JP2009244605A - Toner and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner and an image forming method that implement satisfactory character reproducibility and produce a stably developed image free from quality degradation due to fogs and developing streaks even after a long period of copying or printing in a high temperature and high humidity environment. <P>SOLUTION: The image forming method has a charging step, an exposure step, a step of regulating the toner on a toner carrier with a toner layer regulation member, a developing step of development with the toner, and a transfer step of transferring the toner image to a transfer medium. The toner carrier 2 has a surface layer 3 containing a binding resin and particles 31 and 32. The skewness Rsk of the roughness curve of the surface of the toner carrier is 0.15 to 0.70. The particles have two peaks in a volume size distribution. The toner has toner particles and silica powders. The weight average size D<SB>4</SB>(T) of the toner in the size distribution is 3.0 to 8.0 μm. At least one kind of the silica powders is hydrophobized with silicone oil. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner used in a recording method such as an electrophotographic method, an electrostatic recording method, and a toner jet method, and an image forming method using the toner.

  In recent years, with the development of computers and multimedia, there is a demand for means for outputting high-definition images in a wide range of fields from offices to homes. For example, users who mainly output photographs and graphic patterns demand image quality characteristics without graininess, and users who mainly output text documents demand image quality characteristics with high character reproducibility. Furthermore, heavy users demand high durability without deterioration in image quality even when a large number of copies or prints are made.

  In order to improve the granularity and the character reproducibility, it is one of effective means to reduce the average particle diameter of the toner (for example, see Patent Document 1).

  On the other hand, the improvement of the characteristics of the toner carrier is one means for achieving high durability without deterioration in image quality. The properties required for the toner carrier generally include (1) uniform and high charge imparting property to the toner and (2) uniform toner transportability. In order to improve these characteristics, it is effective to have an elastic layer on the outer periphery of the shaft core of the toner carrier, and further to have a resin surface layer on the outer periphery, and to disperse the fine particles in the resin surface layer. It is disclosed that there is (see, for example, Patent Documents 2 to 5). In particular, it has been disclosed that the effect of improving the characteristics is remarkable by incorporating large and small particles in the resin surface layer of the toner carrier (see, for example, Patent Documents 6 and 7).

  However, when the particle size of the toner is reduced, the number of contact / collision between the toners or between the toner and the toner carrier or the toner regulating member increases, so that the toner easily deteriorates. Image defects such as fogging and development streaks are likely to occur. Specifically, fog is generated when the toner charge amount is reduced on the surface of the toner carrying member, resulting in a decrease in the charge amount of the toner. The development streaks are generated when toner fusion partially occurs on the surface of the toner regulating member and the amount of toner coating on the toner carrying member becomes non-uniform. In particular, toner deterioration is promoted in a severe environment such as high temperature and high humidity, and these image defects are remarkably likely to occur.

  Therefore, when reducing the particle size of the toner in order to improve the graininess and character reproducibility, in order to suppress fogging and development streaks that are easily induced by the toner, each of the toner and the toner carrier, or those Further ingenuity is necessary for the combination of.

Japanese Patent Laid-Open No. 08-227171 JP-A-11-212354 JP 2003-263019 A JP 2004-191561 A JP 2005-115265 A Japanese Patent No. 02940071 JP-A-2005-258201

  An object of the present invention is to provide a toner having excellent character reproducibility and capable of obtaining an image having a stable developability without deterioration in image quality due to fogging or development streaks even by copying or printing for a long period of time under high temperature and high humidity. It is to provide a forming method.

  The present invention for solving the above problems is as follows.

<1> A charging step of charging the electrostatic latent image carrier with charging means, an exposure step of exposing the charged electrostatic latent image carrier to form an electrostatic latent image, and a toner carrier with a toner layer regulating member A step of regulating the toner above, a development step of developing the electrostatic latent image carrier with the toner on the toner carrier, and a transfer step of transferring the toner image to the transfer material with or without the intermediate transfer member. In an image forming method having
The toner carrier is a toner carrier having an elastic layer on the outer periphery of the shaft core and a surface layer containing at least a binder resin and particles on the outer periphery.
The degree of distortion Rsk of the roughness curve of the toner carrier surface is 0.15 to 0.70,
The particles have two peaks in the volume particle size distribution, and each peak position is D _P (A) [μm] and D _P (B) [μm], and the peak heights are D _H (A) and D _H ( B) and the weight average particle diameter D ₄ (T) of the toner,
2.0 ≦ D _P (B) −D _P (A) ≦ 12.0
3.0 ≦ D ₄ (T) <D _P (A) <D _P (B) ≦ 30.0
1.0 ≦ D _H (A) / D _H (B) ≦ 8.0
And
The toner has toner particles containing at least a binder resin, a colorant, and a wax component, and silica fine powder,
In the particle size distribution of the toner, the weight average particle diameter D ₄ (T) is 3.0 to 8.0 μm,
At least one of the silica fine powders is a silica fine powder hydrophobized with silicone oil,
The amount of the silica fine powder with respect to 100 parts by mass of toner particles is 0.05 to 2.5 parts by mass,
The silica fine powder has a BET of 40 to 150 m ² / g,
When the amount of carbon of the silica fine powder is C amount (mass%) and the BET before the hydrophobic treatment of the silica fine powder is the base BET (m ² / g), the C amount / base BET = 0.020 to An image forming method, wherein the image forming method is 0.060.

