JP2009109815A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide spherical toner high in offset resistance, excellent also in electrostatic chargeability, while using capsule type toner excellent in low-temperature fixability, precise in a black character, line and a dot, capable of obtaining an image of high quality, small in a particle size, and sharp in a particle size distribution thereof. <P>SOLUTION: This toner contains a capsule type toner particle having a surface layer B, on a surface of a toner base particle A containing at least a resin a containing a polyester as a main component, a magnetic substance, and wax, the surface layer B contains a resin b, the resin b contains a resin selected from the group comprising a polyester resin b1, a vinyl resin b2 and an urethane resin b3, a glass transition temperature Tg(a) of the resin a and a glass transition temperature Tg(b) of the resin b satisfy a relation of Tg(a)<Tg(b), the magnetization of the toner in 79.6 kA/m of external magnetic field is 12 Am<SP>2</SP>/kg or more to 30 Am<SP>2</SP>/kg or less, and an average adhesion F50 of the toner is 50 (nN) or less when measured by a centrifugal method adhesion measuring instrument. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a toner used in a recording method using an electrophotographic method, an electrostatic recording method, a toner jet method recording method or the like. More specifically, the present invention relates to a copying machine and printer in which a toner image is formed on an electrostatic latent image carrier and then transferred onto a transfer material to form a toner image and fixed under thermal pressure to obtain a fixed image. , Relating to toner used in fax machines.

  In recent years, energy saving has been considered as a major technical problem in electrophotographic apparatuses, and the amount of heat applied to a fixing apparatus has been greatly reduced. Accordingly, there is a growing need for so-called “low-temperature fixability” that can fix toner with lower energy.

  Conventionally, in order to enable low-temperature fixing, a technique of making the binder resin more sharp melt is known as one of the effective methods. In this respect, the polyester resin exhibits excellent characteristics.

  On the other hand, from the viewpoint of high image quality, the toner is reduced in particle size and particle size distribution for the purpose of high resolution and high definition, and spherical toner is used for the purpose of improving transfer efficiency and fluidity. It has come to be used suitably. As a method for efficiently preparing spherical toner particles having a small particle size, a wet method has been used.

As a wet method in which a sharp melt polyester resin can be used, a resin component is dissolved in an organic solvent immiscible with water, and this solution is dispersed in an aqueous phase to form oil droplets. A “dissolution suspension method” for producing toner particles has been proposed (for example, Patent Document 1).
According to this method, a spherical toner having a small particle diameter using polyester having excellent low-temperature fixability as a binder resin can be easily obtained.

  Further, capsule-type toner particles have been proposed for the purpose of further low-temperature fixability in the toner particles produced by the above-described dissolution suspension method using polyester as a binder resin.

  For example, in Patent Document 2, a polyester resin, a low-molecular compound having an isocyanate group, and other components are dissolved and dispersed in ethyl acetate to prepare an oil layer, and a droplet is prepared in water. A method for preparing capsule toner particles having polyurethane or polyurea as the outermost shell by interfacial polymerization of a group-containing compound has been proposed.

  In Patent Documents 3 and 4, toner mother particles are prepared by a dissolution suspension method in the presence of resin fine particles of any of vinyl resins, polyurethane resins, epoxy resins, polyester resins, or combinations thereof, and the fine particles. A method for preparing toner particles coated with a toner surface is proposed.

Further, Patent Document 5 proposes toner particles by a dissolution suspension method using urethane-modified polyester resin fine particles as a dispersant. Patent Document 6 discloses a polyurethane resin (a
Core-shell type toner particles composed of one or more film-like shell layers (P) and a core layer (Q) made of resin (b) have been proposed.
This core-shell type toner particle has a structure in which the core portion has a low viscosity and the heat resistance storage stability of the shell portion compensates for the inferior heat resistance storage stability. In this case, since the shell portion is somewhat thermally hard, it is necessary to devise such as highly cross-linking and high molecular weight, so that the low-temperature fixability tends to be hindered.

  On the other hand, monochrome printers tend to be smaller in size for personal use and office installation area. For this reason, the one-component development method is preferably used because of the merit of reducing the size of the apparatus. The one-component development method includes a magnetic one-component development method in which magnetic particles are contained in toner and the developer is carried and conveyed by the action of magnetic force, and the developer is caused by the action of triboelectric charge of the developer without using magnetic particles. There is a non-magnetic one-component developing method in which the toner is carried on a developer carrying member (developing sleeve). In the magnetic one-component development system, a colorant such as carbon black is not used, and magnetic particles can also be used as a colorant.

  Various toners have been proposed for magnetic toners used in the magnetic one-component development system. For example, a dry toner that uses magnetic powder melted, kneaded and pulverized in a binder resin, and Patent Document 7 proposes a polymerization toner in which magnetic powder is dispersed in a styrene resin by suspension polymerization. Patent Document 8 proposes a solution suspension method toner using polyester.

  However, various problems are likely to occur in the magnetic toner using the dissolution suspension method. First, if the dispersion of the magnetic material is insufficient, a large amount of desorbed magnetic material is generated, and the resistance of the toner is likely to be lowered. As a result, the toner charge amount is lowered, and development failure, transfer failure, etc. are likely to occur. It was easy to cause agent contamination. Further, when the amount of the release agent added was increased, the release agent was likely to be formed on the toner particle surface, and the image quality was liable to deteriorate due to poor fluidity.

As a means for improving image quality in these electrophotographic processes such as development and transfer, a method for controlling the charging characteristics of the toner has been generally used, but on the other hand, developing property and transfer can be controlled by controlling the adhesion force of the toner itself. In recent years, knowledge to improve the property is being obtained.
However, most of them have a lot of knowledge in the form of the adhesion force between the toner and the latent image carrier, the contact between the toner and the development, and a member associated with the transfer process, and few have been discussed about the adhesion force of the toner itself. For example, Patent Document 9 and Patent Document 10 propose the adhesive force between the toner and the carrier particles, but the measurement method is different, and it is premised on the use of a two-component developer. At present, no proposal has been made to improve the developability and transferability by the adhesion force of the toner.
Japanese Patent Laid-Open No. 08-248680 JP 05-297622 A JP 2004-226572 A JP 2004-271919 A Japanese Patent No. 3455523 WO2005 / 073287 JP 2003-043737 A JP-A-8-286423 JP 2006-195079 A JP 2006-276062 A

  The present invention has been made in view of the above problems, and is to provide a toner having a high offset resistance and an excellent charging property while being a capsule-type toner excellent in low-temperature fixability. . Furthermore, black characters, lines, and dots are fine, and a high-quality image is obtained. It is another object of the present invention to provide a spherical toner having a small particle size and a sharp particle size distribution.

The toner of the present invention contains capsule-type toner particles having a surface layer (B) on the surface of toner base particles (A) containing at least a resin (a) containing polyester as a main component, a magnetic material and wax. Toner,
The surface layer (B) contains a resin (b), and the resin (b) is a resin containing a resin selected from a polyester resin (b1), a vinyl resin (b2), or a urethane resin (b3),
The glass transition temperature Tg (a) of the resin (a) and the glass transition temperature Tg (b) of the resin (b) satisfy the relationship of the following formula (1):
Tg (a) <Tg (b) (1)
Magnetization of the toner in an external magnetic field of 79.6 kA / m is 12 Am ² / kg or more and 30 Am ² / kg or less,
The average adhesion force (F50) measured by the toner centrifugal adhesion force measuring device is 50 (nN) or less.

According to a preferred embodiment of the present invention, the toner has a capsule-type structure. Then, the toner base particles (A) are provided with functions such as low viscosity, releasability, and coloring power, and the surface layer (B) is provided with functions such as heat resistance and chargeability related to developability. With this functional separation structure, it is possible to provide a toner that satisfies both the thermal properties of the toner with low-temperature fixability and heat-resistant storage and the electrical properties of the toner such as developability and transferability.
In particular, by using the resin (a) containing polyester as a main component for the toner base particles (A), it is possible to control the dispersibility of the magnetic substance and the wax while improving the sharp melt property of the toner. It was.
In addition, the surface layer (B) having a capsule structure can reduce the surface exposure of the magnetic material and provide a toner with excellent chargeability, which can solve the problems of black toner such as toner scattering and fogging. It was.
Furthermore, according to a preferred embodiment of the present invention, not only can the surface property of the toner be controlled and the average adhesion force (F50) is suppressed to be low, but not only stable charging property, developing property and transfer property can be obtained, It has become possible to provide a toner that can satisfy other characteristics required for electrophotographic characteristics such as chargeability and cleanability.

The toner of the present invention contains capsule-type toner particles having a surface layer (B) on the surface of toner base particles (A) containing at least a resin (a) containing polyester as a main component, a magnetic material and wax. Toner,
The surface layer (B) contains a resin (b), and the resin (b) is a resin containing a resin selected from a polyester resin (b1), a vinyl resin (b2), or a urethane resin (b3),
The glass transition temperature Tg (a) of the resin (a) and the glass transition temperature Tg (b) of the resin (b) satisfy the relationship of the following formula (1):
Tg (a) <Tg (b) (1)
Magnetization of the toner in an external magnetic field of 79.6 kA / m is 12 Am ² / kg or more and 30 Am ² / kg or less,
The average adhesion force (F50) measured by the toner centrifugal adhesion force measuring device is 50 (nN) or less.

The toner particles of the present invention have a capsule type structure having a surface layer (B) on the surface of toner base particles (A) containing at least a resin (a) containing polyester as a main component, a magnetic material and wax. Yes. When the capsule type structure is not employed, for example, in the case of a wax-containing toner, the toner is likely to aggregate due to precipitation of the wax on the surface of the toner, which may cause poor stirring in the developing region and clogging with a cleaner. Further, since the magnetic substance comes out on the toner surface, the resistance on the toner surface is lowered and the charge amount is likely to be lowered. The decrease in charge is likely to occur not only in the development area, but also in the change in the toner charge amount due to charge injection into the photoreceptor and peeling discharge during transfer.

The surface layer (B) used in the present invention contains a resin (b), and the resin (b) contains a resin selected from a polyester resin (b1), a vinyl resin (b2), or a urethane resin (b3). Resin.
Further, the glass point transfer Tg (a) of the resin (a) mainly composed of polyester used in the present invention and the glass point transfer Tg (b) of the resin (b) satisfy the relationship of the following formula (1).
Tg (a) <Tg (b) (1)
That is, by making Tg (b) of the capsule-type toner larger than Tg (a), it is possible to maintain heat resistance while realizing a low viscosity at a low temperature.

In the present invention, the magnetization (σt) of the toner in an external magnetic field of 79.6 kA / m is 12 Am ² / kg or more and 30 Am ² / kg or less.
When the magnetization (σt) of the toner is smaller than 12 Am ² / kg, the holding ability of the toner carrier is reduced, which is likely to cause toner scattering and fogging on paper. Further, when the magnetization (σt) of the toner exceeds 30 Am ² / kg, it tends to cause a dispersion failure due to excessive magnetic material and a decrease in fixing property due to a decrease in resin component. More preferably, the magnetization (σt) of the toner in an external magnetic field of 79.6 kA / m is 15 Am ² / kg or more and 28 Am ² / kg or less.
The magnetization (σt) of the toner can satisfy the above range by adjusting the addition amount of the magnetic material, the magnetization of the magnetic material to be used, and the like.

The present inventors have intensively studied to improve developability and transferability while maintaining the fixability of the capsule-type toner, and as a result, paying attention to the adhesion energy on the toner surface, it is optimal to control the adhesion energy. I found out.
Regarding the adhesion energy of the toner surface, in the present invention, when the average adhesion force (F50) measured by an adhesion force measuring device using a centrifugal method (centrifugal adhesion force measuring device) is 50 (nN) or less, It has been found that developability and transferability are improved while maintaining fixability.

The background focusing on the adhesion force of the toner is as follows.
In general, in the electrophotographic process, the toner behavior is largely influenced by the electrostatic charge force. In either case, the toner moves from the toner carrier to the latent image carrier or from the latent image carrier to the transfer medium, and the toner flies by electrostatic force or Coulomb force in a bias electric field. This is conventionally known.
In recent years, with the trend toward higher image quality in electrophotography, as countermeasures for higher image quality with toner, stabilization of the toner charge amount generated by friction from an electrostatic standpoint, and the average of toner We tried to achieve high image quality by reducing the grain size and making it possible to reproduce dots more faithfully to the latent image.
Certainly, these means have had a great influence on the improvement of the image quality of electrophotography. However, further improvement is required in view of further improvement in image quality such as photographic image quality and print image quality.

As a factor that hinders the improvement in image quality, the present inventors have made extensive studies on the latent image, and the dot reproduction has deteriorated. It has been found that image quality problems such as fatness and scattering occur.
In order to solve these problems, it is preferable that the toner moves from the toner carrier to the latent image holder in units of one particle with respect to the latent image. Therefore, it is considered preferable to lower the adhesion force of the toner as the behavior of the toner surface. By suppressing the adhesion force of the toner to a low level, the toner is easily released and the cohesiveness between the toners is not only suppressed, but also by exhibiting a high frictional charging ability, there is an effect of stabilizing the charging.
In addition, since the toner is easily released, development efficiency and transfer efficiency are improved, and in the future, waste toner is not generated, and it is considered that it leads to a main body support such as cleaner-less.

In the present invention, the adhesion force of toner refers to an average adhesion force (F50) measured by a toner centrifugal adhesion force measuring device (NS-C100: manufactured by Nano Seeds). In the present invention, the average adhesion force (F50) is 50 (nN) or less. Preferably it is 45 (nN) or less, More preferably, it is 40 (nN) or less. On the other hand, the average adhesive force (F50) is preferably 5 (nN) or more.
In the toner having a capsule structure of the present invention, satisfying the range of the above average adhesive force (F50) is important in terms of having high developability and transferability in addition to improvement of fixability and heat-resistant storage stability.
When the average adhesion force (F50) is 50 (nN) or less, the toner is more easily released and developability and transferability are improved.
On the other hand, when the average adhesion force (F50) is 50 (nN) or more, the aggregating property of the toner increases, the charging characteristics become unstable, the developability and transferability deteriorate, the image density decreases, It tends to cause quality degradation such as toner dropout.
The average adhesion force (F50) can satisfy the above range by adjusting the average roughness (Ra), average circularity, toner particle size distribution and the like of the toner particle surface.

In the present invention, the average roughness (Ra) of the toner particle surface (hereinafter also simply referred to as average roughness (Ra)) is preferably 1.0 nm or more and 5.0 nm or less, more preferably 1.5 nm or more and 5. It is 0 nm or less, more preferably 2.0 nm or more and 5.0 nm or less.
Since the surface of the toner particles has the above average roughness, the contact area between the toners can be reduced, the fluidity of the toner can be improved, and better developability can be brought about. In particular, in order to make the average adhesion (F50), which is a feature of the toner of the present invention, 50 or less (nN), it is important to control the average roughness.
When the average roughness is less than 1.0 nm, sufficient cleaning performance is difficult to be exhibited when the toner on the latent image carrier remains, and problems such as slip-through are likely to occur. When frictional charging is caused by contact with the frictional charging member, slipping occurs and it is difficult to obtain good chargeability.
On the other hand, when the average roughness (Ra) is larger than 5.0 nm, the voids between the toners are excessively increased, so that the average adhesion force (F50) is larger than 50 (nN) and developability and transferability are deteriorated. There is a fear.

