washing with water through ion-exchanged water was freeze-dried to obtain cyan toner mother particles 4. The obtained cyan toner base particles 4 had an average particle diameter D ₅₀ of 6.6 μm and an average value of the shape factor SF1 of 134.

(Preparation of cyan toner (toner C4))
A cyan toner (toner C4) was produced with the same external composition and production conditions as the cyan toner (toner C1) except that the obtained toner base particles 4 were used.

[Production of Toner C5]
(Preparation of resin particle dispersion (5))
14.6 parts by weight of terephthalic acid 35.4 parts by weight of bisphenol A 2 ethylene oxide adduct (4 mol adduct in terms of both ends)
0.11 part by weight of dodecylbenzenesulfonic acid The above materials were mixed, put into a reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 25 hours under a nitrogen atmosphere, but no polymerization was performed. Therefore, the temperature was raised to 220 ° C., the pressure was reduced to 0.5 Mpa, and polycondensation was further performed for 48 hours. As a result, a uniform transparent but soft amorphous polyester resin was obtained.
A small sample was taken and the following physical properties were measured.
Weight average molecular weight by GPC 6,200
Glass transition temperature (onset) 36 ° C

  The resin was put into a three-necked flask equipped with a stirrer and a condenser, and stirring was continued while gradually adding 1N and NaOH while maintaining the temperature at 95 ° C. When 50 parts by weight of NaOH aqueous solution was added in total, the resin became a slurry. The slurry was charged into a flask adjusted to 180 parts by weight of ion-exchanged water at 85 ° C., emulsified with a homogenizer (IKA, Ultra Turrax) for 12 minutes, and then further emulsified for 12 minutes in an ultrasonic bath. The flask was cooled with water at 25 ° C. The median diameter of the obtained resin particles was measured using a laser diffraction particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.) to obtain an amorphous polyester resin particle dispersion (5) having a median diameter of 690 nm. Moreover, the solid content concentration of the resin particle dispersion (5) was 40%.

(Preparation of cyan toner mother particles 5)
Resin particle dispersion (5) 120 parts by weight Resin particle dispersion A 40 parts by weight Release agent particle dispersion (W1) 33 parts by weight Cyan pigment dispersion (C1) 60 parts by weight Polyaluminum chloride 10% by weight aqueous solution 15 parts by weight (Asada Chemical Co., PAC100W)
1% nitric acid aqueous solution 3 parts by weight The above components were dispersed in a round stainless steel flask for 3 minutes at 5,000 rpm using a homogenizer (manufactured by IKA, Ultra Turrax T50), and then magnetically sealed to the flask. The lid is equipped with a stirring device, a thermometer and a pH meter, and a heating mantle heater is set, and the whole dispersion in the flask is appropriately adjusted to the minimum number of rotations with which the stirring is performed and stirred. The mixture was heated to 1 ° C. at 1 ° C./1 min, held at 62 ° C. for 30 minutes, and the particle size of the aggregated particles was measured. Immediately after the temperature increase was stopped, 50 parts by weight of the resin particle dispersion (5) was added and held for 30 minutes. Heated to 97 ° C. After the temperature rise, an aqueous nitric acid solution was added to adjust the pH in the system to 5.0, and the aggregated particles were heated and fused by holding for 10 hours. Thereafter, the temperature in the system was lowered to 50 ° C., an aqueous sodium hydroxide solution was added to adjust the pH to 12.0, and the mixture was maintained for 10 minutes. After removing from the flask, sufficiently filtering with ion-exchanged water and washing with water, dispersed in ion-exchanged water so that the solid content becomes 10% by weight, and added with nitric acid and stirred at pH 3.0 for 10 minutes. Thereafter, the slurry obtained by sufficiently filtering and washing with water through ion-exchanged water again was freeze-dried to obtain cyan toner mother particles 5. The cyan toner base particles 5 thus obtained had an average particle diameter D ₅₀ of 6.5 μm and an average value of the shape factor SF1 of 135.