<2> The image forming method according to <1>, wherein the silica fine powder has a BET of 50 to 90 m ² / g.

<3> When the amount of carbon of the silica fine powder is C amount (mass%) and the BET before the hydrophobic treatment of the silica fine powder is the base BET (m ² / g), the amount of C / base BET = 0 The image forming method according to <1> or <2>, wherein the image forming method is from .030 to 0.060.

<4> When the amount of carbon of the silica fine powder is C amount (mass%) and the BET before the hydrophobic treatment of the silica fine powder is the base BET (m ² / g), the amount of C / base BET = 0 The image forming method according to any one of <1> to <3>, wherein the image forming method is 0.035 to 0.055.

<5> The image according to any one of <1> to <4>, wherein the toner has a viscosity at 100 ° C. of 1.5 × 10 ^{4 to} 5.5 × 10 ⁴ Pa · s. Forming method.

<6> In the toner carrier surface layer, when the blending amount of the particles with respect to 100 parts by mass of the binder resin is C [parts by mass] and the thickness of the surface layer is t [μm],
15.0 ≦ C ≦ 40.0
8.0 ≦ t ≦ 15.0
The image forming method according to any one of <1> to <5>, wherein:

  <7> The image forming method according to any one of <1> to <6>, wherein the toner carrier has a surface hardness of 30.0 to 38.0.

  <8> The particles on the surface layer of the toner carrier are composed of A and B, and the mixing mass ratio of A and B is A: B = 60: 40 to 90:10 <1> to < 7> The image forming method as described in any one of 7>.

  <9> Any one of <1> to <8>, wherein the particles of the toner carrier surface layer are resin particles, and the binder resin and resin particles of the toner carrier surface layer are urethane resins The image forming method according to one item.

<10> The particles of the toner carrier surface layer are composed of A and B, and the weight average particle diameter D ₄ (A) [μm] of A is 6.0 ≦ D ₄ (A) ≦ 10.0. The image forming method according to any one of <1> to <9>, wherein:

<11> The particles of the toner carrier surface layer are composed of A and B, and the weight average particle diameter D ₄ (B) [μm] of B is 12.0 ≦ D ₄ (B) ≦ 20.0. The image forming method according to any one of <1> to <10>, wherein:

<12> The particles of the surface layer of the toner carrier are composed of A and B, and the weight average particle diameter D ₄ (A) [μm] of A and the weight average particle diameter D ₄ (B) [μm] of B are The image forming method according to any one of <1> to <11>, wherein D ₄ (B) −D ₄ (A) ≧ 4.0.

<13> A charging step of charging the electrostatic latent image carrier with a charging unit, an exposure step of exposing the charged electrostatic latent image carrier to form an electrostatic latent image, and a toner carrier with a toner layer regulating member A step of regulating the toner above, a development step of developing the electrostatic latent image carrier with the toner on the toner carrier, and a transfer step of transferring the toner image to the transfer material with or without the intermediate transfer member. A toner used in an image forming method comprising:
The toner carrier is a toner carrier having an elastic layer on the outer periphery of the shaft core and a surface layer containing at least a binder resin and particles on the outer periphery.
The degree of distortion Rsk of the roughness curve of the toner carrier surface is 0.15 to 0.70,
The particles have two peaks in the volume particle size distribution, and each peak position is D _P (A) [μm] and D _P (B) [μm], and the peak heights are D _H (A) and D _H ( B) and the weight average particle diameter D ₄ (T) of the toner,
2.0 ≦ D _P (B) −D _P (A) ≦ 12.0
3.0 ≦ D ₄ (T) <D _P (A) <D _P (B) ≦ 30.0
1.0 ≦ D _H (A) / D _H (B) ≦ 8.0
And
The toner has toner particles containing at least a binder resin, a colorant, and a wax component, and silica fine powder,
In the particle size distribution of the toner, the weight average particle diameter D ₄ (T) is 3.0 to 8.0 μm,
At least one of the silica fine powders is a silica fine powder hydrophobized with silicone oil,
The amount of the silica fine powder with respect to 100 parts by mass of toner particles is 0.05 to 2.5 parts by mass,
The silica fine powder has a BET of 40 to 150 m ² / g,
When the amount of carbon of the silica fine powder is C amount (mass%) and the BET before the hydrophobic treatment of the silica fine powder is the base BET (m ² / g), the C amount / base BET = 0.020 to A toner characterized by 0.060.

<14> The toner according to <13>, wherein the silica fine powder has a BET of 50 to 90 m ² / g.

<15> When the amount of carbon of the silica fine powder is C amount (mass%) and the BET before the hydrophobic treatment of the silica fine powder is the base BET (m ² / g), the amount of C / base BET = 0 The toner according to <13> or <14>, wherein the toner is from .030 to 0.060.

<16> When the amount of carbon of the silica fine powder is C amount (mass%) and the BET before the silica fine powder is hydrophobized is the base BET (m ² / g), the amount of C / base BET = 0 The toner according to any one of <13> to <15>, which is 0.035 to 0.055.

<17> The toner according to any one of <13> to <16>, wherein the toner has a viscosity at 100 ° C. of 1.5 × 10 ^{4 to} 5.5 × 10 ⁴ Pa · s. .