In the present invention, as a means for controlling the average roughness (Ra) of the toner particle surface, the following method can be mentioned, but it is not limited to the following method.
For example, in the dissolution suspension method, which is a method for easily preparing capsule-type toner particles in the present invention, the desired average roughness (Ra) of the toner particle surface can be controlled by the following method.
That is, a solution or dispersion obtained by dissolving or dispersing at least the resin (a), the magnetic substance and the wax in an organic medium in an aqueous medium in which resin fine particles containing the resin (b) are dispersed ( In the production method in which toner particles are obtained by dispersing an oil phase), producing a dispersion containing oil droplets, removing the solvent by heating or the like, and then drying the dispersion. The average roughness (Ra) of the toner particle surface can be controlled by controlling the speed at which the solvent is removed from the toner particles.
By increasing the time for removing the solvent, the solvent in the oil droplets is slowly discharged, so that the toner surface is maintained in a smooth state and the average roughness (Ra) tends to decrease.
On the contrary, the average roughness (Ra) tends to increase by shortening the solvent removal time. It is considered that by shortening the removal time, the solvent is discharged from the formed oil droplets at a stretch, so that voids are easily formed on the toner particle surfaces.

A preferable solvent removal time for setting the average roughness (Ra) of the toner particle surface to 1.0 nm or more and 5.0 nm or less is 4 hours or more, more preferably 8 hours or more, and further preferably 24 hours or more.
Further, by heating the dispersion during the removal of the solvent, the surface layer (B) adheres uniformly to the surface of the toner particles, and there is almost no grain boundary of the resin (b), and a smoother surface state is likely to occur.
The heating temperature at this time is preferably 23 ° C. to 60 ° C., more preferably 25 ° C. to 50 ° C., and further preferably 25 ° C. to 40 ° C. in consideration of the boiling point of the solvent and coalescence of oil droplets.

  Further, in the step of removing the solvent, the container having the dispersion may be replaced with nitrogen gas, or nitrogen gas may be bubbled into the dispersion to reduce the average roughness (Ra) of the toner particle surface. It is one of the means to control. By performing nitrogen gas replacement, it is possible to shorten the solvent removal time while keeping the surface roughness (Ra) small.

As another means for controlling the average roughness (Ra) of the toner particle surface, in the preparation of the toner particles by the above-described dissolution suspension method, by using a wax dispersant together with the wax in the oil phase, The roughness (Ra) can be controlled within the above range.
The reason for this is not clear, but by creating a state in which the wax is finely dispersed in the droplets, the resin (b) can easily form a shell film uniformly on the surface of the toner base particles (A). As a result, the particle size distribution of the droplets tends to be sharp, and it is considered that toner particles having smooth surface properties can be obtained by suppressing the occurrence of poorly emulsified products such as ultrafine particle powder.

  The wax dispersant not only controls the average roughness (Ra) of the toner particle surface, but also has the effect of increasing the dispersibility of the magnetic material. By increasing the dispersibility of the magnetic material, exposure of the magnetic material to the surface of the toner particles is suppressed, and a smoother surface property of the toner particles can be obtained. Stability is also improved.

As another means for controlling the average roughness (Ra) of the toner particle surface, a general-purpose powder surface modifying apparatus that utilizes mechanical impact force or air conveyance at the stage of obtaining dried toner particles is used. And a means for smoothing the surface of the toner particles and controlling the surface roughness (Ra).
However, when a powder surface modification device is used, the damage to the toner particles is large, and toner particles are united together, and problems such as fusion within the device are likely to occur. It may occur.

The average circularity of the toner of the present invention is preferably 0.960 or more and 1.000 or less, and more preferably 0.965 or more and 0.990 or less.
The reason for this is that by controlling the average circularity of the toner to be high, the contact points between the toners are reduced, and the toner is easily separated. As a result, the average adhesion force (F50) of the toner can be controlled to 50 (nN) or less.
As a means for controlling the average circularity of the toner within the above range, it is possible to increase the average circularity of the toner by further providing a heating step after removing the solvent. Specifically, the heating temperature is preferably a temperature close to Tg (b) of the resin (b) constituting the surface layer (B), more preferably 10 ° C to 20 ° C higher than Tg (b). is there.

As another means for controlling the average circularity of the toner within the above range, the toner particles obtained by the dissolution suspension method are subjected to a spheronization treatment (circularity adjustment) in a surface modification step as necessary. It is also possible to do.
For example, the average circularity of the toner may be in the range of 0.960 to 1.000 using a hybridization system manufactured by Nara Machinery Co., Ltd. and a mechano-fusion system manufactured by Hosokawa Micron.

The weight average particle diameter (D4) of the toner of the present invention is preferably 4.0 μm or more and 9.0 μm or less.
When the weight average particle diameter of the toner is smaller than 4.0 μm, the toner tends to aggregate even when the surface roughness (Ra) and the average circularity are satisfied, and the average adhesion force (F50) is increased. It tends to be larger than 50 (nN), and there is a possibility of causing a decrease in developability. In particular, the toner is likely to be charged up after a long period of use or the like, resulting in a decrease in density. On the other hand, when the weight average particle diameter of the toner is larger than 9.0 μm, even when the average adhesion force (F50) is 50 (nN) or less, when a line image or the like is output, the toner scatters or drops off. May be inferior and thin line reproducibility may be inferior.
The weight average particle diameter (D4) of the toner can be adjusted to the above range by controlling the amount of the resin (b) added and the amount of the oil phase or dispersion.

The toner of the present invention preferably has a ratio (D4 / D1) of 1.25 or less of the weight average particle diameter (D4) to the number average particle diameter (D1). More preferably, it is 1.20 or less, More preferably, it is 1.15 or less. On the other hand, the D4 / D1 is preferably 1.00 or more.
When D4 / D1 is greater than 1.25, the toner particle size distribution tends to be broad, and it is difficult to obtain a stable fluidity when the toner is mixed, and the average adhesion force (F50) of the toner tends to increase. .
In the present invention, when D4 / D1 is 1.25 or less, the particle size distribution becomes sharp, and the average adhesion force (F50) of the toner is 50 (nN) or less by approaching the monodispersed particle size. We found it very effective in achieving.
As a means for obtaining the above particle size distribution in the capsule-type toner as in the present invention, as will be described later, a known surfactant, water-soluble polymer, viscosity modifier and the like are added to the aqueous medium. It can also be achieved by addition.

In the present invention, the content of the wax is preferably 5.0% by mass or more and 20.0% by mass or less, and more preferably 5.0% by mass or more and 15.0% by mass or less with respect to the toner.
When the wax content is less than 5.0% by mass, it becomes difficult to maintain the releasability of the toner. On the other hand, when the wax content is more than 20.0% by mass, the wax is likely to be exposed on the toner surface, the toners are likely to be coalesced, and the average adhesion force (F50) of the toner is likely to be high. Tend to decrease. In addition, the frictional charging between the toners becomes unstable due to the coalescence, and there is a possibility that the transfer efficiency is lowered.

The magnetic material used in the present invention is preferably contained in an amount of 30.0% by mass to 120.0% by mass with respect to the resin (a) containing polyester as a main component. More preferably, it is 40.0 mass% or more and 110.0 mass% or less.
When the content of the magnetic material is less than 30.0% by mass, the magnetization of the toner is lowered, so that the binding force on the toner carrier is lowered, and problems such as scattering and fogging are likely to occur. On the other hand, when the content of the magnetic material is more than 120.0% by mass, the magnetization of the toner becomes too high, so that the binding force between the toners becomes high, and the average adhesion force (F50) of the toner is higher than 50 (nN). This tends to cause deterioration in developability and transferability.

In the present invention, the surface layer (B) is preferably 1.0% by mass or more and 15.0% by mass or less based on the toner base particles (A). More preferably, the surface layer (B) is 2.0% by mass or more and 10.0% by mass or less with respect to the toner base particles (A).
When the amount of the surface layer (B) relative to the amount of the toner base particles (A) is less than 1.0% by mass, the encapsulation is insufficient and the toner base particles (A) are easily exposed. As a result, due to the influence of the exposure of the wax and the like, the adhesion force between the toners is increased, and the developability and transferability are liable to occur.
On the other hand, when the amount of the surface layer (B) exceeds 15.0% by mass with respect to the amount of the toner base particles (A), the excess surface layer (B) becomes easy to unite the toners, and the particle size distribution. Tends to be broad, and it is difficult to obtain a stable fluidity at the time of toner mixing, which may cause a decrease in developability.

The surface layer (B) used in the present invention is described below.
The surface layer (B) used in the present invention contains the resin (b). The resin (b) is a resin containing a resin selected from a polyester resin (b1), a vinyl resin (b2), a urethane resin, and (b3). The resin (b) more preferably contains a urethane resin. (B3) As the resin (b), two or more of the above resins may be used in combination.
The glass transition temperature Tg (b) of the resin (b) is higher than the glass transition temperature Tg (a) of the resin (a). Therefore, in order to set the glass transition temperature Tg (b) of the resin (b) to a predetermined value, it is preferable to control the monomer type, molecular weight, and branched structure.
Tg (b) is preferably 45 ° C. or higher and 80 ° C. or lower, and more preferably 50 ° C. or higher and 75 ° C. or lower. As a result, it is possible to obtain a toner that satisfies heat-resistant storage stability and suppresses fixing inhibition.

In this invention, the said polyester resin (b1) can be produced by the same method, using the raw material similar to resin (a) mentioned later.
However, when the same composition as that of the resin (a) is used, it is easy to dissolve in the solvent used, and it becomes difficult to maintain the toner particles during the granulation step or the shell configuration. Therefore, it is preferable to introduce a highly polar monomer to the resin (a).
The polyester resin (b1) preferably has a sulfonic acid group. The sulfonic acid group value of the polyester resin (b1) is preferably 1 mgKOH / g or more and 25 mgKOH / g or less, more preferably 10 mgKOH / g or more and 25 mgKOH / g or less.

The vinyl resin (b2) is a polymer obtained by homopolymerizing or copolymerizing vinyl monomers. Examples of the vinyl monomer used include the following monomers.
(1) Vinyl hydrocarbons:
(1-1) Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, α-olefins other than the above, etc .; alkadienes such as butadiene , Isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene.
(1-2) Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene and the like; terpenes such as pinene, limonene, Inden etc.
(1-3) Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitutes such as α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethyl Styrene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene, and the like; and vinyl naphthalene.

(2) Carboxyl group-containing vinyl monomers and their metal salts:
C3-C30 unsaturated monocarboxylic acid, unsaturated dicarboxylic acid and its anhydride and its monoalkyl (C1-C24) ester, such as (meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate Carboxyl group-containing vinyl monomers such as esters, fumaric acid, fumaric acid monoalkyl esters, crotonic acid, itaconic acid, itaconic acid monoalkyl esters, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl esters, and cinnamic acid.

(3) Sulfonic group-containing vinyl monomers, vinyl sulfate monoesters and their salts:
Alkene sulfonic acids having 2 to 14 carbon atoms such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfonic acid; and alkyl derivatives having 2 to 24 carbon atoms such as α-methyl styrene sulfonic acid Sulfo (hydroxy) alkyl- (meth) acrylate or (meth) acrylamide, such as sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2 , 2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, 3- (Meth) acrylamide-2- Droxypropanesulfonic acid, alkyl (C3-18) allylsulfosuccinic acid, poly (n = 2-30) oxyalkylene (ethylene, propylene, butylene: single, random or block) sulfuric acid of mono (meth) acrylate Esters [poly (n = 5 to 15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl ether sulfate, and sulfates represented by the following general formulas (1-1) to (1-3) Sulfonic acid group-containing monomers; and salts thereof.

（上記式（１−１）〜（１−３）中、Ｒは炭素数１〜１５のアルキル基、Ａは炭素数２〜４のアルキレン基を示し、ｎが複数の場合同一でも異なっていてもよく、異なる場合はランダムでもブロックでもよい。Ａｒはベンゼン環を示し、ｎは１〜５０の整数を示し、Ｒ’はフッ素原子で置換されていてもよい炭素数１〜１５のアルキル基を示す。）

(In the above formulas (1-1) to (1-3), R represents an alkyl group having 1 to 15 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and when n is plural, they may be the same or different. If different, they may be random or block, Ar represents a benzene ring, n represents an integer of 1 to 50, and R ′ represents an alkyl group having 1 to 15 carbon atoms which may be substituted with a fluorine atom. Show.)

  The vinyl resin (b2) preferably has a sulfonic acid group. The sulfonic acid group value of the vinyl resin (b2) is preferably 1 mgKOH / g or more and 25 mgKOH / g or less, more preferably 10 mgKOH / g or more and 25 mgKOH / g or less.

  In the capsule-type toner particles of the present invention, the resin (b) preferably contains a urethane resin (b3). In particular, in order to achieve an average adhesion force (F50) of the toner of 50 (nN) or less, the resin (b) is particularly preferably a urethane resin (b3) which is a compound formed by a urethane bond. The reason for this is not clear, but it is considered that the adjustment of the viscosity and the particle size are relatively easy, and thus the above-described surface property and circularity of the toner can be easily increased.

  The urethane resin (b3) is a reaction product of a diol component that is a prepolymer and a substance containing a diisocyanate component, and resins having various functions can be obtained by adjusting the diol component and the diisocyanate component.

Examples of the substance containing the diisocyanate component include the following.
Carbon number (excluding carbon in NCO group, the same shall apply hereinafter) 6 to 20 aromatic diisocyanate, C2 to C18 aliphatic diisocyanate, C4 to C15 alicyclic diisocyanate, C8 to C15 aroma Hydrocarbon diisocyanates and modified products of these diisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, oxazolidone group-containing modified products, etc., hereinafter modified diisocyanates. Also a mixture of two or more thereof.

Examples of the aromatic diisocyanate include the following.
1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'-diphenylmethane Diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof]].

Examples of the aliphatic diisocyanate include the following.
Ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl carbonate Proate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

The following are mentioned as said alicyclic diisocyanate.
Isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1, 2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate.

  Examples of the aromatic hydrocarbon diisocyanate include the following. m-xylylene diisocyanate, p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI).

Examples of the modified diisocyanate include the following.
Modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), isocyanate-modified products such as urethane-modified TDI, and mixtures of two or more thereof (for example, modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)) Together with].
Among these, preferred are 6-15 aromatic diisocyanates, aliphatic diisocyanates having 4-12 carbon atoms, and alicyclic diisocyanates having 4-15 carbon atoms, and particularly preferred are TDI, MDI, HDI, water. Attached MDI and IPDI.

  In addition to the above-mentioned diisocyanate component, the resin (b) can also use a tri- or higher functional isocyanate compound as the urethane resin (b3). Examples of the trifunctional or higher functional isocyanate compound include polyallyl polyisocyanate (PAPI), 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate, and p-isocyanatophenylsulfonyl isocyanate. Is mentioned.

Moreover, the following are mentioned as a diol component which can be used for the said urethane resin (b3).
Alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol, dodecanediol, tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.);
Alkylene ether glycols (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.);
Alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.);
Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above alicyclic diol; alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above bisphenols;
In addition, polylactone diol (such as poly ε-caprolactone diol), polybutadiene diol.
The alkyl part of the above-described alkylene ether glycol may be linear or branched. In the present invention, alkylene glycol having a branched structure can also be preferably used.
Among these, an alkyl structure is preferable in view of solubility (affinity) in ethyl acetate, and an alkylene glycol having 2 to 12 carbon atoms is preferably used.

In the urethane resin (b3), in addition to the diol component described above, a polyester oligomer having a terminal hydroxyl group (terminal diol polyester oligomer) can also be used as a suitable diol component.
At this time, the molecular weight (number average molecular weight) of the terminal diol polyester oligomer is preferably 3000 or less, more preferably 800 or more and 2000 or less.

When the molecular weight of the terminal diol polyester oligomer is larger than the above, the reactivity with the isocyanate-terminated compound is lowered, and the properties of the polyester become too strong and become soluble in ethyl acetate.
In addition, the content of the terminal diol polyester oligomer described above is preferably 1 mol% or more and 10 mol% or less, more preferably 3 mol% or more and 6 mol% in the monomer constituting the reaction product of the diol component and the diisocyanate component. It is as follows.