(Preparation of cyan toner (toner C5))
A cyan toner (toner C5) was produced under the same external additive composition and production conditions as those of the cyan toner (toner C1) except that the obtained toner base particles 5 were used.

[Production of Toner C6]
(Preparation of resin particle dispersion (6))
Cyclohexanedicarboxylic acid 23.0 parts by weight Bisphenol A non-adduct 27.0 parts by weight Dodecylbenzenesulfonic acid 0.15 parts by weight The above materials were mixed, put into a reactor equipped with a stirrer, and added at 25 ° C. under a nitrogen atmosphere at 120 ° C. Although time polycondensation was carried out, no polymerization was performed. Therefore, the temperature was raised to 220 ° C., the pressure was reduced to 0.5 Mpa, and polycondensation was further performed for 48 hours. As a result, a uniform transparent but soft amorphous polyester resin was obtained.
A small sample was taken and the following physical properties were measured.
Weight average molecular weight by GPC 6,400
Glass transition temperature (onset) 36 ° C
The resin was put into a three-necked flask equipped with a stirrer and a condenser, and stirring was continued while gradually adding 1N and NaOH while maintaining the temperature at 95 ° C. When 50 parts by weight of NaOH aqueous solution was added in total, the resin became a slurry. The slurry was put into a flask adjusted to 85 parts by weight of ion-exchanged water at 85 ° C., emulsified with a homogenizer (IKA, Ultra Turrax) for 12 minutes, and then further emulsified for 12 minutes in an ultrasonic bath. The flask was cooled with water at 25 ° C. The median diameter of the obtained resin particles was measured using a laser diffraction particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.) to obtain a non-crystalline polyester resin particle dispersion (6) having a median diameter of 790 nm. Moreover, the solid content concentration of the resin particle dispersion (6) was 41%.

(Preparation of cyan toner mother particles 6)
Resin particle dispersion (6) 120 parts by weight Resin particle dispersion A 40 parts by weight Release agent particle dispersion (W1) 33 parts by weight Cyan pigment dispersion (C1) 60 parts by weight Polyaluminum chloride 10% by weight aqueous solution 15 parts by weight (Asada Chemical Co., PAC100W)
1% nitric acid aqueous solution 3 parts by weight The above components were dispersed in a round stainless steel flask for 3 minutes at 5,000 rpm using a homogenizer (manufactured by IKA, Ultra Turrax T50), and then magnetically sealed to the flask. The lid is equipped with a stirring device, a thermometer and a pH meter, and a heating mantle heater is set, and the whole dispersion in the flask is appropriately adjusted to the minimum number of rotations with which the stirring is performed and stirred. The mixture was heated to 1 ° C. at 1 ° C./1 min, held at 62 ° C. for 30 minutes, and the particle size of the aggregated particles was measured. Immediately after the temperature rise was stopped, 50 parts by weight of the resin particle dispersion (6) was added and held for 30 minutes. Then, an aqueous sodium hydroxide solution was added until the pH in the system reached 6.5, and then at 1 ° C./1 min. Heated to 97 ° C. After the temperature rise, an aqueous nitric acid solution was added to adjust the pH in the system to 5.0, and the aggregated particles were heated and fused by holding for 10 hours. Thereafter, the temperature in the system was lowered to 50 ° C., an aqueous sodium hydroxide solution was added to adjust the pH to 12.0, and the mixture was maintained for 10 minutes. After removing from the flask, sufficiently filtering with ion-exchanged water and washing with water, dispersed in ion-exchanged water so that the solid content becomes 10% by weight, added with nitric acid, and stirred at pH 3.0 for 10 minutes. Thereafter, the slurry obtained by sufficiently filtering and washing with water through ion-exchanged water again was freeze-dried to obtain cyan toner mother particles 6. The obtained cyan toner base particles had an average particle diameter D ₅₀ of 6.5 μm and an average value of the shape factor SF1 of 135.