<18> In the toner carrier surface layer, when the blending amount of the particles with respect to 100 parts by mass of the binder resin is C [parts by mass] and the thickness of the surface layer is t [μm],
15.0 ≦ C ≦ 40.0
8.0 ≦ t ≦ 15.0
The toner according to any one of <13> to <17>, wherein

  <19> The toner according to any one of <13> to <18>, wherein the toner carrier has a surface hardness of 30.0 to 38.0.

  <20> The particles on the surface layer of the toner carrier are composed of A and B, and the mixing mass ratio of A and B is A: B = 60: 40 to 90:10. The toner according to any one of 19>.

  <21> Any one of <13> to <20>, wherein the particles of the toner carrier surface layer are resin particles, and the binder resin and resin particles of the toner carrier surface layer are urethane resins The toner according to one item.

<22> The particles of the toner carrier surface layer are composed of A and B, and the weight average particle diameter D ₄ (A) [μm] of A is 6.0 ≦ D ₄ (A) ≦ 10.0. The toner according to any one of <13> to <21>, wherein:

<23> The particles of the surface layer of the toner carrier are composed of A and B, and the weight average particle diameter D ₄ (B) [μm] of B is 12.0 ≦ D ₄ (B) ≦ 20.0. The toner according to any one of <13> to <22>, wherein

<24> The particles of the surface layer of the toner carrier are composed of A and B, and the weight average particle diameter D ₄ (A) [μm] of A and the weight average particle diameter D ₄ (B) [μm] of B are The toner according to any one of <13> to <23>, wherein D ₄ (B) −D ₄ (A) ≧ 4.0.

  According to the present invention, when the particle size of the toner is reduced in order to improve the granularity and character reproducibility, the degree of distortion Rsk of the roughness curve of the surface roughness of the toner carrier, and the surface of the toner carrier By controlling the particle size distribution of the layer particles to an appropriate range and adjusting the silica fine powder in the toner to the optimum processing conditions, fogging and development streaks can be achieved even during long-term copying or printing under high temperature and high humidity. Thus, it is possible to provide an image with stable developability without image quality degradation.

The image forming method of the present invention comprises a charging step of charging an electrostatic latent image carrier by a charging means, an exposure step of exposing the charged electrostatic latent image carrier to form an electrostatic latent image, toner layer regulation A step of regulating the toner on the toner carrier with a member, a development step of developing the electrostatic latent image carrier with the toner on the toner carrier, and a toner image to a transfer material with or without an intermediate transfer member In the image forming method having a transfer step of transferring,
The toner carrier is a toner carrier having an elastic layer on the outer periphery of the shaft core and a surface layer containing at least a binder resin and particles on the outer periphery.
The degree of distortion Rsk of the roughness curve of the toner carrier surface is 0.15 to 0.70,
The particles have two peaks in the volume particle size distribution, and each peak position is D _P (A) [μm] and D _P (B) [μm], and the peak heights are D _H (A) and D _H ( B) and the weight average particle diameter D ₄ (T) of the toner,
2.0 ≦ D _P (B) −D _P (A) ≦ 12.0
3.0 ≦ D ₄ (T) <D _P (A) <D _P (B) ≦ 30.0
1.0 ≦ D _H (A) / D _H (B) ≦ 8.0
And
The toner has toner particles containing at least a binder resin, a colorant, and a wax component, and silica fine powder,
In the particle size distribution of the toner, the weight average particle diameter D ₄ (T) is 3.0 to 8.0 μm,
At least one of the silica fine powders is a silica fine powder hydrophobized with silicone oil,
The amount of the silica fine powder with respect to 100 parts by mass of toner particles is 0.05 to 2.5 parts by mass,
The silica fine powder has a BET of 40 to 150 m ² / g,
When the amount of carbon of the silica fine powder is C amount (mass%) and the BET before the hydrophobic treatment of the silica fine powder is the base BET (m ² / g), the C amount / base BET = 0.020 to It is characterized by 0.060.

The toner of the present invention includes a charging step of charging the electrostatic latent image carrier with a charging means, an exposure step of exposing the charged electrostatic latent image carrier to form an electrostatic latent image, and toner layer regulation. A step of regulating the toner on the toner carrier with a member, a development step of developing the electrostatic latent image carrier with the toner on the toner carrier, and a toner image to a transfer material with or without an intermediate transfer member A toner used in an image forming method having a transfer step of transferring,
The toner carrier is a toner carrier having an elastic layer on the outer periphery of the shaft core and a surface layer containing at least a binder resin and particles on the outer periphery.
The degree of distortion Rsk of the roughness curve of the toner carrier surface is 0.15 to 0.70,
The particles have two peaks in the volume particle size distribution, and each peak position is D _P (A) [μm] and D _P (B) [μm], and the peak heights are D _H (A) and D _H ( B) and the weight average particle diameter D ₄ (T) of the toner,
2.0 ≦ D _P (B) −D _P (A) ≦ 12.0
3.0 ≦ D ₄ (T) <D _P (A) <D _P (B) ≦ 30.0
1.0 ≦ D _H (A) / D _H (B) ≦ 8.0
And
The toner has toner particles containing at least a binder resin, a colorant, and a release agent, and silica fine powder,
In the particle size distribution of the toner, the weight average particle diameter D ₄ (T) is 3.0 to 8.0 μm,
At least one of the silica fine powders is a silica fine powder hydrophobized with silicone oil,
The amount of the silica fine powder with respect to 100 parts by mass of toner particles is 0.05 to 2.5 parts by mass,
The silica fine powder has a BET of 40 to 150 m ² / g,
When the amount of carbon of the silica fine powder is C amount (mass%) and the BET before the hydrophobic treatment of the silica fine powder is the base BET (m ² / g), the C amount / base BET = 0.020 to It is characterized by 0.060.