  When the terminal diol polyester oligomer is contained in an amount exceeding 10 mol%, the reaction product of the diol component and the diisocyanate component may be soluble in ethyl acetate.

  On the other hand, when the amount of terminal diol polyester oligomer is less than 1 mol%, the reaction product of the diol component and the diisocyanate component becomes too hard and inhibits the fixing property, or the affinity with the resin (a) decreases. The surface layer may be difficult to form.

  The polyester skeleton of the terminal diol polyester oligomer and the polyester skeleton of the resin (a) described later are preferably the same in order to form good capsule-type toner particles. This is related to the affinity between the reaction product of the diol component and diisocyanate component of the surface layer (B) and the resin (a).

  Moreover, the terminal diol polyester oligomer mentioned above may have an ether bond modified with ethylene oxide, propylene oxide or the like.

  Moreover, in the said urethane resin (b3), in addition to the reaction material of a diol component and a diisocyanate component, the reaction material (compound with a urea bond) of an amino compound and an isocyanate compound can also be used together.

The following are mentioned as an amino compound which can be used for the said urethane resin. Diamines (eg, diaminoethane, diaminopropane, diaminobutane, diaminohexane, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine, IPDA), 4,4 '-Diaminodicyclohexylmethane, 1,4-diaminocyclohexane, aminoethylethanolamine, hydrazine, hydrazine hydrate), or triamines (eg, triethylamine, diethylenetriamine and 1,8-diamino-4-aminomethyloctane).
In the urethane resin (b3), in addition to the reaction product of the amino compound and the isocyanate compound described above, the urethane resin (b3) has a group in which highly reactive hydrogen such as an isocyanate compound and a carboxylic acid group, a cyano group, or a thiol group exists. A reaction product with a compound may be used in combination.

In the urethane resin (b3), the reaction product of at least the diisocyanate component and the diol component preferably has a carboxylic acid group, a sulfonic acid group, a carboxylate salt, or a sulfonate salt in the side chain. The carboxylic acid group, sulfonic acid group, carboxylate or sulfonate is a carboxylic acid group, sulfonic acid group, carboxylate or sulfonate on the side chain of a monomer that forms a reaction product of a diol component and a diisocyanate component. Can be easily manufactured.

  Diol carboxylic acids such as dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolbutyric acid, dimethylolpentanoic acid, and metal salts thereof are used as diol compounds having a carboxylic acid group or carboxylate introduced in the side chain. Can be mentioned.

  A monomer having a sulfonic acid group or a sulfonate introduced in the side chain can easily form an aqueous dispersion, and is effective for stably forming a capsule structure without being dissolved in an organic solvent in the oil phase. Examples of the diol compound having a sulfonic acid group or sulfonate introduced in the side chain include sulfoisophthalic acid, N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid, and metal salts thereof. it can.

  The content of the diol component in which a carboxylic acid group, a sulfonic acid group, a carboxylate salt or a sulfonate salt is introduced into the side chain is preferably based on all monomers forming a reaction product of the diol component and the diisocyanate component. It is 10 mol% or more and 50 mol% or less, More preferably, it is 20 mol% or more and 30 mol% or less.

  When the diol component is less than 10 mol%, the dispersibility of resin fine particles, which will be described later, tends to deteriorate, and the granulation property may be impaired. On the other hand, when it is more than 50 mol%, the reaction product of the diol component and the diisocyanate component may be dissolved in the aqueous medium, and the function as a dispersant may not be achieved.

  The surface layer (B) is preferably formed using resin fine particles containing a resin (b) having a number average particle diameter of 30 nm to 100 nm. The method for preparing the resin fine particles is not particularly limited, and is an emulsion polymerization method or a method in which the resin is dissolved or melted in a solvent to be liquefied and granulated by suspending it in an aqueous medium. Can be used.

  For the preparation of the resin fine particles, a known surfactant or dispersant can be used, or the resin constituting the resin fine particles can be made self-emulsifying.

The solvent that can be used when the resin fine particles are prepared by dissolving the resin in a solvent is not particularly limited, but includes the following.
Hydrocarbon solvents such as ethyl acetate, xylene and hexane, halogenated hydrocarbon solvents such as methylene chloride, chloroform and dichloroethane, ester solvents such as methyl acetate, ethyl acetate, butyl acetate and isopropyl acetate, ethers such as diethyl ether Solvent, ketone solvent such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexane, alcohol solvent such as methanol, ethanol and butanol.

  Moreover, when preparing the said resin fine particle, the manufacturing method using the resin fine particle containing the reaction material of a diol component and a diisocyanate component as a dispersing agent is one of the preferable forms. In this production method, a prepolymer having a diisocyanate component is produced, which is rapidly dispersed in water, followed by the addition of a diol component, thereby extending or crosslinking the chain.

That is, a prepolymer having a diisocyanate component and other necessary components as necessary are dissolved or dispersed in a solvent having high solubility in water such as acetone or alcohol among the above solvents. By throwing this into water, the prepolymer having a diisocyanate component is rapidly dispersed. And it is the method of adding the said diol component continuously and preparing the reaction material of the diol component and diisocyanate component with a desired physical property.

For the formation of the surface layer (B), the resin fine particles having a number average particle diameter of 30 nm or more and 100 nm or less are used to control the average adhesion force (F50) of the toner to 50 (nN) or less. Preferred above.
That is, when the number average particle size is smaller than 30 nm, the capsule structure is difficult to be formed due to a decrease in granulation stability and the like, the surface property and circularity of the toner are deteriorated, and the average adhesion force (F50) of the toner is reduced. ) Tends to be larger than 50 (nN), and developability and transferability tend to decrease.
On the other hand, when the number average particle diameter is larger than 100 nm, the dispersibility in the aqueous phase is reduced, as in the case where the coating amount of the resin fine particles is large, the particles are coalesced, and the irregularly shaped particles are formed. With similar results.

The toner base particles (A) used in the present invention are described in detail below.
The toner base particles (A) used in the present invention contain at least a resin (a) containing polyester as a main component, a magnetic material and a wax. Therefore, if necessary, other additives may be included in addition to the above.

  The resin (a) used in the present invention contains polyester as a main component. Here, “main component” means that the polyester occupies 50% by mass or more based on the total amount of the resin (a). For the polyester, it is preferable to use a polyester using an aliphatic diol as a main component as an alcohol component and / or a polyester using an aromatic diol as a main component.

The aliphatic diol preferably has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms.
Examples of the aliphatic diol having 2 to 8 carbon atoms include the following.
Ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-butenediol, 1 , 7-heptanediol, diols such as 1,8-octanediol, trihydric or higher polyhydric alcohols such as glycerin, pentaerythritol and trimethylolpropane. Among these, α, ω-linear alkanediol is preferable, and 1,4-butanediol and 1,6-hexanediol are more preferable.
Furthermore, from the viewpoint of durability, the content of the aliphatic diol is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, in the alcohol component constituting the polyester.

Examples of the aromatic diol include the following.
Polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane.

Examples of the carboxylic acid component constituting the polyester include the following.
Aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid, fumaric acid, maleic acid, adipic acid, succinic acid, dodecenyl succinic acid and octenyl succinic acid. Aliphatic polycarboxylic acids such as succinic acid substituted with alkyl groups or alkenyl groups having 2 to 20 carbon atoms, anhydrides of these acids and alkyl (1 to 8 carbon atoms) esters of these acids.

From the viewpoint of chargeability, the carboxylic acid preferably contains an aromatic polyvalent carboxylic acid compound, and the content thereof is preferably 30 to 100 mol% in the carboxylic acid component constituting the polyester, 50-100 mol% is more preferable.
In addition, the raw material monomer may contain a trivalent or higher polyvalent monomer, that is, a trivalent or higher polyhydric alcohol and / or a trivalent or higher polyvalent carboxylic acid compound from the viewpoint of fixability.

  The manufacturing method of the said polyester is not specifically limited, What is necessary is just to follow a well-known method. For example, a production method in which an alcohol component and a carboxylic acid component are subjected to polycondensation at a temperature of 180 to 250 ° C. in an inert gas atmosphere using an esterification catalyst as necessary.

  The resin (a) preferably contains as a main component a polyester using the aliphatic diol as an alcohol component. On the other hand, even when the resin (a) contains a polyester using a bisphenol monomer as an alcohol component, there is no significant difference in the melting characteristics of the resin (a). However, in order to affect the granulation property in relation to the resin (b), it is effective to select an appropriate polyester as appropriate.

  The resin (a) is a resin other than a polyester using a specific amount of an aliphatic diol as an alcohol component, for example, a polyester, a styrene-acrylic resin, a polyester and a styrene acrylic in which the amount of the aliphatic diol is outside the above range. Mixed resin and epoxy resin may be contained. In that case, the content of the polyester using the specific amount of aliphatic diol as an alcohol component is preferably 50% by mass or more, and more preferably 70% by mass or more based on the total amount of the resin (a).

  Furthermore, in the present invention, in the molecular weight distribution measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble matter of the resin (a), the peak molecular weight (Mp) is preferably 8000 or less, more preferably less than 5500. It is. Furthermore, the ratio of molecular weight 100,000 or more is preferably 5.0% or less, more preferably 1.0% or less.

  If the peak molecular weight exceeds 8000 or the ratio of the molecular weight of 100,000 or more exceeds 5.0%, the fixability may be impaired depending on the type and amount of the resin in the surface layer.

In the present invention, the proportion of the resin (a) having a molecular weight of 1000 or less is preferably 10.0% or less, more preferably less than 7.0%.
When the ratio of the molecular weight of 1000 or less is more than 10.0%, a low molecular weight component that is relatively thermally unstable may contaminate the member.

In the present invention, the following preparation method can be preferably used in order to make the ratio of the molecular weight of 1000 or less particularly 10.0% or less.
In order to reduce the ratio of molecular weight of 1000 or less, the ratio of molecular weight of 1000 or less can be effectively reduced by dissolving the binder resin in a solvent and leaving the solution in contact with water. That is, by such an operation, the low molecular weight component having a molecular weight of 1000 or less is eluted in water and can be effectively removed from the resin solution.

  For the above reasons, for example, the above-described dissolution suspension method is preferably used as a toner production method. The low molecular weight component is efficiently removed by using a method in which a solution in which the resin (a), the magnetic material and the wax are dissolved or dispersed is left in contact with the aqueous medium before being suspended in the aqueous medium. can do.

In the present invention, the toner particles contain a wax. Examples of the wax used in the present invention include the following.
Low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax; fat Waxes based on fatty acid esters such as aromatic hydrocarbon-based ester waxes; and partially or fully deoxidized fatty acid esters such as deoxidized carnauba wax; partial esters of fatty acids and polyhydric alcohols such as behenic acid monoglyceride A methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and fats.
The wax particularly preferably used in the present invention is, in the dissolution suspension method, easy preparation of the wax dispersion, easy incorporation into the prepared toner, seepage from the toner during fixing, releasability Therefore, ester wax is preferable.

  In the present invention, the ester wax only needs to have at least one ester bond in one molecule, and either natural ester wax or synthetic ester wax may be used.

Examples of the synthetic ester wax include a monoester wax synthesized from a long-chain linear saturated fatty acid and a long-chain linear saturated alcohol. Long chain straight chain saturated fatty acids are represented by the general formula C _n
When represented by H _{2n + 1} COOH, n = about 5 to 28 is preferably used. Also when it represents a long-chain linear saturated alcohol _C n _{H 2n +} 1 OH, of about n = 5 to 28 is preferably used.

Examples of the long-chain linear saturated fatty acid include the following.
Capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, pentadecylic acid, heptadecanoic acid, tetradecanoic acid, stearic acid, nonadecanoic acid, aramonic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid And melicic acid.

On the other hand, examples of the long-chain linear saturated alcohol include the following.
Amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, capryl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol , Nonadecyl alcohol, eicosyl alcohol, seryl alcohol and heptadecanool.

Examples of the ester wax having two or more ester bonds per molecule include the following.
Trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerol tribehenate, 1,18-
Octadecanediol-bis-stearate, polyalkanol ester (tristearyl trimellitic acid, distearyl maleate).

Moreover, the following are mentioned as an example of a natural ester wax.
Candelilla wax, carnauba wax, rice wax, wax, jojoba oil, beeswax, lanolin, castor wax, montan wax and derivatives thereof.

Other modified waxes include the following.
Polyalkanoic acid amides (such as ethylenediamine dibehenyl amide); polyalkylamides (such as trimellitic acid tristearyl amide); and dialkyl ketones (distearyl ketone).

  The wax may be partially saponified.

  Among the above, more preferable waxes are synthetic ester waxes composed of long-chain linear saturated fatty acids and long-chain linear saturated aliphatic alcohols, or natural waxes based on the above esters.

The reason for this is not clear, but it is thought that the mobility in the molten state is increased due to the wax having a linear structure. In other words, it is necessary for the wax to permeate into the toner surface layer through a relatively high-polarity substance such as polyester as a binder resin or a resin containing a reaction product of diol and diisocyanate in the surface layer at the time of fixing. However, it seems that it is advantageous that the wax has a linear structure as much as possible to pass between such highly polar substances.
Furthermore, it is considered that the ester wax acts as a dispersion aid for the magnetic substance in the toner and works advantageously for reducing aggregates and free substances.

  Further, in the present invention, it is more preferable that the ester is a monoester in addition to the linear structure described above. For the same reason as described above, in a bulky structure in which esters are bonded to the branched chains, it penetrates through a highly polar substance such as polyester or the surface layer of the present invention and oozes out to the surface. The authors speculate that it may be difficult.

  In the present invention, it is also one of preferred modes to use a hydrocarbon wax other than the ester wax as needed.

Examples of hydrocarbon waxes other than the ester wax include the following.
Natural waxes such as paraffin wax, microcrystalline wax, petroleum-based natural waxes such as petrolatum and derivatives thereof, synthetic hydrocarbons such as Fischer-Tropsch wax, polyolefin waxes and derivatives thereof (polyethylene wax, polypropylene wax), ozokerite, ceresin.

In the present invention, the wax content in the toner is preferably 5.0% by mass or more and 20.0% by mass or less, more preferably 5.0% by mass or more and 15.0% by mass or less. When the wax content is less than 5.0% by mass, it becomes difficult to maintain the releasability of the toner. When the wax content is more than 20.0% by mass, the wax is easily exposed on the surface of the toner, and the heat-resistant storage stability. There is a risk of lowering.

  In the present invention, the wax preferably has a maximum endothermic peak at 60 ° C. or higher and 90 ° C. or lower in differential scanning calorimetry (DSC). If the maximum endothermic peak is lower than 60 ° C., the wax is likely to be exposed on the toner surface, which may cause a decrease in heat resistant storage stability. On the other hand, if the maximum endothermic peak is higher than 90 ° C., the wax does not melt properly at the time of fixing, and the low-temperature fixability and offset resistance may be poor.

In the present invention, the toner base particles (A) are one or two selected from a styrene monomer, a nitrogen-containing vinyl monomer, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an acrylate monomer, and a methacrylic acid ester monomer. It is preferable to contain 2.5% by mass or more and 10.0% by mass or less of a copolymer synthesized using the above monomers and a wax dispersion medium having at least polyolefin.
In addition, a copolymer synthesized using one or more monomers selected from styrene monomers and nitrogen-containing vinyl monomers, carboxyl group-containing monomers, hydroxyl group-containing monomers, acrylate monomer, and methacrylate monomer. The wax dispersion medium having at least a polymer and a polyolefin is one or more selected from a styrene monomer, a nitrogen-containing vinyl monomer, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an acrylate monomer, and a methacrylate ester monomer. Copolymers synthesized using two or more monomers and those obtained by grafting polyolefin are preferred.
In the present invention, the wax dispersion includes (i) an ester wax and (ii) a wax dispersion medium [styrene monomer, nitrogen-containing vinyl monomer, carboxyl group-containing monomer, hydroxyl group-containing monomer, acrylate monomer and methacrylic acid. It is preferable that a copolymer synthesized by using one or two or more monomers selected from acid ester monomers and a product obtained by grafting with a polyolefin] can be dissolved in ethyl acetate.