(Preparation of cyan toner (toner C6))
A cyan toner (toner C6) was prepared with the same external additive composition and preparation conditions as the cyan toner (toner C1) except that the obtained toner base particles 6 were used.

[Production of Toner C7]
(Preparation of resin particle dispersion (7))
Dimethyl terephthalate 19.0 parts by weight Bisphenol A 2 ethylene oxide adduct 31.0 parts by weight (both end equivalent 4 mol adduct)
0.13 parts by weight of dibutyltin oxide The above materials were mixed, put into a reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 25 hours in a nitrogen atmosphere, but no polymerization was performed. Then, the pressure in the reactor was reduced to 0.5 Mpa and the temperature was raised to 220 ° C., and polycondensation was further performed for 48 hours. As a result, a uniform transparent but soft amorphous polyester resin was obtained.
A small sample was taken and the following physical properties were measured.
Weight average molecular weight by GPC 7,400
Glass transition temperature (onset) 38 ° C

  The resin was put into a three-necked flask equipped with a stirrer and a condenser, and stirring was continued while gradually adding 1N and NaOH while maintaining the temperature at 95 ° C. When 50 parts by weight of NaOH aqueous solution was added in total, the resin became a slurry. The slurry was charged into a flask adjusted to 180 parts by weight of ion-exchanged water at 85 ° C., emulsified with a homogenizer (IKA, Ultra Turrax) for 12 minutes, and then further emulsified for 12 minutes in an ultrasonic bath. The flask was cooled with water at 25 ° C. The median diameter of the obtained resin particles was measured using a laser diffraction particle size distribution measuring apparatus (LA-920, manufactured by Horiba, Ltd.) to obtain a non-crystalline polyester resin particle dispersion (7) having a median diameter of 770 nm. Moreover, the solid content concentration of the resin particle dispersion (7) was 41%.

(Preparation of cyan toner mother particles 7)
Resin particle dispersion (7) 117 parts by weight Resin particle dispersion A 40 parts by weight Release agent particle dispersion (W1) 33 parts by weight Cyan pigment dispersion (C1) 60 parts by weight Polyaluminum chloride 10% by weight aqueous solution 15 parts by weight (Asada Chemical Co., PAC100W)
1% nitric acid aqueous solution 3 parts by weight The above components were dispersed in a round stainless steel flask for 3 minutes at 5,000 rpm using a homogenizer (manufactured by IKA, Ultra Turrax T50), and then magnetically sealed to the flask. The lid is equipped with a stirring device, a thermometer and a pH meter, and a heating mantle heater is set, and the whole dispersion in the flask is appropriately adjusted to the minimum number of rotations with which the stirring is performed and stirred. The mixture was heated to 1 ° C. at 1 ° C./1 min, held at 62 ° C. for 30 minutes, and the particle size of the aggregated particles was measured. Immediately after the temperature increase was stopped, 50 parts by weight of the resin particle dispersion (7) was added and held for 30 minutes. Then, an aqueous sodium hydroxide solution was added until the pH in the system reached 6.5, and then at 1 ° C./1 min. Heated to 97 ° C. After the temperature rise, an aqueous nitric acid solution was added to adjust the pH in the system to 5.0, and the aggregated particles were heated and fused by holding for 10 hours. Thereafter, the temperature in the system was lowered to 50 ° C., an aqueous sodium hydroxide solution was added to adjust the pH to 12.0, and the mixture was maintained for 10 minutes. After removing from the flask, sufficiently filtering with ion-exchanged water and washing with water, dispersed in ion-exchanged water so that the solid content becomes 10% by weight, added with nitric acid, and stirred at pH 3.0 for 10 minutes. Thereafter, the slurry obtained by sufficiently filtering and washing with water through ion exchange water again was freeze-dried to obtain cyan toner mother particles 7. The cyan toner base particles 7 thus obtained had an average particle diameter D ₅₀ of 6.5 μm and an average value of the shape factor SF1 of 131.

(Preparation of cyan toner (toner C7))
A cyan toner (toner C7) was produced with the same external composition and production conditions as the cyan toner (toner C1) except that the obtained toner base particles 7 were used.