  In general, when the toner has a smaller particle size, the character reproducibility is improved, but the number of contacts / collisions between the toners or between the toner and the toner carrier or the toner regulating member increases, and the toner tends to deteriorate. As a result, the toner carrier and the toner regulating member are contaminated with toner, and image defects such as development streaks and fog are likely to occur. In particular, in an environment where the charge amount of toner that is copied or printed over a long period of time under high temperature and high humidity is likely to decrease, image adverse effects such as development streaks and fog are likely to be further deteriorated.

  As a result of intensive studies by the present inventors, the degree of contact between the toner and the toner carrier or the toner regulating member is greatly involved in development streaks and fog, and the charging stability of the toner is effective particularly under high temperature and high humidity. It became clear that

  In order to improve the development streak associated with the reduction in the toner particle size, it is necessary to reduce the number of contact points between the toner carrier and the toner regulating member and to suppress the toner fusion to the toner regulating member. That is, it is necessary to increase the degree of distortion Rsk of the roughness curve of the surface roughness of the toner carrier and to maintain the toner charge amount high so that the toner does not adhere to the toner regulating member.

  On the other hand, in order to improve the fog caused by the reduction in the particle size of the toner, it is necessary not to cause toner retention on the toner carrier. In other words, the toner carrier has a surface roughness roughness curve distortion Rsk close to 0 so that the surface can be easily scraped off by a toner regulating member, and the toner maintains a high toner charge amount and reduces selective developability. There is a need.

  Here, the skewness of the roughness curve of the surface roughness of the toner carrier will be described with reference to FIGS. FIG. 2 is a schematic sectional view of the vicinity of the surface of the toner carrier. A surface layer 3 is disposed on the outer periphery of the elastic layer 2. In the surface layer 3, particles 31 having a relatively large particle diameter and particles 32 having a relatively small particle diameter are dispersed and contained. FIG. 3 is a schematic diagram of the roughness curve of the surface roughness of the toner carrier. The horizontal direction in the figure indicates the axial direction of the toner carrier surface, and the vertical direction in the figure indicates the roughness shape of the toner carrier surface. .

  As shown in FIG. 2A, when a small amount of large particles are contained in the surface layer of the toner carrier, the roughness curve in the surface roughness of the toner carrier has a profile as shown in FIG. Thus, the value of the skewness Rsk of the roughness curve becomes larger than 0. In this case, the number of contact points between the toner regulating member and the surface of the toner carrier is reduced, and the development streak is improved. However, in the non-existing part of the particle, the gap (G in FIG. 2) formed by the toner carrier and the toner regulating member becomes large and wide. Since it becomes easy to stay, fog will deteriorate.

  On the other hand, as shown in FIG. 2B, when a large amount of particles are contained in the surface layer of the toner carrier, the roughness curve in the surface roughness of the toner carrier is as shown in FIG. Profile, and the value of the skewness Rsk of the roughness curve is approximately zero. In this case, retention of toner on the toner carrier can be prevented, and fogging is improved. However, the number of contact points between the toner carrier and the toner regulating member increases, and the development streak deteriorates.

  That is, it is difficult to improve both the fog and the development streak at the same time by controlling only the addition amount of the particles and controlling the profile of the toner carrier surface indicated by Rsk.

  Therefore, as shown in FIG. 2C, the surface layer has a structure in which particles having a relatively large specific particle size range and particles having a relatively small specific particle size range are contained at the same time, and is represented by Rsk. It was found that by controlling the profile of the surface of the toner carrier, both fog and development streak can be improved at the same time.

  As shown in FIG. 1, the toner carrier used in the present invention has an elastic layer 2 on the outer periphery of the shaft core 1, and has a surface layer 3 containing at least a binder resin and particles on the outer periphery. Yes. The toner carrier, as shown in FIG. 2C, simultaneously contains particles having a relatively large specific particle size range and particles having a relatively small specific particle size range in the surface layer. The skewness Rsk of the roughness curve of the surface roughness of the toner carrier is 0.15 to 0.70.

Further, the particles in the toner carrier surface layer have two peaks in the volume particle size distribution. The respective peak positions are D _P (A) [μm] and D _P (B) [μm], and the peak height is D _H (A) and D _H (B), and the weight average particle diameter D ₄ (T) of the toner,
2.0 ≦ D _P (B) −D _P (A) ≦ 12.0 [Formula 1]
3.0 ≦ D ₄ (T) <D _P (A) <D _P (B) ≦ 30.0 [Formula 2]
1.0 ≦ D _H (A) / D _H (B) ≦ 8.0 [Formula 3]
The following relational expression holds. FIG. 4 shows the relationship between the weight average particle diameter D ₄ (T) of the toner of the present invention and the volume particle size distribution of the particles in the toner carrier surface layer.