A solution obtained by melting and mixing the wax dispersion as a master batch in the resin (a) containing polyester as a main component is added and used as a “wax dispersion master batch” at the time of oil phase adjustment.
The ester wax used in the present invention is preferably finely dispersed in advance in the wax dispersion.

The wax dispersion medium not only enhances the dispersibility of the wax, but also has the effect of enhancing the dispersibility of the magnetic substance. In order to exert these effects, the wax dispersion medium is used in the toner base particles (A). The content in is preferably 2.5% by mass or more and 10.0% by mass or less, more preferably 2.5% by mass or more and 7.5% by mass or less. When the content of the wax dispersion medium is less than 2.5% by mass, the dispersibility of the wax itself is deteriorated, and the wax is easily exposed to the toner surface, and is fused to the developer carrier or the latent image carrier. Or the surface smoothness of the toner tends to deteriorate, and the developability and transferability tend to be reduced.
On the other hand, if it exceeds 10.0% by mass, the wax itself may be exposed to the toner surface, and the glossiness of the image after fixing tends to vary, and the heat-resistant storage stability tends to deteriorate.

An example of the structure and manufacturing method of the magnetic material used in the present invention will be described.
Examples of the magnetic material used in the present invention include magnetite, iron oxide such as ferrite, iron, cobalt and nickel, or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, And alloys with metals such as bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof.

  The magnetic material used in the present invention is produced, for example, by the following method. After adding a predetermined amount of Zn metal salt and silicate to the ferrous salt aqueous solution, add an alkali such as sodium hydroxide or more equivalent to the iron component to prepare an aqueous solution containing ferrous hydroxide To do. Air is blown in while maintaining the pH of the prepared aqueous solution at pH 7 or higher (preferably pH 8 to 10), and iron oxide is oxidized while heating the aqueous solution to 70 ° C. or higher, which becomes the core of the magnetic body. First, seed crystals are formed.

Next, an aqueous solution containing a first equivalent of ferrous sulfate is added to the slurry-like liquid containing seed crystals based on the amount of alkali added previously. Thereafter, while maintaining the pH of the solution at 6 to 10, the reaction of ferrous hydroxide is promoted while blowing air, and the magnetic iron oxide particles are grown with the seed crystal as the core. Magnetic iron oxide characterized by maintaining a constant elemental composition ratio on the outermost surface of the body is characterized by advancing the oxidation reaction step by step in combination with pH adjustment. For example, the oxidation reaction is allowed to proceed stepwise depending on the pH, such that the pH is 9-10 at the beginning of the reaction, the pH is 8-9 during the middle of the reaction, and the pH is 6-8 during the latter half of the reaction. Thus, the composition ratio of the outermost surface of magnetic iron oxide can be controlled more easily. Further, the pH of the liquid shifts to the acidic side as the oxidation reaction proceeds, but it is preferable that the pH of the liquid not be less than 6.

As metal salts other than iron used for addition, sulfates, nitrates, and chlorides can be used. Moreover, sodium silicate and potassium silicate are illustrated as a silicate which can be used for addition.
As the ferrous salt, iron sulfate generally produced as a by-product in the production of sulfuric acid titanium, iron sulfate produced as a by-product with the surface cleaning of the copper plate can be used, and further iron chloride can be used.
In the method for producing a magnetic substance by the aqueous solution method, an iron concentration of 0.5 to 2 mol / liter is generally used in view of preventing the viscosity from increasing during the reaction and the solubility of iron sulfate. Generally, the lower the iron sulfate concentration, the finer the particle size of the product. In the reaction, the more the amount of air and the lower the reaction temperature, the easier the atomization.

  In the present invention, as the magnetic material, spherical particles, octahedral particles, hexahedral particles and mixtures thereof can be used as observed by transmission electron micrographs.

In the present invention, the magnetic substance has a bulk density based on a measurement method described later, preferably 0.3 to 2.0 g / cm ³ , more preferably 0.5 to 1.3 g / cm ³ . When the bulk density is less than 0.3 g / cm ³ , the physical mixing property of the toner with other constituent materials at the time of toner production tends to be adversely affected, and the dispersibility in the toner may deteriorate.

In the present invention, the magnetic substance has a BET specific surface area based on a measurement method described later, preferably 15.0 m ² / g or less, more preferably 12.0 m ² / g or less. When the BET specific surface area of the magnetic material exceeds 15.0 m ² / g, the moisture adsorption property of the magnetic material increases, which may affect the hygroscopic property and the charging property of the magnetic toner containing the magnetic material.

In the present invention, as the magnetic characteristics of the magnetic material, the magnetization under a magnetic field of 79.6 kA / m is preferably 10 to 200 Am ² / kg, more preferably 50 to 100 Am ² / kg. The residual magnetization is preferably 1 to 100 Am ² / kg, more preferably ^{2 to 20} Am ² / kg. Furthermore, the coercive force is preferably 1 to 30 kA / m, more preferably 2 to 15 kA / m. By having such magnetic characteristics, it is possible to obtain good developability in which the magnetic toner has a balance between image density and fog.

  In the present invention, the number average particle diameter of the magnetic material based on the measurement method described below is preferably 0.10 μm or more and 0.30 μm or less, and more preferably 0.15 μm or more and 0.25 μm or less. By satisfying the above range, the dispersibility of the magnetic substance in the resin (a), the uniformity of toner charging, the coloring power of the toner, and the color tone are improved. Further, the magnetic material used in the present invention preferably has a coefficient of variation in particle size of 50% or less. By adjusting the coefficient of variation to the above range, it is possible to improve the dispersibility of the magnetic material and obtain a toner with excellent color.

  The toner in the present invention contains a magnetic substance and exhibits a black color. However, it can be used in combination with other black colorants. Moreover, it is also possible to use together with another coloring agent as color adjustment.

As other black colorants, organic pigments such as carbon black and aniline black, and metal oxides such as composite oxides having nonmagnetic black can be used in combination. Examples of carbon black include the following. Carbon black such as furnace black, channel black, acetylene black, thermal black, lamp black.
In particular, when a reddish magnetic material is used, it is effective to add a blue or cyan colorant.

  As the cyan colorant, a pigment or a dye can be used. Specific examples include the following. C. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 16, 17, 60, 62, 66; I. Bat Blue 6, C.I. I. Acid Blue 45. Examples of the dye include the following. C. I. Solvent Blue 25, 36, 60, 70, 93, 95. These may be used alone or in combination of two or more.

  In the present invention, it is not preferable to use a dye or pigment having extremely high solubility in water as the colorant. When the above-mentioned dye / pigment is used, it may be dissolved in water during the production process, granulation may be disturbed, and desired coloration may not be obtained.

  In the present invention, a charge control agent can be used as necessary. The charge control agent may be contained in the toner base particles (A) containing at least the resin (a), the magnetic substance and the wax, or may be contained in the surface layer (B).

The charge control agent can be appropriately selected and used from the following in consideration that the charging speed is high and a constant charge amount can be stably maintained.
Negative charge control agents include salicylic acid metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, polymer compounds having sulfonic acid or carboxylic acid in the side chain, boron compounds, urea compounds, silicon compounds, calixarene. Can be mentioned.
Examples of the positive charge control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, and an imidazole compound.
Among these, 3,5-di-tertiary butyl salicylate is particularly preferable because the charge amount rises quickly.
Moreover, the addition amount of the charge control agent is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the resin (a).

Hereinafter, a simple method for preparing the toner particles used in the present invention will be described, but the present invention is not limited thereto.
The toner particles include at least a resin (a) mainly composed of polyester, a magnetic material, and a wax in an organic medium in an aqueous medium (hereinafter also referred to as an aqueous phase) in which resin fine particles containing the resin (b) are dispersed. It is preferably obtained by dispersing a solution or dispersion (hereinafter also referred to as an oil phase) obtained by dissolving or dispersing in the solution, removing the solvent from the obtained dispersion, and drying.
In the above system, the resin fine particles function as a dispersant when suspending the dissolved or dispersed material (oil phase) in the aqueous phase. By preparing toner particles by the above method, capsule-type toner particles can be easily prepared without requiring an aggregation step on the toner surface.

In the method for preparing the oil phase, examples of the organic medium for dissolving the resin (a) and the like include the following.
Hydrocarbon solvents such as ethyl acetate, xylene and hexane, halogenated hydrocarbon solvents such as methylene chloride, chloroform and dichloroethane, ester solvents such as methyl acetate, ethyl acetate, butyl acetate and isopropyl acetate, ethers such as diethyl ether Ketone solvents such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexane.

  The resin (a) is preferably used in the form of a resin dispersion dissolved in the organic medium. In this case, although depending on the viscosity and solubility of the resin, the resin (a) is blended in the range of 40% by mass to 60% by mass as a resin component in the organic solvent in consideration of ease of production in the next step. Is preferred. In addition, heating at the melting point or lower of the organic medium at the time of dissolution is preferable because the solubility of the resin increases.

  The wax and magnetic material are also preferably dispersed in the organic medium. That is, it is preferable to disperse the wax and magnetic material, which have been wet or dry mechanically ground in advance, in an organic medium to prepare a wax dispersion and a magnetic material dispersion, respectively.

  The dispersibility of the wax and the magnetic material can also be improved by adding a dispersant and a resin that match each of them. Since these differ depending on the wax, magnetic substance, resin, and organic solvent used, they can be selected and used as appropriate. In particular, the magnetic material is preferably used after being dispersed in an organic medium together with the resin (a).

  The oil phase can be prepared by blending a desired amount of the resin dispersion, wax dispersion, magnetic dispersion, and organic medium, and dispersing each of the components in the organic medium.

Hereinafter, the method for preparing the magnetic dispersion liquid will be further described with examples.
In the present invention, the following method was used in order to increase the dispersibility of the magnetic material beyond normal.
(1) Wet dispersion (media dispersion)
In this method, a magnetic material is dispersed in a solvent in the presence of a dispersing medium. For example, a magnetic material, resin, other additives and the organic solvent are mixed, and the mixture is dispersed using a disperser in the presence of a dispersion medium. The used dispersion medium is collected to obtain a magnetic dispersion. As the dispersing machine, for example, an attritor (Mitsui Miike Koki Co., Ltd.) is used. Examples of the dispersing medium include alumina, zirconia, glass and iron beads, but zirconia beads with very little media contamination are preferred. In this case, the bead diameter is preferably 2 mm to 5 mm because of excellent dispersibility.
(2) Dry kneading Resin, magnetic material, and other additives are melt kneaded with a kneader and roll type disperser (dry type), and the resulting melt kneaded product of resin and magnetic material is pulverized and dissolved in the organic solvent. By doing so, a magnetic dispersion liquid is obtained.

Furthermore, the following method is effective for increasing the dispersibility of the magnetic material.
(3) Wet dispersion of dry-type melt-kneaded product A magnetic dispersion prepared by using the melt-kneaded product of resin and magnetic material obtained by the above-described dry-type is further wet-dispersed using the above-mentioned dispersion media and disperser. .
(4) Solvent addition at the time of preparation of the dry melt kneaded product A solvent is added at the time of preparation of the dry melt kneaded product. The temperature during melt kneading is preferably not less than the glass transition temperature (Tg) of the resin and not more than the boiling point of the solvent. The solvent to be used is preferably a solvent capable of dissolving the resin, and a solvent used in the oil phase is preferable.
(5) Wax addition at the time of preparing the dry melt-kneaded product A wax is added at the time of preparing the dry melt-kneaded product. The temperature during melt kneading is preferably not less than the glass transition temperature (Tg) of the resin and not more than the boiling point of the solvent. As the wax to be used, a wax that dissolves in the oil phase may be used, but other relatively high melting point wax may be used.
(6) A resin having high affinity with the magnetic material is used as the resin.
A resin having a high affinity with the magnetic material is used as the resin used for the production of the dry melt kneaded product. For example, at least two types of resins (a1) and (a
2) and using one resin (a2), the magnetic material is dispersed.
Here, it is preferable that a resin synthesized from at least an aliphatic diol is used for the resin (a1), and a crystalline polyester or a resin synthesized from at least an aromatic diol is used for the resin (a2). One.

  Furthermore, after mixing each dispersion liquid, a fine dispersion process using ultrasonic waves is effective. In this case, after the oil phase is prepared, the aggregates of the magnetic material in the dispersion are loosened and further fine dispersion is possible.

  The aqueous medium may be water alone, but a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), and lower ketones (acetone, methyl ethyl ketone, etc.). It is also a preferable method to mix an appropriate amount of the organic medium used for the oil phase in the aqueous medium used in the present invention. This seems to have the effect of enhancing droplet stability during granulation and making the aqueous medium and the oil phase more easily suspended.

  In the present invention, it is preferable to use the resin fine particles containing the resin (b) dispersed in an aqueous medium. The resin fine particles containing the resin (b) are used in a desired amount according to the stability of the oil phase in the next step and the encapsulation of the toner base particles. In the present invention, when resin fine particles are used for forming the surface layer (B), the amount of the resin fine particles used is 1.0% by mass or more and 15.0% by mass or less based on the toner base particles (A). It is preferable that

  In the aqueous medium, a known surfactant, dispersant, dispersion stabilizer, water-soluble polymer, or viscosity modifier may be added.

  Examples of the surfactant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. These can be arbitrarily selected according to the polarity at the time of toner particle formation.

  Specifically, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters; alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, and alkyltrimethyl Ammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, quaternary ammonium salt type cationic surfactants such as benzethonium chloride; fatty acid amide derivatives, polyhydric alcohol derivatives, etc. Nonionic surfactants; amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine.

The following are mentioned as said dispersing agent.
Acids such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride;
Β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloro-2-acrylate Hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-methylolacrylamide, N-methylolmethacrylamide, etc. (Meth) acrylic monomers containing the hydroxyl groups of
Ethers with vinyl alcohol or vinyl alcohol such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether;
Esters of vinyl alcohol and compounds containing a carboxyl group, such as vinyl acetate, vinyl propionate and vinyl butyrate;
Acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds; acid chlorides such as acrylic acid chloride and methacrylic acid chloride;
Homopolymers or copolymers of those having a nitrogen atom, such as vinylpyridine, vinylpyrrolidone, vinylimidazole, ethyleneimine, or a heterocyclic ring thereof;
Polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl Polyoxyethylenes such as phenyl ester, polyoxyethylene nonylphenyl ester;
Celluloses such as methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose.

  When a dispersant is used, the dispersant can remain on the surface of the toner particles. However, it is preferable to dissolve and remove it from the charged surface of the toner.

In the present invention, a solid dispersion stabilizer may be used to maintain a more preferable dispersion state. The reason is as follows. The organic medium in which the resin (a) as the main component of the toner is dissolved has a high viscosity. Therefore, the dispersion stabilizer surrounds the oil droplets formed by finely dispersing the organic medium with a high shearing force, preventing the oil droplets from reaggregating and stabilizing.