[Preparation of Toner C8]
(Preparation of resin particle dispersion (8))
22.4 parts by weight of terephthalic acid 31.0 parts by weight of bisphenol A 1 propylene oxide adduct (2 mol adduct in terms of both ends)
0.15 parts by weight of dodecylbenzenesulfonic acid The above materials were mixed, put into a reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 25 hours under a nitrogen atmosphere, but no polymerization was performed. Then, the pressure in the reactor was reduced to 0.5 Mpa and the temperature was raised to 220 ° C., and polycondensation was further performed for 48 hours. As a result, a uniform transparent but soft amorphous polyester resin was obtained.
A small sample was taken and the following physical properties were measured.
Weight average molecular weight by GPC 6,900
Glass transition temperature (onset) 36 ° C

  The resin was put into a three-necked flask equipped with a stirrer and a condenser, and stirring was continued while gradually adding 1N and NaOH while maintaining the temperature at 95 ° C. When 50 parts by weight of NaOH aqueous solution was added in total, the resin became a slurry. The slurry was charged into a flask adjusted to 180 parts by weight of ion-exchanged water at 85 ° C., emulsified with a homogenizer (IKA, Ultra Turrax) for 12 minutes, and then further emulsified for 12 minutes in an ultrasonic bath. The flask was cooled with water at 25 ° C. The median diameter of the obtained resin particles was measured using a laser diffraction particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.) to obtain a non-crystalline polyester resin particle dispersion (8) having a median diameter of 840 nm. The solid content concentration of the resin particle dispersion (8) was 41%.

(Preparation of cyan toner mother particles 8)
Resin particle dispersion (8) 117 parts by weight Resin particle dispersion A 40 parts by weight Release agent particle dispersion (W1) 33 parts by weight Cyan pigment dispersion (C1) 60 parts by weight Polyaluminum chloride 10% by weight aqueous solution 15 parts by weight (Asada Chemical Co., PAC100W)
1% nitric acid aqueous solution 3 parts by weight The above components were dispersed in a round stainless steel flask for 3 minutes at 5,000 rpm using a homogenizer (manufactured by IKA, Ultra Turrax T50), and then magnetically sealed to the flask. The lid is equipped with a stirring device, a thermometer and a pH meter, and a heating mantle heater is set, and the whole dispersion in the flask is appropriately adjusted to the minimum number of rotations with which the stirring is performed and stirred. The mixture was heated to 1 ° C. at 1 ° C./1 min, held at 62 ° C. for 45 minutes, and the particle size of the aggregated particles was measured. Immediately after the temperature rise was stopped, 50 parts by weight of the resin particle dispersion (8) was added and held for 30 minutes, and then an aqueous sodium hydroxide solution was added until the pH in the system reached 6.5, and then at 1 ° C./1 min. Heated to 97 ° C. After the temperature rise, an aqueous nitric acid solution was added to adjust the pH in the system to 5.0, and the aggregated particles were heated and fused by holding for 10 hours. Thereafter, the temperature in the system was lowered to 50 ° C., an aqueous sodium hydroxide solution was added to adjust the pH to 12.0, and the mixture was maintained for 10 minutes. After removing from the flask, sufficiently filtering with ion-exchanged water and washing with water, dispersed in ion-exchanged water so that the solid content becomes 10% by weight, added with nitric acid, and stirred at pH 3.0 for 10 minutes. Thereafter, the slurry obtained by sufficiently filtering and washing with water through ion-exchanged water again was freeze-dried to obtain cyan toner mother particles 8. The cyan toner base particles 8 thus obtained had an average particle diameter D ₅₀ of 9.3 μm and an average value of the shape factor SF1 of 125.

(Preparation of cyan toner (toner C8))
A cyan toner (toner C8) was produced with the same external additive composition and production conditions as the cyan toner (toner C1) except that the obtained toner base particles 8 were used.