  [Equation 1] and [Equation 2] show the relationship between the particle size range of the large and small particles in the surface layer of the toner carrier as shown in FIG. [Equation 3] shows the quantitative relationship between the large and small particles in the toner carrier surface layer. The distortion degree Rsk of the roughness curve of the surface roughness of the toner carrier at this time is 0.15 to 0.70, preferably 0.30 to 0.60. When this relational expression is satisfied, the number of contact points between the toner carrying member and the toner regulating member is reduced, so that toner fusion to the toner regulating member can be suppressed and development streaks can be improved. At the same time, the non-existing portion of the large particle on the surface of the toner carrier is also finely roughened by the small particle, so that toner retention can be suppressed and fogging can be improved. If the degree of distortion Rsk of the roughness curve of the surface roughness of the toner carrier is less than 0.15, the number of contact points between the toner carrier and the toner regulating member increases, and development streaks are likely to occur. On the other hand, if it is larger than 0.70, the gap indicated by G in FIG. 2C becomes excessively large, and the toner tends to stay.

In [Formula 1], a more preferable range is 4.0 ≦ D _P (B) −D _P (A) ≦ 10.0. When D _P (B) −D _P (A) is smaller than 2.0, the gap indicated by G in FIG. 2C is too small, and the toner is coated on the small particles on the surface layer of the toner carrier. However, as with the large particles, the toner is rubbed by the toner restricting member to cause toner deterioration. When D _P (B) −D _P (A) is greater than 12.0, the toner tends to stay in the gap indicated by G in FIG.

In [Formula 2], a more preferable range is 3.0 ≦ D ₄ (T) <D _P (A) <D _P (B) ≦ 20.0. When D ₄ (T) ≧ D _P (A), the effect of fine roughening due to small particles on the surface layer of the toner carrier is lost, and it is difficult to suppress toner retention. If D _P (B) is greater than 30.0, the toner tends to stay in the gap indicated by G in FIG.

In [Formula 3], a more preferable range is 2.0 ≦ D _H (A) / D _H (B) ≦ 6.0. When D _H (A) / D _H (B) is smaller than 1.0, that is, when the ratio of large particles in the surface layer of the toner carrier increases, the number of contact points between the toner carrier and the toner regulating member increases. This induces toner fusion to the toner regulating member. When D _H (A) / D _H (B) is greater than 8.0, that is, when the ratio of large particles in the surface layer of the toner carrier is significantly lower, the gap indicated by G in FIG. And the toner tends to stay.

  Furthermore, in the present invention, by providing the toner with the above characteristics, the above improvement effect can be further exerted in a severe environment such as high temperature and high humidity.

The toner of the present invention has a weight average particle diameter D ₄ (T) of 3.0 to 8.0 μm, preferably 3.5 to 7.0 μm. If it is smaller than 3.0 μm, even in the toner carrier used in the present invention, the toner tends to stay in the absence of large particles on the surface layer of the toner carrier. When it is larger than 8.0 μm, the character reproducibility is remarkably deteriorated.

  The toner of the present invention has a silica fine powder, and at least one of the silica fine powders is a silica fine powder hydrophobized with silicone oil, and the amount of the silica fine powder with respect to 100 parts by mass of toner particles is 0. .05 to 2.5 parts by mass. The silica fine powder is externally added to the toner particles to improve the toner fluidity and to make the toner particles uniform. The silica fine powder is hydrophobized with silicone oil to adjust the charge amount of the toner. Improvement of environmental stability, improvement of characteristics under high temperature and high humidity environment can be achieved, and selective developability can be reduced. If the amount of the silica fine powder is less than 0.05 parts by mass with respect to 100 parts by mass of the toner particles, the above effect cannot be exhibited sufficiently. When the amount is more than 2.5 parts by mass, excessive silica fine powder is released from the toner particles and contaminates the members in the developing device.

The BET of the fine silica powder used in the present invention is 40 to 150 m ² / g, preferably 50 to 90 m ² / g. If the BET of the silica fine powder is less than 40 m ² / g, the toner fluidity cannot be sufficiently obtained. If it is larger than 150 m ² / g, the number of particles of the silica fine powder itself increases, so the number of particles of the silica fine powder that can be released from the toner particles also increases, and the contamination in the developing unit and the development induced thereby. Streaks are significantly worsened. In particular, in an environment where the chargeability of toner particles is likely to be lowered, such as in a high-temperature and high-humidity environment, the silica fine powder that has electrostatically adhered to the toner particles is likely to be released. As a result, the development lines induced are further deteriorated.