  As the above dispersion stabilizer, inorganic dispersion stabilizers and organic dispersion stabilizers can be used. In the case of inorganic dispersion stabilizers, toner particles are granulated in a state of adhering to the particle surface after dispersion. Those that can be removed by non-acidic acids such as hydrochloric acid are preferred. For example, calcium carbonate, calcium chloride, sodium hydrocarbon, potassium hydrocarbon, sodium hydroxide, potassium hydroxide, hydroxyapatite, and calcium triphosphate can be used.

  The dispersion method used at the time of preparing the toner particles is not particularly limited, and general-purpose devices such as a low-speed shear type, a high-speed shear type, a friction type, a high-pressure jet type, and an ultrasonic wave can be used. In order to make it about 20 μm, a high-speed shearing type is preferable.

If it is a stirrer which has a rotary blade, there will be no restriction | limiting in particular, If it is a general thing as an emulsifier and a disperser, it can be used for the said dispersion | distribution method.
For example, the following are mentioned. Ultra Thalax (manufactured by IKA), Polytron (manufactured by Kinematica), TK auto homomixer (manufactured by Special Mechanized Industry Co., Ltd.), Ebara Milder (manufactured by Ebara Corporation), TK homomic line flow (special Kika Kogyo Co., Ltd.), colloid mill (Shinko Pantech Co., Ltd.), slasher, trigonal wet milling machine (Mitsui Miike Kako Co., Ltd.), Cavitron (Eurotech Co., Ltd.), Fine Flow Mill (Pacific Ocean) Continuous type emulsifiers such as Kiko (manufactured by Kiko Co., Ltd.), batch-type emulsifiers such as Claremix (made by M Technique Co., Ltd.) and Fillmix (made by Tokushu Kika Kogyo Co., Ltd.).

  When a high-speed shearing disperser is used for the dispersion method, the rotation speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 3000 to 20000 rpm.

  In the case of a batch method, the dispersion time in the dispersion method is usually 0.1 to 5 minutes. The temperature during dispersion is usually 10 to 150 ° C. (under pressure), preferably 10 to 100 ° C.

  In order to remove the organic solvent from the obtained dispersion, it is possible to gradually elevate the temperature of the entire system and completely evaporate and remove the organic solvent in the droplets.

  Alternatively, the dispersion liquid can be sprayed in a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the water in the dispersion liquid can be removed by evaporation.

  In that case, as the dry atmosphere in which the dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, etc., especially various air currents heated to a temperature higher than the boiling point of the highest boiling solvent used is generally used. It is done. Even in a short time using a spray dryer, belt dryer or rotary kiln, the desired quality can be obtained sufficiently.

  When the dispersion obtained by the above dispersion method has a wide particle size distribution, and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classification into a desired particle size distribution.

  The dispersant used in the dispersion method is preferably removed from the obtained dispersion as much as possible, but more preferably it is performed simultaneously with the classification operation.

  In the production method, it is also possible to provide a heating step after removing the organic solvent. By providing the heating step, the toner particle surface can be smoothed and the sphericity of the toner particle surface can be adjusted.

  In the classification operation, the fine particles can be removed in the liquid by a cyclone, a decanter, a centrifugal separator or the like. Of course, the classification operation may be performed after obtaining the powder after drying, but it is preferable in the liquid to perform the classification operation.

  Unnecessary fine particles or coarse particles obtained by the classification operation can be returned to the dissolving step and used for forming particles. At that time, fine particles or coarse particles may be wet.

  In the toner of the present invention, inorganic fine particles can be used as an external additive for assisting the fluidity, developability and chargeability of the toner.

The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method of an inorganic fine particle is 20-500 m < ² > / g.

  The use ratio of the inorganic fine particles is preferably 0.01 parts by mass to 5 parts by mass, and more preferably 0.01 parts by mass to 2.0 parts by mass with respect to 100 parts by mass of the toner particles.

Specific examples of the inorganic fine particles include the following.
Silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara , Antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride. These inorganic fine particles may be used alone or in combination of plural kinds.

The inorganic fine particles are preferably increased in hydrophobicity by using a surface treatment agent in order to prevent deterioration of toner flow characteristics and charging characteristics even under high humidity.
The following are mentioned as a preferable surface treating agent.
Silane coupling agent, silylating agent, silane coupling agent having a fluoroalkyl group, organic titanate coupling agent, aluminum coupling agent, silicone oil, modified silicone oil.

Examples of the external additive (cleaning improver) for removing the toner after transfer remaining on the photosensitive member and the primary transfer medium include the following.
Polymer fine particles produced by soap-free emulsion polymerization of fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, for example, polymethyl methacrylate fine particles, polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

A method for measuring various physical properties of the toner of the present invention will be described below.
<Measuring method of average adhesion force (F50) of toner by centrifugal method>
The average adhesion force (F50) of the toner was measured according to the operation manual using a centrifugal adhesion measuring device NS-C100 (manufactured by Nano Seeds). The apparatus is roughly composed of an image analysis unit and a centrifuge unit. The image analysis unit includes a metal microscope, an image analysis device, and a video monitor. The centrifuge is composed of a high-speed centrifuge and a sample cell (material is aluminum A5052).
(Measuring method)
After the toner is adhered to a glass substrate (slide glass manufactured by Matsunami Glass Industrial Co., Ltd.), the glass substrate is fixed to the sample cell, and is set at 5 levels of 2000, 4000, 6000, 8000, and 10,000 rotations with a high-speed centrifuge. Centrifugation was performed and the toner separation state was recorded.
At this time, the separation force acting on the toner was calculated from the true specific gravity, particle diameter, rotation speed, and rotation radius of the toner.
The toner residual ratio R after rotation is measured with respect to the adhesion amount at the initial stage of measurement, the residual ratio is plotted on the vertical axis, and the separation force is plotted on the horizontal axis, and the separation force (in this case, 50% of toner is separated from the approximate line) The separation force was equivalent to the adhesion force), and the average adhesion force (F50) was calculated.
(Measurement environment) Normal room temperature environment (analysis method)
The rotational angular velocity ω at which the residual toner ratio R after rotation was 50% was calculated by the above-described measurement method, and the average adhesion force (F50) was calculated from the following equation.
Average adhesion force (F50) = (π / 6) · ρ · d ³ · r · ω ²
Where ρ is the particle density, d is the particle diameter, r is the rotational radius, and ω is the rotational angular velocity when the toner is separated by 50%.

<Method for Measuring Average Roughness (Ra) of Toner Particle Surface>
In the present invention, the surface roughness (Ra) of the toner was measured using a scanning probe microscope. The measurement conditions and methods are shown below.
Probe station: SPI3800N (manufactured by Seiko Instruments Inc.)
Measurement unit: SPA400
Measurement mode: DFM (resonance mode) shape image Cantilever: SI-DF40P
Resolution: X data number 256
Number of Y data 128
In the present invention, an area of 1 μm square on the toner particle surface was measured. The area to be measured was a 1 μm square area at the center of the toner particle surface measured with a scanning probe microscope. As the toner particles to be measured, toner particles having a particle diameter equal to the weight average particle diameter (D4) measured by the Coulter counter method described later were randomly selected. The measured data was subjected to secondary correction. Five or more different toner particles were measured, and the average value of the obtained data was calculated to obtain the average roughness (Ra) of the toner particle surface.
The average roughness (Ra) obtained as described above is obtained by extending the centerline average roughness Ra defined in JIS B0601 to three dimensions so that it can be applied to the measurement surface. It is a value obtained by averaging the absolute values of deviations from the reference surface to the designated surface, and is expressed by the following equation.

Ｆ（Ｘ，Ｙ）：全測定データの示す面
Ｓ０ ：指定面が理想的にフラットであると仮定したときの面積
Ｚ０ ：指定面内のＺデータ（指定面に対して垂直方向のデータ）の平均値
指定面とは、本発明においては１μｍ四方の測定エリアを意味する。

F (X, Y): Surface indicated by all measurement data S0: Area when the designated surface is assumed to be ideally flat Z0: Z data in the designated surface (data perpendicular to the designated surface) The average value designation surface means a measurement area of 1 μm square in the present invention.

<Measuring method of glass transition temperature (Tg) of resin>
The glass transition temperature (Tg) of the resin was measured in accordance with ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).
For the temperature correction of the device detection unit, the melting points of indium and zinc were used, and for the correction of the heat amount, the heat of fusion of indium was used.
Specifically, about 2 mg of a sample is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measurement was performed in min. In this temperature raising process, a specific heat change was obtained in the temperature range of 40 ° C to 100 ° C. The intersection between the baseline midpoint line before and after the change in specific heat at this time and the differential heat curve was taken as the glass transition temperature (Tg) of the sample.

<Method for measuring BET specific surface area of magnetic substance>
The BET specific surface area of the magnetic material of the present invention was measured as follows.
The BET specific surface area was obtained by a BET multipoint method using a fully automatic gas adsorption amount measuring device (Autosoap 1) manufactured by Yuasa Ionics Co., Ltd., using nitrogen as the adsorption gas. As a sample pretreatment, deaeration was performed at 50 ° C. for 10 hours.

<Measurement method of softening point (Tm) of resin>
The softening point (Tm) of the resin was measured under the following conditions using a flow characteristic evaluation device Flow Tester CFT500C (manufactured by Shimadzu Corporation), which is a constant load extruded capillary rheometer, according to the operation manual of the device. The flow tester curve based on the obtained data was in a state as shown in FIGS. 1A and 1B, and each temperature was read therefrom. In FIG. 1B, the melting temperature in the 1/2 method was defined as the softening point (Tm). Ts is a softening temperature and Tfb is an outflow start temperature.
(Measurement condition)
Load: 10 kgf / cm ² (9.807 × 10 ⁵ Pa)
Temperature increase rate: 4.0 ° C./min
Die diameter: 1.0mm
Die length: 1.0mm

<Measurement method of molecular weight distribution and molecular weight of resin>
The molecular weight distribution, weight average molecular weight, number average molecular weight and peak molecular weight measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble content of the resin were measured as follows.
First, the sample was dissolved in tetrahydrofuran (THF) at room temperature over 24 hours. The obtained solution was filtered through a solvent resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution was prepared so that the concentration of components soluble in THF was about 0.8% by mass. Using this sample solution, measurement was performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Shodex KF-801, 802, 803, 804, 805,
7 series of 806, 807 (made by Showa Denko)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min
Oven temperature: 40.0 ° C
Sample injection amount: 0.10 mL
In calculating the molecular weight of the sample, standard polystyrene resin (trade names “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) were used.

<Measuring method of dispersed particle diameter of wax particles in resin fine particles and wax dispersion>
The dispersion particle diameter of the resin fine particles and the wax particles in the wax dispersion is measured using a Microtrac particle size distribution measuring device HRA (X-100) (manufactured by Nikkiso Co., Ltd.) with a range setting of 0.001 μm or more and less than 10 μm. The number average particle diameter was measured.

<Measurement method of solid content ratio of resin fine particles and wax>
Using a moisture meter FD240 (manufactured by Kett Science Laboratory Co., Ltd.), set the temperature to 120 ° C., and evaporating the water until no change in weight is observed for 1 minute. Was measured.

<Measurement Method of Toner Weight Average Particle Size (D4) and Number Average Particle Size (D1)>
The weight average particle diameter (D4) and the number average particle diameter (D1) of the toner are determined by a fine particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, Beckman Coulter, Inc.) equipped with a 100 μm aperture tube. ) And the dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for setting measurement conditions and analyzing measurement data, the number of effective measurement channels is 25,000. The measurement data was analyzed and analyzed.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter) can be used.
Prior to measurement and analysis, dedicated software was set up as follows.
In the “Standard measurement method (SOM) change screen” of the dedicated software, set the total count in the control mode to 50000 particles, the number of measurements is 1 and the Kd value is “standard particles 10.0 μm” (Beckman Coulter, Inc.) The value obtained using the above was set. The threshold and noise level were automatically set by pressing the threshold / noise level measurement button. Further, the current was set to 1600 μA, the gain was set to 2, the electrolyte was set to ISOTON II, and the aperture tube flash after the measurement was checked.
In the “Pulse to Particle Size Conversion Setting Screen” of the dedicated software, the bin interval was set to logarithmic particle size, the particle size bin to 256 particle size bin, and the particle size range from 2 μm to 60 μm.
The specific measurement method is as follows.
(1) About 200 mL of the electrolytic solution was placed in a glass 250 mL round-bottom beaker dedicated to Multisizer 3, set on a sample stand, and the stirrer rod was stirred counterclockwise at 24 rpm. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 mL of the electrolytic aqueous solution is put in a glass 100 mL flat-bottom beaker, and “Contaminone N” (nonionic surfactant, anionic surfactant, organic builder consisting of an organic builder) is used as a dispersant. About 0.3 mL of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (made by Wako Pure Chemical Industries, Ltd.) 3 times with ion exchange water was added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and placed in a water tank of an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikkiki Bios Co., Ltd.) having an electrical output of 120 W. A predetermined amount of ion-exchanged water was added, and about 2 mL of the contamination N was added to this water tank.
(4) The beaker of (2) was set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser was operated. Then, the height position of the beaker was adjusted so that the resonance state of the electrolytic aqueous solution liquid level in the beaker was maximized.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) was irradiated with ultrasonic waves, about 10 mg of toner was added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion treatment was further continued for 60 seconds. In the ultrasonic dispersion, the water temperature in the water tank was appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker (1) installed in the sample stand, the electrolyte aqueous solution (5) in which the toner is dispersed is dropped using a pipette, and the measured concentration is adjusted to about 5%. . The measurement was performed until the number of measured particles reached 50,000.
(7) The measurement data was analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) were calculated. When the graph / volume% is set with the dedicated software, the “average diameter” on the analysis / volume statistics (arithmetic average) screen is the weight average particle size (D4), and the graph / number% is set with the dedicated software. The “average diameter” on the analysis / number statistics (arithmetic average) screen is the number average particle diameter (D1).

<Measurement method of magnetization>
The strength of magnetization of the magnetic material and the toner was determined from the magnetic properties and the mass. The magnetic properties of the magnetic material and the toner were measured using a “vibration data type magnetometer VSM-3S-15” (manufactured by Toei Industry Co., Ltd.). As a measuring method, a cylindrical plastic container is filled with a magnetic substance or toner so as to be sufficiently dense, while an external magnetic field of 1.00 kilo Oersted (79.6 kA / m) is created, and in this state, the container The magnetization moment of the magnetic material or toner filled in was measured. Next, the actual mass of the magnetic material or toner filled in the container was measured to determine the magnetization intensity (Am ² / kg) of the magnetic material or toner.
Further, the residual magnetization (σr) was obtained by drawing a hysteresis loop when the maximum applied magnetic field was set to 1.00 kilo Oersted (79.6 kA / m).

<Measurement method of sulfonic acid group value>
The resin fine particle dispersion with a solid content of 20% by mass is made neutral (pH = 7.0 ± 0.1) with hydrochloric acid or sodium hydroxide, and then the pH and zeta potential of the dispersion are titrated while hydrochloric acid is titrated. Measure. It is observed that the zeta potential changes from a negative value to a positive value in the pH range of 2.0 to 3.0. The point at which the zeta potential is 0 in this range is determined, and the number of moles of hydrochloric acid required is determined. The mass of potassium hydroxide with the same number of moles is determined. On the other hand, the value of the sulfonic acid group value per unit mass was determined by determining the mass of the solid content of the resin fine particle dispersion.
When the pH is 3.0 or more and the zeta potential changes from a negative value to a positive value, the sulfonic acid group value is 0 mgKOH / g.