[Preparation of Toner C9]
(Preparation of resin particle dispersion (9))
Dimethyl terephthalate 22.4 parts by weight Hydrogenated bisphenol A adduct 27.6 parts by weight Dodecylbenzenesulfonic acid 0.15 parts by weight The above materials are mixed, put into a reactor equipped with a stirrer, and 120 ° C. in a nitrogen atmosphere. The polycondensation was carried out for 25 hours, but no polymerization was performed. Then, the pressure in the reactor was reduced to 0.5 Mpa and the temperature was raised to 220 ° C., and polycondensation was further performed for 48 hours. As a result, a uniform transparent but soft amorphous polyester resin was obtained.
A small sample was taken and the following physical properties were measured.
Weight average molecular weight by GPC 6,900
Glass transition temperature (onset) 21 ° C
The resin was put into a three-necked flask equipped with a stirrer and a condenser, and stirring was continued while gradually adding 1N and NaOH while maintaining the temperature at 95 ° C. When 50 parts by weight of NaOH aqueous solution was added in total, the resin became a slurry. The slurry was put into a flask adjusted to 85 parts by weight of ion-exchanged water at 85 ° C., emulsified with a homogenizer (IKA, Ultra Turrax) for 12 minutes, and then further emulsified for 12 minutes in an ultrasonic bath. The flask was cooled with water at 25 ° C. The median diameter of the obtained resin particles was measured using a laser diffraction particle size distribution measuring device (LA-920, manufactured by Horiba, Ltd.) to obtain a non-crystalline polyester resin particle dispersion (9) having a median diameter of 840 nm. The solid content concentration of the resin particle dispersion (9) was 41%.

(Preparation of cyan toner mother particles 9)
Resin particle dispersion (9) 120 parts by weight Resin particle dispersion A 40 parts by weight Release agent particle dispersion (W1) 33 parts by weight Cyan pigment dispersion (C1) 60 parts by weight Polyaluminum chloride 10% by weight aqueous solution 15 parts by weight (Asada Chemical Co., PAC100W)
1% nitric acid aqueous solution 3 parts by weight The above components were dispersed in a round stainless steel flask for 3 minutes at 5,000 rpm using a homogenizer (manufactured by IKA, Ultra Turrax T50), and then magnetically sealed to the flask. The lid is equipped with a stirring device, a thermometer and a pH meter, and a heating mantle heater is set, and the whole dispersion in the flask is appropriately adjusted to the minimum number of rotations with which the stirring is performed and stirred. The mixture was heated to 1 ° C. at 1 ° C./1 min, held at 62 ° C. for 30 minutes, and the particle size of the aggregated particles was measured. Immediately after the temperature rise was stopped, 50 parts by weight of the resin particle dispersion (9) was added and held for 30 minutes, and then an aqueous sodium hydroxide solution was added until the pH in the system reached 6.5, and then at 1 ° C./1 min. Heated to 97 ° C. After raising the temperature, an aqueous nitric acid solution was added to adjust the pH in the system to 5.0, and the mixture was held for 2 hours to heat and coalesce the aggregated particles. Thereafter, the temperature in the system was lowered to 50 ° C., an aqueous sodium hydroxide solution was added to adjust the pH to 12.0, and the mixture was maintained for 10 minutes. Then, after removing from the flask, sufficiently filtering with ion-exchanged water and washing with water, dispersed in ion-exchanged water so that the solid content becomes 10% by weight, added with nitric acid, and stirred at pH 3.0 for 10 minutes. Then, the slurry obtained by sufficiently filtering and washing with water again using ion exchange water was freeze-dried to obtain cyan toner mother particles 9. The cyan toner base particles 9 thus obtained had an average particle diameter D ₅₀ of 6.5 μm and an average value of the shape factor SF1 of 146.

(Preparation of cyan toner (toner C9))
A cyan toner (toner C9) was produced with the same external composition and production conditions as the cyan toner (toner C1) except that the obtained toner base particles 9 were used.