In addition, the silica fine powder used in the present invention has a carbon amount of the silica fine powder of C amount (mass%), and the BET before the hydrophobic treatment of the silica fine powder is the original BET (m ² / g). , C amount / base BET = 0.020 to 0.060, preferably 0.030 to 0.060, more preferably 0.035 to 0.055. The amount of carbon (C amount) of the silica fine powder represents the amount of silicone oil treated, and the amount of C / base BET = 0.020 to 0.060 is the silica fine powder silicone oil used in the present invention. This indicates an appropriate range of the surface treatment amount. If the amount of carbon (C amount) in the silica fine powder is larger than the appropriate amount relative to the base BET, the environmental stability is improved and the characteristics are improved in a high-temperature and high-humidity environment. Contamination of the inner member deteriorates and the fluidity of the toner decreases. On the other hand, if the amount of carbon (C amount) of the silica fine powder is less than that of the base BET, the chargeability in a high temperature and high humidity environment is significantly deteriorated. In the present invention, if the amount of C / base BET is less than 0.020, the chargeability cannot be sufficiently maintained in a high temperature and high humidity environment. As a result, the toner easily adheres to the toner regulating member and induces development streaks, and the selective development is likely to occur, so that the toner on the toner carrier is easily retained and fogged. If the amount of C / base BET is larger than 0.060, excessive silicone oil will deteriorate the contamination of the members in the developing device or decrease the fluidity of the toner.

The toner of the present invention preferably has a toner viscosity at 100 ° C. (hereinafter also simply referred to as 100 ° C. viscosity) of 1.5 × 10 ^{4 to} 5.5 × 10 ⁴ Pa · s. If the viscosity at 100 ° C. is smaller than 1.5 × 10 ⁴ Pa · s, it is not preferable because the adhesion of the toner to the toner regulating member tends to deteriorate. When the viscosity at 100 ° C. is larger than 5.5 × 10 ⁴ Pa · s, particularly when the binder resin and resin particles of the surface layer of the toner carrier of the present invention are urethane resins, the surface layer of the toner carrier is a toner layer. This is not preferable because the possibility of deterioration due to friction increases.

  The viscosity of the toner at 100 ° C. by the flow tester heating method can satisfy the above range by adjusting the production conditions of the toner particles, the composition of the binder resin, and the like.

The toner carrier used in the present invention has a surface layer of the toner carrier in which the amount of the particles is 100 [parts by mass] with respect to 100 parts by mass of the binder resin and the thickness of the surface layer is t [μm]. ,
15.0 ≦ C ≦ 40.0
8.0 ≦ t ≦ 15.0
It is preferable that the degree of distortion Rsk of the roughness curve of the surface roughness of the toner carrier can be controlled to 0.15 to 0.70. Furthermore,
25.0 ≦ C ≦ 35.0
9.0 ≦ t ≦ 12.0
It is more preferable that the degree of distortion Rsk of the roughness curve of the surface roughness of the toner carrier can be controlled to a more preferable range of 0.30 to 0.60.

  The toner carrier used in the present invention preferably has a surface hardness of the toner carrier of 30.0 to 38.0. When the surface hardness of the toner carrier is 30.0 to 38.0, that is, the surface hardness is moderately reduced, damage to the toner from the toner carrier is reduced, and a decrease in charge amount due to toner deterioration can be suppressed.

In the toner carrier used in the present invention, the particles on the surface layer of the toner carrier are preferably composed of particles A and particles B, and the mixing mass ratio of particles A and particles B is preferably 60:40 to 90:10. More preferably, it is 70:30 to 90:10. When the mixing mass ratio of the particles A and the particles B is 60:40 to 90:10, the particles in the surface layer of the toner carrier have two peaks in the volume particle size distribution, and the peak height D _H (A) and D _H (B) are preferred because D _H (A) / D _H (B) can be controlled within the above range.

  In the toner carrier used in the present invention, the particles of the surface layer of the toner carrier are preferably resin particles, and the binder resin and resin particles of the surface layer of the toner carrier are preferably urethane resins.

  The binder resin for the surface layer of the toner carrier is preferably a polyurethane resin from the viewpoint of toner chargeability and wear resistance, and is particularly preferably a polyether polyurethane resin that can reduce the hardness of the film and has high toner chargeability.

  The polyether polyurethane resin can be obtained by a reaction between a known polyether polyol and an isocyanate compound. Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. In addition, these polyol components may be prepolymers that are chain-extended with an isocyanate such as 2,4-tolylene diisocyanate (TDI), 1,4 diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI) as necessary.

  Isocyanate compounds to be reacted with these polyol components are not particularly limited, but aliphatic polyisocyanates such as ethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), cyclohexane 1,3 -Arocyclic polyisocyanates such as diisocyanate, cyclohexane 1,4-diisocyanate, aromatic polyisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and these A modified product, a copolymer, or a block body thereof can be used.

  The particles in the surface layer of the toner carrier are preferably urethane spherical particles in view of adhesion to the binder resin and charge imparting property to the toner. Further, as described above, from the viewpoint of fogging and development streaks, the particles must satisfy the above relational expressions [1] to [3] in the volume particle size distribution. If these characteristics are satisfied, the contained particles may be used alone or in combination. Further, the particles may be classified in order to control the volume particle size distribution of the particles. The classification method is not particularly limited, and usual classification methods such as a sieving machine, a gravity classifier, a centrifugal classifier, and an inertia classifier can be used. However, productivity is good and the classification point can be easily changed. Since it can do, it is preferable to use wind classifiers, such as a gravity classifier, a centrifugal classifier, and an inertia classifier.