<Method for measuring acid value of resin>
The acid value is the number of mg of potassium hydroxide necessary to neutralize the acid contained in 1 g of the sample.
The acid value of the resin is measured according to JIS K 0070-1966, and specifically, it is measured according to the following procedure.
(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 mL of ethyl alcohol (95 vol%), and ion exchange water is added to make 100 mL to obtain a “phenolphthalein solution”.
7 g of special grade potassium hydroxide is dissolved in 5 mL of water, and ethyl alcohol (95 vol%) is added to make 1 l. Place in an alkali-resistant container so as not to touch carbon dioxide gas, leave it for 3 days, and filter to obtain a “potassium hydroxide solution”. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The orientation is performed according to JIS K 0070-1996.
(2) Operation (A) Main test 2.0 g of the pulverized sample is precisely weighed into a 200 mL Erlenmeyer flask, and 100 mL of a mixed solution of toluene / ethanol (2: 1) is added and dissolved over 5 hours. Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titrated with the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test Titration is performed in the same manner as described above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(BC) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (mL) of potassium hydroxide solution in blank test, C: addition amount (mL) of potassium hydroxide solution in final test, f: potassium hydroxide Solution factor, S: sample (g).

<Measurement of bulk density of magnetic material>
For the bulk density of the magnetic material, a powder tester PT-R (manufactured by Hosokawa Micron) is used.
Measurement was performed according to the operation manual of the instrument.
Using a sieve with a mesh opening of 500 μm, while vibrating with an amplitude of 1 mm, replenishing the magnetic material to just 10 ml, tapping the metallic cup up and down 180 times with an amplitude of 18 mm, and the amount of magnetic material after tapping From the above, the bulk density (g / cm ³ ) was calculated.

<Measuring method of number average particle diameter (D50) of magnetic substance and coefficient of variation of particle diameter of magnetic substance>
The number average particle diameter (D50) and standard deviation σ of the magnetic material were calculated by measuring particle images (arbitrarily 350) taken with an electron microscope using a statistical analysis (Digitizer KD4620 manufactured by Graphtec Corporation). .
Further, the coefficient of variation of the particle diameter of the magnetic material was calculated according to the following formula from the number average diameter D50 (μm) and the standard deviation σ (μm). The smaller the value of the particle size distribution, the better the particle size distribution.
(Expression) Coefficient of variation of particle size of magnetic material = σ / D50 × 100 (%)

<Measuring method of average circularity of toner>
The average circularity of the toner particles was measured under calibration and measurement conditions using a flow particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation).
As a specific measurement method, an appropriate amount of a surfactant as a dispersant, preferably sodium dodecylbenzenesulfonate, is added to 20 ml of ion-exchanged water, 0.02 g of a measurement sample is added, an oscillation frequency of 50 kHz, electrical output Dispersion treatment was carried out for 2 minutes using a 150 W desktop ultrasonic cleaner / disperser (for example, “VS-150” (manufactured by Vervo Creer)) to obtain a dispersion for measurement. In that case, it cooled suitably so that the temperature of a dispersion liquid might be 10 degreeC or more and 40 degrees C or less.
The flow type particle image analyzer equipped with a standard objective lens (10 ×) was used for the measurement, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion prepared and prepared according to the above procedure is introduced into the flow type particle image analyzer, 3000 toner particles are measured in the total count mode in the HPF measurement mode, and the binarization threshold at the time of particle analysis is 85. %, And the analysis particle diameter is equivalent to a circle equivalent diameter of 2.00 μm or more, 200.00 μm
The average circularity of the toner particles was determined by limiting to m or less.
In the measurement, before starting the measurement, standard latex particles (for example, Duke Scientific)
automatic focusing is performed using “5100A” manufactured by ific Co., Ltd.). Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.
In this embodiment, a flow type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, has an analysis particle diameter of 2.00 μm. The measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that it was limited to 200.00 μm or less.

<Measurement method of melting point of wax>
The melting point of the wax was measured using a differential scanning calorimeter (DSC) “Q1000” (manufactured by TA Instruments) according to ASTM D3418-82.
For the temperature correction of the device detection unit, the melting points of indium and zinc were used, and for the correction of the heat amount, the heat of fusion of indium was used.
Specifically, about 10 mg of a sample is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measurement was performed in min. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 30 ° C., and then the temperature is raised again. In this second temperature raising process, the temperature showing the maximum endothermic peak of the DSC curve in the temperature range of 30 to 200 ° C. was taken as the melting point of the wax. The maximum endothermic peak means a peak having the largest endothermic amount when there are a plurality of peaks.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In addition, the number of parts in the following composition is part by mass unless otherwise specified.

[Preparation of Resin Fine Particle Dispersion-1]
120 parts by mass of a polyester diol having a number average molecular weight of about 2000 obtained from an equimolar mixture of propylene glycol, ethylene glycol, and butanediol with a 40:50:10 molar mixture of terephthalic acid and isophthalic acid 94 masses of dimethylolpropanoic acid Part 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid
8 parts by mass / isophorone diisocyanate 120 parts by mass

The raw material was dissolved in 60 parts by mass of acetone and reacted at 67 ° C. for 1 hour.
Then, 271 parts by mass of isophorone diisocyanate was added, and the mixture was further reacted at 67 ° C. for 30 minutes and cooled. After adding 100 parts by mass of acetone to the reaction product, 80 parts by mass of triethylamine was added and stirred.
The acetone solution was added dropwise to 1000 parts by mass of ion-exchanged water with stirring at 500 rpm to prepare a fine particle dispersion.
Then, an elongation solution was carried out by adding an aqueous solution in which 50 parts by mass of triethylamine was dissolved in 100 parts by mass of 10% ammonia water and reacting at 50 ° C. for 8 hours. Furthermore, ion-exchange water was added until the solid content became 20% by mass to obtain a resin fine particle dispersion-1. The characteristics are shown in Table 1.

[Preparation of resin fine particle dispersion-2]
In an autoclave equipped with a thermometer and a stirrer,
Dimethyl terephthalate 116 parts by weight dimethyl isophthalate 66 parts by weight 5-sodium sulfoisophthalate methyl ester 3 parts by weight trimellitic anhydride 5 parts by weight propylene glycol 150 parts by weight tetra 0.1 part by weight of butoxy titanate was charged and heated at 200 ° C. for 120 minutes to conduct a transesterification reaction. Next, the temperature of the reaction system was raised to 220 ° C., and the reaction was continued for 60 minutes with the system pressure set to 1 to 10 mmHg to obtain a polyester resin. After dissolving 40 parts by mass of the polyester resin, 15 parts by mass of methyl ethyl ketone, and 10 parts by mass of tetrahydrofuran at 80 ° C., 60 parts by mass of 80 ° C. water was added with stirring, the solvent was removed under reduced pressure, and ion-exchanged water. Was added to obtain a fine resin particle dispersion-2 having a solid content of 20% by mass. The characteristics are shown in Table 1.

[Preparation of resin fine particle dispersion-3]
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
-Styrene 330 parts by weight-n-butyl acrylate 110 parts by weight-Acrylic acid 10 parts by weight-2-butanone (solvent) 50 parts by weight 2,2'-azobis (2,4-dimethylvaleronitrile) 8 weights as a polymerization initiator A part was dissolved in the raw material to prepare a polymerizable monomer composition. The polymerizable monomer composition was subjected to a polymerization reaction at 60 ° C. for 8 hours, then heated to 150 ° C., desolvated under reduced pressure, and taken out from the reaction vessel. After cooling to room temperature, it was pulverized and granulated to obtain a binder resin that was a linear vinyl resin. 100 parts by mass of the taken out resin was mixed with 400 parts by mass of toluene and heated to 80 ° C. to dissolve the resin.
Next, 360 parts by mass of ion exchange water and 40 parts by mass of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7”, manufactured by Sanyo Chemical Industries) were added to the above resin solution and mixed and stirred. A milky white liquid was obtained. Toluene was removed under reduced pressure, and ion-exchanged water was added to obtain Resin Fine Particle Dispersion-3 having a solid content of 20% by mass. The characteristics are shown in Table 1.

[Preparation of Resin Fine Particle Dispersion-4]
Polyester diol having a number average molecular weight of about 2000, obtained from an equimolar mixture of propylene glycol, ethylene glycol, and butanediol, 40:50:10 mol, and terephthalic acid, isophthalic acid, 100 parts by mass, propylene glycol, 16 parts by mass 94 parts by mass of dimethylolpropanoic acid / sodium N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonate
8 parts by mass, 30 parts by mass of tolylene diisocyanate

The raw material was dissolved in 60 parts by mass of acetone and reacted at 67 ° C. for 1 hour.
Further, 271 parts by mass (1.2 mol) of isophorone diisocyanate was added, and the mixture was further reacted at 67 ° C. for 30 minutes and cooled.
After adding 100 parts by mass of acetone to the reaction product, 80 parts by mass (0.8 mol) of triethylamine was added and stirred.
The acetone solution was added dropwise to 1000 parts by mass of ion-exchanged water with stirring at 500 rpm to prepare a fine particle dispersion.
Then, an elongation solution was carried out by adding an aqueous solution in which 50 parts by mass of triethylamine was dissolved in 100 parts by mass of 10% aqueous ammonia and reacting at 50 ° C. for 8 hours. Further, ion-exchanged water was added until the solid content became 20% by mass to obtain resin fine particle dispersion-4. The characteristics are shown in Table 1.

[Preparation of resin fine particle dispersion-5]
120 parts by mass of a polyester diol having a number average molecular weight of about 2000, obtained from an equimolar mixture of 40:50:10 moles of propylene glycol, ethylene glycol and butanediol and terephthalic acid and isophthalic acid. 8 parts by weight of propylene glycol 94 parts by mass of dimethylolpropanoic acid, 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid
8 parts by mass, isophorone diisocyanate 39 parts by mass

The raw material was dissolved in 60 parts by mass of acetone and reacted at 67 ° C. for 1 hour.
Next, 271 parts by mass of isophorone diisocyanate was added, and the mixture was further reacted at 67 ° C. for 30 minutes and cooled.
The acetone solution was added dropwise to 1000 parts by mass of ion-exchanged water with stirring at 500 rpm to prepare a fine particle dispersion.
After adding 100 parts by mass of acetone to the reaction product, 80 parts by mass of triethylamine was added and stirred.
Then, an elongation solution was carried out by adding an aqueous solution in which 50 parts by mass of triethylamine was dissolved in 100 parts by mass of 10% aqueous ammonia and reacting at 50 ° C. for 8 hours. Further, ion-exchanged water was added until the solid content became 20% by mass to obtain a resin fine particle dispersion-5. The characteristics are shown in Table 1.

[Preparation of Resin Fine Particle Dispersion-6]
120 parts by mass of a polyester diol having a number average molecular weight of about 2000, obtained from an equimolar mixture of 40:50:10 moles of propylene glycol, ethylene glycol and butanediol and terephthalic acid and isophthalic acid. 8 parts by weight of propylene glycol 94 parts by mass of dimethylolpropanoic acid, 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid
8 parts by mass, isophorone diisocyanate 39 parts by mass

The raw material was dissolved in 60 parts by mass of acetone and reacted at 67 ° C. for 1 hour.
Next, 150 parts by mass of isophorone diisocyanate was added, and the mixture was further reacted at 65 ° C. for 20 minutes and cooled.
The acetone solution was added dropwise to 1000 parts by mass of ion-exchanged water with stirring at 500 rpm to prepare a fine particle dispersion.
After adding 100 parts by mass of acetone to the reaction product, 80 parts by mass of triethylamine was added and stirred.
Then, an elongation solution was carried out by adding an aqueous solution in which 50 parts by mass of triethylamine was dissolved in 100 parts by mass of 10% aqueous ammonia and reacting at 50 ° C. for 8 hours. Furthermore, ion-exchanged water was added until the solid content became 20% by mass to obtain a resin fine particle dispersion-6. The characteristics are shown in Table 1.

[Preparation of polyester-1 and polyester resin solution-1]
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
・ 928 parts by mass of 1,4-butanediol, 776 parts by mass of dimethyl terephthalate, 292 parts by mass of 1,6-hexanedioic acid, 3 parts by mass of tetrabutoxy titanate (condensation catalyst), and methanol produced at 160 ° C. under a nitrogen stream. Was allowed to react for 8 hours while distilling off. Next, while gradually raising the temperature to 210 ° C., the reaction was carried out for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further carried out for 1 hour under a reduced pressure of 20 mmHg. Next, the mixture was cooled to 160 ° C., 173 parts by weight of trimellitic anhydride and 125 parts by weight of 1,3-propanedioic acid were added, reacted for 2 hours under normal pressure sealing, and then reacted at 200 ° C. and normal pressure, and the softening point was 170 ° C. When it became, it took out. The resin taken out was cooled to room temperature and then pulverized and granulated to obtain polyester-1 which is a nonlinear polyester resin. Table 2 shows Tg and acid value.
Next, ethyl acetate is put into a closed vessel with stirring blades, and the polyester-1 powder is put into 50% by mass with respect to the added ethyl acetate while stirring at 100 rpm and stirred at room temperature for 3 days. Thus, a polyester resin solution-1 was prepared.

[Preparation of polyester-2 and polyester resin solution-2]
・ Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane

30 parts by mass-polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane
33 parts by mass, 21 parts by mass of terephthalic acid, 1 part by mass of trimellitic anhydride, 3 parts by mass of fumaric acid, 12 parts by mass of dodecenyl succinic acid, 0.1 part by mass of dibutyltin oxide are placed in a 4-liter 4-neck flask made of glass. Then, a thermometer, a stirring bar, a condenser and a nitrogen introduction tube were attached and placed in a mantle heater. Under a nitrogen atmosphere, the mixture was reacted at 215 ° C. for 5 hours to obtain polyester-2. Table 2 shows Tg and acid value.
Next, ethyl acetate is put into a closed vessel with stirring blades, and the polyester-2 powder is added so as to be 50% by mass with respect to the charged ethyl acetate, and stirred at room temperature for 3 days. Thus, a polyester resin solution-2 was prepared.

[Preparation of polyester-3 and polyester resin solution-3]
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
-1,2-propanediol 799 parts by mass-terephthalic acid dimethyl ester 815 parts by mass-1,5-pentanedioic acid 238 parts by mass-tetrabutoxy titanate (condensation catalyst) 3 parts by mass Methanol produced under nitrogen flow at 180 ° C Was allowed to react for 8 hours while distilling off. Then, while gradually raising the temperature to 230 ° C., the reaction was carried out for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further carried out for 1 hour under a reduced pressure of 20 mmHg. Next, the mixture was cooled to 180 ° C., 173 parts by mass of trimellitic anhydride was added, reacted for 2 hours under sealed at normal pressure, reacted at 220 ° C. normal pressure, and taken out when the softening point reached 180 ° C. The resin taken out was cooled to room temperature and then pulverized and granulated to obtain polyester-3, which is a nonlinear polyester resin. Table 2 shows Tg and acid value.
Next, ethyl acetate is put into a closed vessel with stirring blades, and the polyester-3 powder is put into 50% by mass with respect to the added ethyl acetate while stirring at 100 rpm, and stirred at room temperature for 3 days. Thus, a polyester resin solution-3 was prepared.

[Preparation of polyester-4 and polyester resin solution-4]
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
-1,3-butanediol 1036 parts by mass-terephthalic acid dimethyl ester 892 parts by mass-1,6-hexanedioic acid 205 parts by mass-tetrabutoxy titanate (condensation catalyst) 3 parts by mass Methanol produced in a nitrogen stream at 180 ° C Was allowed to react for 8 hours while distilling off. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water in a nitrogen stream, and further the reaction was performed under a reduced pressure of 20 mmHg, and the softening point was 150 ° C. Removed at the time. The taken-out resin was cooled to room temperature and then pulverized and granulated to obtain polyester-4, which is a linear polyester resin. Table 2 shows Tg and acid value.
Next, ethyl acetate is put into a closed vessel with stirring blades, and the polyester-4 powder is put so as to be 50% by mass with respect to the added ethyl acetate, and stirred at room temperature for 3 days. Thus, a polyester resin solution-4 was prepared.