[Production of Cyan Toner (Toners C10 to C16)]
After blending for 15 minutes at a peripheral speed of 30 m / s using a 5 liter Henschel mixer in the same manner as the toner C1, the external additive is added to 100 parts by weight of the toner base particles 1 at a composition ratio that gives the coverage shown in Table 1 below. Coarse particles were removed using a sieve having an opening of 45 μm, and toners C10 to C16 were produced.

Each of the above external additives is
Rutile-type titanium oxide: average particle diameter 20 nm, n-decyltrimethoxysilane treatment, true specific gravity 4.2
RX50: manufactured by Nippon Aerosil Co., Ltd., average particle diameter of 40 nm, true specific gravity of 2.2
Spherical silica: average primary particle size 140 nm, sol-gel method, hexamethyldisilazane treatment, sphericity Ψ0.90, true specific gravity: 1.7
It is.
Here, the relationship between the coverage of the external additive and the amount added was calculated using the above formula.

-Fabrication of carrier-
Toluene 20 parts by weight Styrene-methyl methacrylate copolymer 3 parts by weight (component ratio: 20/80: weight average molecular weight 85,000)
Carbon black (R330: manufactured by Cabot Corporation) 0.2 parts by weight The above components were mixed and stirred with a stirrer for 10 minutes to prepare a coating layer forming solution in which carbon black was dispersed. Next, this coating layer forming solution and 100 parts by weight of ferrite particles (volume average particle diameter: 45 μm) are put in a vacuum degassing type kneader, stirred at 60 ° C. for 30 minutes, and then further depressurized while heating. The carrier was prepared by degassing and drying. This carrier had a volume resistivity of 10 ^13.5 Ωcm when an electric field of 10 ^3.5 V / cm was applied.

[Example 1]
The electrostatic charge image developer (1) is prepared by stirring 100 parts by weight of the carrier and 6 parts by weight of toner C1 with a V-blender at 40 rpm for 20 minutes and sieving with a sieve having an opening of 212 μm. Was made.

[Comparative Example 1]
Further, 100 parts by weight of the carrier and 6 parts by weight of toner C2 were stirred with a V-blender at 40 rpm for 20 minutes, and sieved with a sieve having an opening of 212 μm to obtain an electrostatic charge image developer (2). Produced.

[Examples 2-6, Comparative Examples 2-10]
The electrostatic charge image developer (3- 16) were prepared, and as shown in Table 2 below, Examples 2 to 6 and Comparative Examples 2 to 10 were obtained.

Each of the above developers was used to evaluate developability, transferability, and potential unevenness due to contamination of external additives on the charging roll by Docu Center Color 400 (manufactured by Fuji Xerox Co., Ltd.).
<Evaluation of initial developability and transferability>
In a high-temperature and high-humidity environment (30 ° C, 80% RH), a solid patch of 5 cm x 2 cm is developed for each color, and the developed toner image on the surface of the photoreceptor is transferred using the adhesiveness of the tape surface. The weight (W1) was measured. At the same time, the background portion was also transferred to the tape surface, and the fog was visually observed. Similarly, the degree of unevenness was visually evaluated on the developed toner image on the surface of the photoreceptor on which the solid patch was developed. Next, the same developed toner image was transferred onto the surface of paper (J paper: manufactured by Fuji Xerox Office Supply), and the weight (W2) of the transferred image was measured. From these, the transfer efficiency was determined by the following formula, and the transferability was evaluated.
Transfer efficiency (%) = (W2 / W1) × 100
[Development evaluation criteria]
The developability was evaluated by the weight of W1 during the above test.
○: W1 is 4.5 g / m ² or more Δ: W1 is 4.0 or more and less than 4.5 g / m ² ×: W1 is less than 4.0 g / m ²

[Evaluation criteria for fogging]
○: No toner in the background area △: There is toner in the background area but cannot be seen with the naked eye ×: There is a large amount of toner in the background area, and the color can be confirmed visually.