In the toner carrier used in the present invention, from the viewpoint of satisfying the following formulas [1] and [2], the particles of the surface layer of the toner carrier are composed of particles A and B, and the weight average particle diameter D ₄ ( A) [μm] is 6.0 ≦ D ₄ (A) ≦ 10.0 and / or the weight average particle diameter D ₄ (B) of the particle B is 12.0 ≦ D ₄ (B) ≦ 20.0 is preferred.
2.0 ≦ D _P (B) −D _P (A) ≦ 12.0 [Formula 1]
3.0 ≦ D ₄ (T) <D _P (A) <D _P (B) ≦ 30.0 [Formula 2]

Furthermore, the toner carrier used in the present invention has a weight average particle diameter of particles A and B of the toner carrier surface layer from the viewpoint of satisfying the following formula [1]: D ₄ (B) −D ₄ (A ) ≧ 4.0 is preferable.
2.0 ≦ D _P (B) −D _P (A) ≦ 12.0 [Formula 1]

When D ₄ (B) −D ₄ (A) <4.0, the gap indicated by G in FIG. 2C is too small, and the toner is coated on the small particles on the surface of the toner carrier. As with the large particles, the toner is rubbed by the toner regulating member to cause toner deterioration, which is not preferable.

  The toner particles used in the present invention may be produced by any method, but a production method of granulating in an aqueous medium such as a suspension polymerization method, an emulsion polymerization method, or a suspension granulation method. It is preferable that it is manufactured by. In the case of toner particles produced by a general pulverization method, it is very difficult to add a large amount of the wax component to the toner particles. In the production method of granulating toner particles in an aqueous medium, even if a large amount of wax component is added to the toner particles, the wax component does not exist on the surface of the toner particles and can be encapsulated. Among these production methods, the suspension polymerization method is one of the most preferred production methods from the viewpoint of long-term development stability due to the inclusion of the wax component in the toner particles and the production cost such that no solvent is used. That is, the toner particles are obtained by dispersing a polymerizable monomer composition containing at least a polymerizable monomer, a colorant and a wax component in an aqueous medium, granulating the polymerized monomer. The toner particles obtained by the above are preferable.

  Hereinafter, the most suitable suspension polymerization method for obtaining the toner particles used in the present invention will be exemplified and the production method of the toner particles will be described. A polymerizable monomer, a colorant, a wax component and other additives as necessary are uniformly dissolved or dispersed by a disperser such as a homogenizer, a ball mill, a colloid mill, or an ultrasonic disperser, and polymerized therein. An initiator is dissolved to prepare a polymerizable monomer composition. Next, toner particles are produced by dispersing the polymerizable monomer composition in an aqueous medium containing a dispersion stabilizer, granulating, and polymerizing the polymerizable monomer. The polymerization initiator may be added simultaneously with the addition of other additives to the polymerizable monomer, or may be mixed immediately before being suspended in the aqueous medium. Also, a polymerization initiator dissolved in a polymerizable monomer or solvent can be added immediately after granulation and before starting the polymerization reaction.

  Examples of the binder resin constituting the toner include commonly used styrene-acrylic copolymers, styrene-methacrylic copolymers, epoxy resins, and styrene-butadiene copolymers. Therefore, as the polymerizable monomer, a vinyl polymerizable monomer capable of radical polymerization can be used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

  Examples of the polymerizable monomer include the following. Styrene; Styrenic monomers such as o- (m-, p-) methylstyrene, m- (p-) ethylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, Propyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, dodecyl acrylate, dodecyl methacrylate, stearyl acrylate, stearyl methacrylate, behenyl acrylate, behenyl methacrylate, 2-ethylhexyl acrylate, Acrylic acid ester monomers such as 2-ethylhexyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethylaminoethyl methacrylate, Ether-based monomers; butadiene, isoprene, cyclohexene, acrylonitrile, methacrylonitrile, acrylic acid amide, such as ene-based monomers methacrylamide.

  These polymerizable monomers are used alone or in general, and the theoretical glass transition temperature (Tg) described in publication polymer handbook 2nd edition III-p139-192 (John Wiley & Sons) is 40 ° C. or higher. A polymerizable monomer is appropriately mixed and used so as to exhibit 75 ° C. or lower. If the theoretical glass transition temperature is less than 40 ° C., problems are likely to occur from the viewpoint of storage stability and durability stability of the toner, while if it exceeds 75 ° C., the fixability is lowered.

  In the case of producing toner particles for use in the toner of the present invention, a low molecular weight polymer may be added. The low molecular weight polymer can be added to the polymerizable monomer composition when toner particles are produced by suspension polymerization. As the low molecular weight polymer, the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is in the range of 2,000 to 5,000, and Mw / Mn is less than 4.5, preferably Is preferably less than 3.0.

  Examples of the low molecular weight polymer include low molecular weight polystyrene, low molecular weight styrene-acrylic acid ester copolymer, and low molecular weight styrene-acrylic copolymer.

  A preferable addition amount of the low molecular weight polymer is 1 part by mass or more and 50 parts by mass or less, and more preferably 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.

  In the present invention, a polar resin having a carboxyl group such as a polyester resin or a polycarbonate resin can be used in combination with the above-described binder resin.

  For example, in the case of directly producing toner particles by a suspension polymerization method, when a polar resin is added during the polymerization reaction from the dispersion step to the polymerization step, a polymerizable monomer composition that becomes toner particles and an aqueous dispersion medium are exhibited. Depending on the polarity balance, the presence state of the polar resin can be controlled so that the added polar resin forms a thin layer on the surface of the toner particles or exists with a gradient from the toner particle surface toward the center. .