[Preparation of polyester-5 and polyester resin solution-5]
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
-1,2 propanediol 858 parts by mass-terephthalic acid dimethyl ester 873 parts by mass-1,6-hexanedioic acid 219 parts by mass-tetrabutoxy titanate (condensation catalyst) 3 parts by mass Methanol produced at 180 ° C under a nitrogen stream The reaction was allowed to proceed for 8 hours while evaporating. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water in a nitrogen stream, and further the reaction was performed under a reduced pressure of 20 mmHg, and the softening point was 150 ° C. Removed at the time. The resin taken out was cooled to room temperature and then pulverized and granulated to obtain polyester-5, which is a linear polyester resin. Table 2 shows Tg and acid value.
Next, ethyl acetate is put into a closed vessel with stirring blades, and the polyester-5 powder is put so that the mass becomes 50% by mass with respect to the added ethyl acetate, and stirred at room temperature for 3 days. Thus, a polyester resin solution-5 was prepared.

[Preparation of styrene acrylic-1 and styrene acrylic resin solution-1]
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
Styrene 320 parts by mass n-butyl acrylate 110 parts by mass acrylic acid 10 parts by mass 2-butanone (solvent) 50 parts by mass 2,2′-azobis (2,4-dimethylvaleronitrile) 8% as a polymerization initiator A part was dissolved in the raw material to prepare a polymerizable monomer composition. The polymerizable monomer composition was subjected to a polymerization reaction at 60 ° C. for 8 hours, heated to 160 ° C., desolvated under reduced pressure, and taken out from the reaction vessel. After cooling to room temperature, it was pulverized and granulated to obtain styrene acrylic-1 which is a linear vinyl resin. Table 2 shows Tg and acid value.
Next, ethyl acetate is put into a closed vessel with stirring blades and stirred at 100 rpm, and the styrene acrylic-1 powder is put so as to be 50% by mass with respect to the added ethyl acetate and stirred at room temperature for 3 days. Thus, a styrene acrylic resin solution-1 was prepared.

[Preparation of Wax Dispersion-1]
<Wax dispersion medium I>
Copolymer resin (I) 90 parts by mass [nitrile group-containing styrene acrylic resin (styrene 65 parts by mass, n-butyl acrylate 35 parts by mass, acrylonitrile 10 parts by mass, peak molecular weight 8500)]

Polyethylene (I) melting point 107 ° C. 10 parts by mass Copolymer resin (I) was grafted onto polyethylene (I) at the above blending ratio to obtain a wax dispersion medium (I).
Subsequently, the following was put into a glass beaker (made by IWAKI glass) with a stirring blade, and the system was heated to 70 ° C. to be dissolved in ethyl acetate.
・ Wax dispersion medium (I) 8 parts by mass ・ Carnauba wax (melting point 81 ° C.) 16 parts by mass ・ Ethyl acetate 76 parts by mass To obtain a milky white liquid.
This solution was put into a heat-resistant container together with 20 parts by mass of 1 mm glass beads, and dispersed for 3 hours with a paint shaker (manufactured by Toyo Seiki) to obtain wax dispersion-1. The dispersed particle size of the wax particles in the wax dispersion-1 was measured with a Microtrac particle size distribution analyzer HRA (X-100) (manufactured by Nikkiso Co., Ltd.). The characteristics are shown in Table 3.

[Preparation of Wax Dispersion-2]
-Wax dispersion medium (I) 8 parts by mass
-Stearyl stearate (melting point: 67 ° C) 16 parts by mass-Ethyl acetate: 76 parts by mass -1) was dissolved in ethyl acetate.
Subsequently, the same operation as wax dispersion-1 was performed to obtain wax dispersion-2. The dispersed particle size of the wax particles in the wax dispersion-2 was measured with a Microtrac particle size distribution analyzer HRA (X-100) (manufactured by Nikkiso Co., Ltd.). The characteristics are shown in Table 3.

[Preparation of Wax Dispersion-3]
Trimethylolpropane tribehenate (melting point: 58 ° C.) 20 parts by mass Ethyl acetate 80 parts by mass The above is put into a glass beaker (made by IWAKI glass) with a stirring blade, and the system is heated to 60 ° C. Methylolpropane tribehenate (ester-2) was dissolved in ethyl acetate.
Subsequently, the same operation as wax dispersion-1 was performed to obtain wax dispersion-3. The dispersed particle size of the wax particles in the wax dispersion-3 was measured with a Microtrac particle size distribution analyzer HRA (X-100) (manufactured by Nikkiso Co., Ltd.). The characteristics are shown in Table 3.

[Preparation of Wax Dispersion-4]
-Wax dispersion medium (I) 8 parts by mass
-Paraffin wax (melting point 74 ° C) 16 parts by mass-Ethyl acetate 76 parts by mass ) Was dissolved in ethyl acetate.
Then, the same operation as in wax dispersion-1 was performed to obtain wax dispersion-4. The dispersed particle size of the wax particles in the wax dispersion-4 was measured with a Microtrac particle size distribution analyzer HRA (X-100) (manufactured by Nikkiso Co., Ltd.). The characteristics are shown in Table 3.

[Preparation of Wax Dispersion-5]
Carnauba wax (melting point 81 ° C.) 20 parts by mass Ethyl acetate 80 parts by mass ) Was dissolved in ethyl acetate.
Next, the system was gradually cooled while gently stirring at 50 rpm, and cooled to 25 ° C. over 3 hours to obtain a milky white liquid.
This solution was put into a heat-resistant container together with 20 parts by mass of 1 mm glass beads and dispersed for 3 hours with a paint shaker (manufactured by Toyo Seiki Co., Ltd.) to obtain a wax dispersion-5. The dispersed particle size of the wax particles in the wax dispersion-5 was measured with a Microtrac particle size distribution analyzer HRA (X-100) (manufactured by Nikkiso Co., Ltd.). The characteristics are shown in Table 3.

The characteristics of the following magnetites 1 to 5 are shown in Table 4.
[Preparation of Magnetic Dispersion-1]
-100 parts by weight of ethyl acetate-50 parts by weight of polyester-1-100 parts by weight of magnetite-1-100 parts by weight of glass beads (1 mm) The above substances are put into a heat-resistant glass container, and a paint shaker (manufactured by Toyo Seiki) The dispersion was performed for 5 hours, and the glass beads were removed with a nylon mesh to obtain a magnetic dispersion-1.

[Preparation of magnetic dispersion-2]
・ Polyester-2 50 parts by mass Magnetite-2 100 parts by mass (kneading step)
The above raw materials are charged into a kneader-type mixer, and the temperature is raised under no pressure while mixing. The temperature is raised to 130 ° C., and melted and kneaded for about 10 minutes to disperse the magnetite in the resin. Thereafter, kneading is continued while cooling, cooling to 80 ° C., and 50 parts by mass of ethyl acetate is gradually added. After adding ethyl acetate, the system was fixed at 75 ° C. and kneaded for 30 minutes. After the process was completed, the system was cooled and the kneaded product was taken out to obtain a kneaded product.
Next, the kneaded product is coarsely pulverized with a hammer, mixed with ethyl acetate so that the solid content concentration becomes 60% by mass, and then stirred with a disper at 8000 rpm for 10 minutes to obtain magnetic properties. Body dispersion-2 was obtained.

[Preparation of magnetic dispersion-3]
・ Magnetite-3 250 parts by mass ・ Ethyl acetate 250 parts by mass ・ Glass beads (1 mm) 300 parts by mass The above substances were put into a heat-resistant glass container and dispersed for 5 hours in a paint shaker (manufactured by Toyo Seiki). The glass beads were removed with a mesh to obtain a magnetic dispersion liquid-3.

[Preparation of magnetic dispersion-4]
-Polyester-4 50 mass parts-Magnetite-4 100 mass parts The above-mentioned raw materials are charged into a kneader mixer, and heated under non-pressurization while mixing. The temperature is raised to 130 ° C., and melted and kneaded for about 60 minutes to disperse the magnetite in the resin.
After finishing this step, the mixture was cooled and the kneaded product was taken out to obtain a kneaded product.
Next, the kneaded product is coarsely pulverized using a hammer, mixed with ethyl acetate so that the solid content concentration is 60% by mass, and then stirred using a disper at 8000 rpm for 10 minutes to obtain magnetic properties. Body dispersion-4 was obtained.

[Preparation of magnetic dispersion-5]
Polyester-5 50 parts by mass Magnetite-5 100 parts by mass The above raw materials are charged into a kneader-type mixer and heated under pressure without mixing. The temperature is raised to 130 ° C., and melted and kneaded for about 60 minutes to disperse the magnetite in the resin.
After finishing this step, the mixture was cooled and the kneaded product was taken out to obtain a kneaded product.
Next, the kneaded product was coarsely pulverized with a hammer and used in the following steps.
-150 parts by weight of the coarsely pulverized product-100 parts by weight of ethyl acetate-100 parts by weight of glass beads (1 mm) The above substances are put into a heat-resistant glass container and dispersed for 5 hours in a paint shaker (manufactured by Toyo Seiki). The glass beads were removed with a nylon mesh to obtain a magnetic dispersion-5.

<Example 1>
(Preparation of oil phase)
Wax dispersion-1 62.5 parts by mass Magnetic substance dispersion-1 75 parts by mass Polyester resin solution-1 80 parts by mass Triethylamine 0.5 parts by mass Ethyl acetate 34.5 parts by mass The mixture was stirred and dispersed for 10 minutes at 1500 rpm with a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.). Furthermore, 100 parts by mass of glass beads were added to the above solution, and dispersed for 1 hour with a paint shaker (manufactured by Toyo Seiki). The glass beads were removed with a nylon mesh, and oil phase 1 was prepared.
(Preparation of aqueous phase)
The following was put into a container and stirred at 5000 rpm for 1 minute with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to prepare an aqueous phase.
・ Ion-exchanged water 245 parts by massResin fine particle dispersion-1 25 parts by mass (preparing resin parts 5.0 parts by mass with respect to 100 parts by mass of toner base particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 25 parts by mass-30 parts by mass of ethyl acetate (emulsification and desolvation step)
Into 335 parts by mass of the water phase, 250 parts by mass of the oil phase was added, and stirring was continued for 3 minutes with a TK homomixer at a rotational speed of up to 8000 rpm, whereby the oil phase 1 was suspended.
Next, a stirring blade is set in the container, the temperature inside the system is raised to 40 ° C. while stirring at 200 rpm, the solvent is removed over 4 hours, and then the system is returned to room temperature and emulsified while stirring for another 4 hours. The droplets were aged and sufficient solvent removal was performed to obtain an aqueous dispersion of toner particles 1.

(Washing to drying process)
Next, the aqueous dispersion of toner particles 1 was filtered and reslurried in 500 parts by mass of ion-exchanged water. Then, while stirring the system, hydrochloric acid was added until the system reached pH 4 and stirred for 5 minutes.
The slurry was filtered again and the operation of adding 200 parts by mass of ion-exchanged water and stirring for 5 minutes was repeated three times to remove triethylamine remaining in the system, and a filter cake of toner particles 1 was obtained.
The above filter cake was dried with a hot air dryer at 45 ° C. for 3 days, and sieved with an opening of 75 μm to obtain toner particles 1.

(Toner preparation)
Next, 0.7 parts by mass of hydrophobic silica having an average diameter of 20 nm and 3.0 parts by mass of strontium titanate having an average diameter of 120 nm are added to Henschel mixer (Mitsui Miike Chemical Co., Ltd.) with respect to 100 parts by mass of the toner particles 1. The toner 1 was obtained by mixing with FM-10B. The component composition ratio of Toner 1 is shown in Table 5, and the physical properties of Toner 1 are shown in Table 6.

<Image evaluation>
A method for evaluating the obtained toner will be described. A commercially available Canon black and white copying machine (trade name: IR3570) was used for image evaluation. Table 7 shows the toner image evaluation results.

After leaving the test machine for image evaluation in an environment of 23 ° C. and 5% RH overnight, the machine temporarily stops between jobs with a horizontal line pattern of 3% print rate per job. Then, in a mode in which the next job is set to start, an image endurance test for 50,000 sheets was performed using A4 plain paper (75 g / m ² ).

<Fog>
In the evaluation of fog, at the end of 1000 sheets during the endurance test, the development bias AC component amplitude was set to 1.8 kV, two solid whites were printed, and the second fog was measured by the following method. did.
Using a reflection densitometer (reflectometer model TC-6DS: manufactured by Tokyo Denshoku Co., Ltd.), the transfer material before and after image formation was measured, Ds was the worst reflection density value after image formation, and the reflection average of the transfer material before image formation The concentration was Dr, and Ds-Dr was determined and evaluated as the amount of fog. The smaller the number, the less the fog. The evaluation standard of fog is shown below.
(Evaluation criteria)
A: Less than 1.0.
B: 1.0 or more and less than 2.0.
C: 2.0 or more and less than 3.5.
D: 3.5 or more.

<Reproducibility of thin lines>
The fine line reproducibility was evaluated at the end of 1000 sheets and 10,000 sheets during the durability test.
First, a fixed image printed on cardboard (105 g / m ² ) by laser exposure so that the line width of the latent image was 85 μm was used as a measurement sample. Using a Luzex 450 particle analyzer (Nireco Co., Ltd.) as a measuring device, the line width was measured from the enlarged monitor image using an indicator. At this time, since the measurement position of the line width is uneven in the width direction of the toner fine line image, the average line width of the unevenness was used as the measurement point. The fine line reproducibility was evaluated by calculating the ratio (line width ratio) of the measured line width value to the latent image line width (85 μm). The evaluation criteria for fine line reproducibility are shown below.
(Evaluation criteria)
The ratio of the line width measurement value to the latent image line width (line width ratio) is
A: Less than 1.08.
B: 1.08 or more and less than 1.12.
C: 1.12 or more and less than 1.18.
D: 1.18 or more.

<Transfer efficiency>
After 1000 sheets, transfer efficiency was measured following fine line reproducibility. A solid image is output under the setting conditions in which fine line reproducibility is measured, and the image transferred onto the transfer paper and the residual image density on the photosensitive member are measured with a densitometer (X-rite 500 Series: manufactured by X-rite). did. From the image density, the applied amount was converted to obtain the transfer efficiency onto the transfer paper.
(Evaluation criteria)
A: The toner transfer efficiency is 95% or more.
B: The transfer efficiency of the toner is 93% or more.
C: The toner transfer efficiency is 90% or more.
D: The transfer efficiency of the toner is less than 90%.

<Image density>
The image density was evaluated by the following procedure. That is, using the above tester, the toner loading amount is 0.35 mg / cm ² in a solid image on Canon Recycle Paper EN-100 (Canon) under normal temperature and normal humidity environment (23 ° C./60% RH). The image after fixing was prepared.
The image was evaluated using a reflection densitometer 500 Series Spectrodensitometer manufactured by X-rite. The evaluation standard of image density is shown below.
(Evaluation criteria)
As a result of calculating the reduction rate of the image density after endurance of 5000 sheets with respect to after endurance of 100 sheets in the above environment, a solid black image was output after 5000 sheets, and the result of visual evaluation was evaluated.

The image density reduction rate was determined using the following equation.
(Formula): {(Image density after endurance of 100 sheets) − (Image density after endurance of 5000 sheets)} / (Reflection density after endurance of 100 sheets)
A: The reduction rate was less than 2%, and a solid black image without density unevenness was obtained even after 5000 sheets.
B: The reduction rate was 2% or more and less than 3%, and a solid black image without density unevenness was obtained even after 5000 sheets.
C: The decrease rate is 3% or more and less than 5%, and slight density unevenness is seen after 5000 sheets.
D: The decrease rate becomes 5% or more, or density unevenness is conspicuous after 5000 sheets.