[Evaluation criteria for transferability (transfer efficiency)]
○: Transfer efficiency is 90% or more Δ: Transfer efficiency is 85% or more and less than 90% ×: Transfer efficiency is less than 85%

[Evaluation criteria for uneven transfer]
○: No visual unevenness in the halftone image Δ: Visually unevenness is seen in the halftone image, but there is no problem in practical use ×: There are many unevennesses visible in the halftone image Table 3 Shown in

<Electric potential unevenness due to external additive contamination on charging roll>
After evaluating the initial developability and transferability, after performing 10,000 continuous prints so that the image density is 2%: the image density is 5% = 1: 1, the potential of the charging roll is measured. The charging unevenness was measured.
[Evaluation criteria for uneven charging]
○: No charging unevenness on the charging roll Δ: Charging roll has uneven charging, but there is no problem in image quality ×: The charging roll has charging unevenness, and the developed image is visually observed. Table 3 shows the results. Show.

From the results in Table 3, it was found that all of the electrostatic charge image developers of Examples had good developability, transfer efficiency, transfer unevenness, and charging unevenness over time. While maintaining high transfer efficiency and high image quality according to the present invention, it is possible to stabilize the development and transfer processes over time, and without causing internal contamination due to desorption of external additives, particularly high image quality, particularly intermediate color reproducibility, An electrophotographic toner and an electrophotographic developer capable of stably obtaining an image having excellent gradation are obtained.

Claims (5)

An electrostatic charge image developing toner comprising an electrostatic charge image developing toner mother particle containing a binder resin for a toner and a colorant obtained by a polycondensation reaction of a polycarboxylic acid and a polyol, and an external additive,
50 mol% or more and 100 mol% or less of the polycarboxylic acid comprises a compound represented by the formula (1) and / or the formula (2),
The toner base particles have an average particle size of 3 μm or more and 9 μm or less,
The toner base particle has a shape factor SF1 of 100 or more and 145 or less,
The external additive contains particles having an average particle size of 80 nm or more and 200 nm or less, and a coverage of 10% or more and 40% or less
An electrostatic charge image developing toner having a total coverage of 80% or more and 100% or less by an external additive.
R ¹ OOCA ¹ _m B ¹ _n A ¹ _l COOR ^{1 ′} (1)
(A ¹ : methylene group, B ¹ : aromatic hydrocarbon group, R ¹ , R ^{1 ′} : hydrogen atom or monovalent hydrocarbon group, 1 ≦ m + l ≦ 12, 1 ≦ n ≦ 3)
R ² OOCA ² _p B ² _q A ² _r COOR ^{2 ′} (2)
(A ² : methylene group, B ² : alicyclic hydrocarbon group, R ² , R ^{2 ′} : hydrogen atom or monovalent hydrocarbon group, 0 ≦ p ≦ 6, 0 ≦ r ≦ 6, 1 ≦ q ≦ 3) The electrostatic charge image developing toner according to claim 1, wherein 50 mol% or more and 100 mol% or less of the polyol is composed of a compound represented by the formula (3).
HOX _h Y _j X _k OH (3)
(X: alkylene oxide group, Y: bisphenol skeleton group, 1 ≦ h + k ≦ 10, 1 ≦ j ≦ 3) A step of aggregating the binder resin particles and the colorant particles in a dispersion containing at least the binder resin particles and the colorant particles to obtain aggregated particles; and
The method for producing an electrostatic image developing toner according to claim 1, comprising a step of fusing the aggregated particles by heating.   An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 1 and a carrier. A latent image forming step for forming an electrostatic latent image on the surface of the latent image holding member;
A developing step of developing the electrostatic latent image formed on the surface of the latent image holding body with toner or an electrostatic charge image developer to form a toner image;
A transfer step of transferring the toner image formed on the surface of the latent image holding member to the surface of the recording material; and
A fixing step of thermally fixing the toner image transferred to the surface of the recording material;
An image forming method comprising:
An image forming method using the electrostatic image developing toner according to claim 1 or 2 as the toner, or the electrostatic image developer according to claim 4 as the developer.