<Evaluation of electrification>
The chargeability was evaluated using the triboelectric charge amount of the toner. Hereinafter, a method for measuring the triboelectric charge amount of the toner will be described.
First, a predetermined carrier (spherical carrier N-01 with a surface treatment of the Japan Imaging Society standard carrier ferrite core) and toner are put in a plastic bottle with a lid, and a shaker (YS-LD, manufactured by Yayoi Co., Ltd.) Shake for 1 minute at a speed of 4 reciprocations per second to charge the developer composed of toner and carrier. Next, the triboelectric charge amount is measured in the apparatus for measuring the triboelectric charge amount shown in FIG. In FIG. 2, about 0.5 to 1.5 g of the developer described above is put in a metal measuring container 2 having a 500 mesh screen 3 at the bottom, and a metal lid 4 is formed. The total mass of the measurement container 2 at this time is weighed and is defined as W1 (g). Next, in the suction machine 1 (at least the part in contact with the measurement container 2) is sucked from the suction port 7 and the air volume control valve 6 is adjusted so that the pressure of the vacuum gauge 5 is 250 mmAq. In this state, the toner is removed by suction for 2 minutes. The potential of the electrometer 9 at this time is set to V (volt). Here, 8 is a capacitor, and the capacity is C (mF). Moreover, the mass of the whole measurement container after suction is weighed and is defined as W2 (g). The triboelectric charge amount (mC / kg) of this sample is calculated as follows.
Sample triboelectric charge (mC / kg) = C × V / (W1-W2)
In the present invention, the initial triboelectric charge amount (Q1) in a normal temperature and normal humidity environment (23 ° C./60% RH).
) And the triboelectric charge amount (Q2) after standing for 1 week, and the charging stability was evaluated based on the rate of change. The evaluation criteria are as follows.
A: Change rate of Q1 → Q2 is 5% or less B: Change rate of Q1 → Q2 is greater than 5, 10% or less C: Change rate of Q1 → Q2 is greater than 10, 15% or less D: Q1 → Q2 The rate of change is greater than 15%

<Low temperature fixability>
Using the above tester, the development contrast was adjusted so that the amount of toner on the paper was 0.35 mg / cm ² in a normal temperature and normal humidity environment (23 ° C./60% RH). A solid 280 mm solid unfixed image was prepared. As the paper, cardboard A4 paper (“Prober Bond paper”: 105 g / m ² , manufactured by Fox River) was used.
The fixing unit of the above tester was modified, and the fixing unit was set in the fixing temperature manually, and in the normal temperature and normal humidity environment (23 ° C / 60%) in the range of 80 ° C to 200 ° C in order. The fixing test was conducted by raising the temperature by 10 ° C.
The image area of the obtained fixed image is rubbed 5 times while applying a load of 4.9 KPa from a soft thin paper (for example, “Dasper”, manufactured by Ozu Sangyo Co., Ltd.), and before and after rubbing. Each subsequent image density was measured, and an image density reduction rate ΔD (%) was calculated by the following equation. The temperature at which ΔD (%) was less than 10% was defined as a fixing start temperature, and was used as a reference for low-temperature fixability.
The image density was measured with an X-Rite color reflection densitometer (Color reflection densitometer X-Rite 404A).
(Formula): ΔD (%) = (Image density before rubbing−Image density after rubbing) × 100 / Image density before rubbing (Evaluation criteria)
A: Fixing start temperature is 120 ° C. or less B: 120 ° C. <fixing start temperature ≦ 140 ° C.
C: 140 ° C. <fixing start temperature ≦ 160 ° C.
D: 160 ° C. <fixing start temperature Note that in the present invention, up to rank B was judged as good low-temperature fixability.

<Evaluation of heat-resistant storage stability of toner>
The heat-resistant storage stability of the toner was evaluated by placing 3 g of toner in a 100 mL plastic cup, leaving it in a thermostatic bath at 50 ° C. (within ± 0.5 ° C.) for 3 days, and then touching it visually and with the belly of a finger.
(Evaluation criteria)
A: No change is observed, and very good heat resistant storage stability is exhibited.
B: Although fluidity | liquidity falls a little, it shows the outstanding heat-resistant storage property.
C: Aggregates are generated, but the heat-resistant storage stability is not a problem in practical use.
D: Aggregates can be pinched and do not collapse easily. Inferior to heat-resistant storage.

<Comparative Example 1>
In the preparation of the oil phase of Example 1, the polyester resin solution-1 was changed to a styrene acrylic resin solution-1, the polyester-1 used for the magnetic dispersion-1 was changed to styrene acrylic-1, and the oil phase 2 Toner 2 was obtained in the same manner except that was prepared. The component composition ratio of Toner 2 is shown in Table 5, the physical properties of Toner 2 are shown in Table 6, and the image evaluation results are shown in Table 7.

<Comparative example 2>
Toner 3 was obtained in the same manner as Example 1 except that resin fine particle dispersion 6 was used instead of resin fine particle dispersion 1. The component composition ratio of Toner 3 is shown in Table 5, the physical properties of Toner 3 are shown in Table 6, and the image evaluation results are shown in Table 7.

<Comparative Example 3>
A toner 4 was obtained in the same manner as in Example 1 except that the following aqueous phase was used. The component composition ratio of Toner 4 is shown in Table 5, the physical properties of Toner 4 are shown in Table 6, and the image evaluation results are shown in Table 7.

(Preparation of inorganic aqueous dispersion medium)
After adding 451 parts by mass of a 0.1 mol / L Na ₃ PO ₄ aqueous solution to 709 parts by mass of ion-exchanged water and heating to 60 ° C., the mixture was stirred at 12,000 rpm with a TK homomixer (manufactured by Special Machine Industries). An inorganic aqueous dispersion medium containing Ca ₃ (PO ₄ ) ₂ was obtained by gradually adding 67.7 parts by mass of 1.0 mol / L CaCl ₂ aqueous solution.

(Preparation of aqueous phase)
・ 200 mass parts of the above inorganic aqueous dispersion medium ・ 50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Kasei Kogyo Co., Ltd.) 4 mass parts ・ 16 mass parts of ethyl acetate The mixture was stirred at 5000 rpm for 1 minute to prepare an aqueous phase.

<Comparative example 4>
In the oil phase preparation of Example 1, polyester resin solution-1 was changed from 80 parts by mass to 122 parts by mass, and magnetic substance dispersion liquid-1 was changed from 75 parts by mass to 40 parts by mass in the same manner except that oil phase 3 was prepared. Toner 5 was obtained. The component composition ratio of the toner 5 is shown in Table 5, the physical properties of the toner 5 are shown in Table 6, and the image evaluation results are shown in Table 7.

<Comparative Example 5>
In the preparation of the oil phase of Example 1, polyester resin solution-1 was changed from 80 parts by mass to 38 parts by mass, and magnetic dispersion liquid-1 was changed from 75 parts by mass to 110 parts by mass in the same manner as in preparing oil phase 4. Toner 6 was obtained. The component composition ratio of the toner 6 is shown in Table 5, the physical properties of the toner 6 are shown in Table 6, and the image evaluation results are shown in Table 7.

<Comparative Example 6>
In the “emulsification and desolvation step” of Example 1, a stirring blade was set in a container, the temperature was raised to 55 ° C. while stirring at 400 rpm, and the solvent was removed over 1 hour in the same manner. Toner 7 was obtained. The component composition ratio of Toner 7 is shown in Table 5, the physical properties of Toner 7 are shown in Table 6, and the image evaluation results are shown in Table 7.

<Example 2>
Toner 8 was obtained in the same manner as Example 1 except that resin fine particle dispersion-2 was used instead of resin fine particle dispersion-1. The component composition ratio of Toner 8 is shown in Table 5, the physical properties of Toner 8 are shown in Table 6, and the image evaluation results are shown in Table 7.

<Example 3>
Toner 9 was obtained in the same manner as in Example 1 except that resin fine particle dispersion-3 was used instead of resin fine particle dispersion-1. The component composition ratio of the toner 9 is shown in Table 5, the physical properties of the toner 9 are shown in Table 6, and the image evaluation results are shown in Table 7.

<Example 4>
In the preparation of the oil phase of Example 1, instead of polyester resin solution-1, polyester resin solution-2 was changed to 38 parts by mass, and 75 parts by mass of magnetic substance dispersion-1 was changed to 110 parts by mass of magnetic substance dispersion-2. Thus, toner 10 was obtained in the same manner except that oil phase 5 was prepared. The component composition ratio of the toner 10 is shown in Table 5, the physical properties of the toner 10 are shown in Table 6, and the image evaluation results are shown in Table 7.

<Example 5>
In the preparation of the oil phase of Example 1, the polyester resin solution-3 was changed to 130 parts by mass instead of the polyester resin solution-1, and 75 parts by mass of the magnetic substance dispersion liquid-1 was changed to 40 parts by mass of the magnetic substance dispersion liquid-3. Thus, the oil phase 6 is prepared, and in the preparation of the aqueous phase, the resin fine particle dispersion 1 is changed from 25 parts by mass to 15 parts by mass (preparing 3.0 parts by mass of resin fine particles with respect to 100 parts by mass of the toner base particles). A toner 11 was obtained in the same manner except that. The component composition ratio of the toner 11 is shown in Table 5, the physical properties of the toner 11 are shown in Table 6, and the image evaluation results are shown in Table 7.

<Example 6>
In the preparation of the oil phase of Example 1, 90 parts by mass of polyester resin solution-1 and 50.0 parts by mass of wax dispersion-1 in 50.0 parts by mass of wax dispersion-3 instead of polyester resin solution-1 In the preparation of the aqueous phase, the resin fine particle dispersion 1 is changed from 25 parts by mass to 35 parts by mass (preparing 7.0 parts by mass of resin fine particles with respect to 100 parts by mass of toner base particles). Toner 12 was obtained in the same manner except that the change was made. The component composition ratio of the toner 12 is shown in Table 5, the physical properties of the toner 12 are shown in Table 6, and the image evaluation results are shown in Table 7.

<Example 7>
In the preparation of the oil phase of Example 1, 90 parts by mass of polyester resin solution-5 and 50.0 parts by mass of wax dispersion-1 in 50.0 parts by mass of wax dispersion-5 instead of polyester resin solution-1 Then, toner 13 was obtained in the same manner except that 75 parts by mass of the magnetic substance dispersion liquid-1 was changed to the magnetic substance dispersion liquid-5 to prepare the oil phase 8. The component composition ratio of the toner 13 is shown in Table 5, the physical properties of the toner 13 are shown in Table 6, and the image evaluation results are shown in Table 7.

<Example 8>
In the preparation of the oil phase of Example 1, the polyester resin solution-4 was used instead of the polyester resin solution-1, the magnetic dispersion liquid-1 was changed to the magnetic dispersion-4, and an oil phase 9 was prepared. Toner 14 was obtained in the same manner except that resin fine particle dispersion-4 was used instead of resin fine particle dispersion-1. The component composition ratio of the toner 14 is shown in Table 5, the physical properties of the toner 14 are shown in Table 6, and the image evaluation results are shown in Table 7.

<Example 9>
In the preparation of the oil phase of Example 1, the polyester resin solution-5 was changed to 95 parts by mass instead of 80 parts by mass of the polyester resin solution-1, and 62.5 parts by mass of the wax dispersion-1 was changed to 31.3. The oil phase 10 was prepared by changing the magnetic material dispersion-1 to the magnetic material dispersion-5, and the resin fine particle dispersion instead of the resin fine particle dispersion-1 in the aqueous phase preparation. A toner 15 was obtained in the same manner except that 65 parts by mass of 5 was used. The component composition ratio of the toner 15 is shown in Table 5, the physical properties of the toner 15 are shown in Table 6, and the image evaluation results are shown in Table 7.

<Example 10>
A toner 16 was obtained in the same manner as in the preparation of the oil phase of Example 1 except that the oil dispersion 11 was prepared by changing the wax dispersion-1 to the wax dispersion-2. The component composition ratio of the toner 16 is shown in Table 5, the physical properties of the toner 16 are shown in Table 6, and the image evaluation results are shown in Table 7.

<Example 11>
A toner 17 was obtained in the same manner as in the preparation of the oil phase of Example 1 except that the oil dispersion 12 was prepared by changing the wax dispersion-1 to the wax dispersion-4. The component composition ratio of the toner 17 is shown in Table 5, the physical properties of the toner 17 are shown in Table 6, and the image evaluation results are shown in Table 7.

It is a flow curve figure based on the data from a flow tester. It is the schematic of the apparatus which measures a triboelectric charge amount.

Explanation of symbols

1 Suction machine (at least the part in contact with the measurement container 2 is an insulator)
2 Metal measuring container 3 500 mesh screen 4 Metal lid 5 Vacuum gauge 6 Air flow control valve 7 Suction port 8 Condenser 9 Electrometer

Claims (13)

A toner containing capsule-type toner particles having a surface layer (B) on the surface of a toner base particle (A) containing at least a resin (a) containing polyester as a main component, a magnetic substance and a wax,
The surface layer (B) contains a resin (b), and the resin (b) is a resin containing a resin selected from a polyester resin (b1), a vinyl resin (b2), or a urethane resin (b3),
The glass transition temperature Tg (a) of the resin (a) and the glass transition temperature Tg (b) of the resin (b) satisfy the relationship of the following formula (1):
Tg (a) <Tg (b) (1)
Magnetization of the toner in an external magnetic field of 79.6 kA / m is 12 Am ² / kg or more and 30 Am ² / kg or less,
A toner having an average adhesion force (F50) of 50 (nN) or less as measured by the centrifugal adhesion force measuring apparatus for toner.   The toner according to claim 1, wherein an average roughness (Ra) of the toner particle surface is 1.0 nm or more and 5.0 nm or less.   The toner according to claim 1, wherein an average circularity of the toner is 0.960 or more and 1.000 or less.   The toner has a weight average particle diameter (D4) of 4.0 μm or more and 9.0 μm or less, and a ratio (D4 / D1) of the weight average particle diameter (D4) to the number average particle diameter (D1) of the toner is 1. The toner according to claim 1, wherein the toner is 25 or less.   The toner according to claim 1, wherein a content of the wax is 5.0% by mass or more and 20.0% by mass or less with respect to the toner.   The toner according to claim 1, wherein the wax is an ester wax.   The toner base particles (A) are one or more monomers selected from a styrene monomer, a nitrogen-containing vinyl monomer, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an acrylate monomer, and a methacrylate ester monomer. 7. The copolymer synthesized using the above and a wax dispersion medium having at least a polyolefin are contained in an amount of 2.5% by mass or more and 10.0% by mass or less. Toner.   The toner according to claim 1, wherein the magnetic substance is contained in an amount of 30.0% by mass to 120.0% by mass with respect to the resin (a).   The toner according to claim 1, wherein the magnetic material is used after being dispersed in an organic medium together with the resin (a).   The toner according to claim 1, wherein the surface layer (B) is 1.0% by mass or more and 15.0% by mass or less based on the toner base particles (A).   The toner according to claim 1, wherein the resin (b) contains a urethane resin (b3).   The said surface layer (B) is formed using the resin microparticles | fine-particles containing the said resin (b) whose number average particle diameters are 30 nm or more and 100 nm or less. Toner.   The toner particles are prepared by dissolving at least the resin (a) containing the polyester as a main component, the magnetic substance and the wax in an organic medium in an aqueous medium in which resin fine particles containing the resin (b) are dispersed. The toner according to claim 1, wherein the toner is obtained by dispersing a solution or dispersion obtained by dispersing, removing the solvent from the obtained dispersion, and drying.

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