  A preferable addition amount of the polar resin is 1 part by mass or more and 25 parts by mass or less, and more preferably 2 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the binder resin. If the amount is less than 1 part by mass, the presence state of the polar resin in the toner particles tends to be non-uniform. On the other hand, if it exceeds 25 parts by mass, the layer of the polar resin formed on the surface of the toner particles becomes thick.

  Examples of the polar resin used in the present invention include polyester resins, epoxy resins, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, and styrene-maleic acid copolymers. In particular, as a polar resin, a polyester resin having a molecular weight of 3,000 to 10,000 and having a main peak molecular weight is preferable because the fluidity and negative triboelectric charging characteristics of toner particles can be improved.

  In the present invention, a crosslinking agent may be used when the binder resin is synthesized in order to increase the mechanical strength of the toner particles and to control the molecular weight of the THF soluble component of the toner.

  Examples of the bifunctional crosslinking agent include the following. Divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene Glycol diacrylate, polyester-type diacrylate (MANDA Nippon Kayaku), and diacrylate above instead of diacrylate Thing.

  The following are mentioned as a polyfunctional crosslinking agent. Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and methacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, diallyl phthalate, tri Allyl cyanurate, triallyl isocyanurate and triallyl trimellitate. The addition amount of these crosslinking agents is preferably 0.05 parts by mass or more and 10 parts by mass or less, more preferably 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

  The following are mentioned as a polymerization initiator used for the toner of the present invention. 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis Azo or diazo polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl Peroxide-based polymerization initiators such as peroxide, lauroyl peroxide, tert-butyl-peroxypivalate.

  Although the usage-amount of these polymerization initiators changes with the target degree of polymerization, generally they are 3 mass parts or more and 20 mass parts or less with respect to 100 mass parts of polymerizable vinylic monomers. The kind of the polymerization initiator varies slightly depending on the polymerization method, but is used alone or in combination with reference to the 10-hour half-life temperature.

  The toner of the present invention contains a colorant as an essential component in order to impart coloring power. Examples of the colorant preferably used in the present invention include the following organic pigments, organic dyes, and inorganic pigments.

  Examples of organic pigments or organic dyes as cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specific examples include the following. C. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment blue.

  Examples of the organic pigment or organic dye as the magenta colorant include the following. Condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds. Specific examples include the following. C. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment violet 19, C.I. I. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 150, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment Red 254.

  Examples of the organic pigment or organic dye as the yellow colorant include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples include the following. C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 176, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 181, C.I. I. Pigment yellow 191, C.I. I. Pigment Yellow 194.

  Examples of the black colorant include carbon black and those prepared by using the above yellow colorant / magenta colorant / cyan colorant to black.

  These colorants can be used alone or in combination and further in the form of a solid solution. The colorant used in the toner of the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner.

  The colorant is preferably used by adding 1 part by mass or more and 20 parts by mass or less to 100 parts by mass of the polymerizable monomer or binder resin.

  In the present invention, when toner particles are obtained using a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and water phase migration property of the colorant, and preferably, a hydrophobic treatment with a substance that does not inhibit polymerization is performed. It is better to apply it to the colorant. In particular, since dye-based colorants and carbon black have many polymerization inhibiting properties, care must be taken when using them.

  In addition, as a method for suppressing the polymerization inhibitory property of the dye-based colorant, a method of polymerizing a polymerizable monomer in the presence of these dyes in advance can be mentioned, and the obtained colored polymer is composed of a polymerizable monomer composition. Add to product.

  Moreover, about carbon black, you may process with the substance (for example, polyorganosiloxane etc.) which reacts with the surface functional group of carbon black besides the process similar to the said dye.

  In the toner of the present invention, a wax component is essential. The content of the wax component is preferably 4.0% by mass or more and 25% by mass or less with respect to the total amount of the binder resin. When the content of the wax component is less than 4.0% by mass, the releasability effect at the time of fixing cannot be sufficiently exhibited, and the transfer paper is likely to be wound when the fixing body is at a low temperature. On the other hand, if it is larger than 25% by mass, the wax component tends to be unevenly distributed on the surface of the toner particles when subjected to mechanical stress such as excessive friction in the developing device, and it tends to cause problems such as fogging and fusing.

  Further, the wax component preferably has a maximum endothermic peak temperature in the range of 60 ° C. or more and 120 ° C. or less in the DSC curve at the time of temperature rise measured by a differential scanning calorimetry (DSC) apparatus, more preferably It is 62 degreeC or more and 110 degrees C or less, More preferably, they are 65 degreeC or more and 90 degrees C or less. When the maximum endothermic peak temperature is less than 60 ° C., the storage stability of the toner and the developability such as fogging are lowered. On the other hand, when the maximum endothermic peak temperature exceeds 120 ° C., the plastic effect imparted to the toner is small and the low-temperature fixability is lowered.

  The wax component used in the present invention preferably contains a hydrocarbon wax. Other wax components include the following. Amide waxes, higher fatty acids, long chain alcohols, ketone waxes, ester waxes, and derivatives such as these graft compounds and block compounds. If necessary, two or more wax components may be used in combination.

  Examples of the hydrocarbon wax used in the present invention include the following. Petroleum waxes and derivatives thereof such as paraffin wax, microcrystalline wax, petrolatum; Fischer-Tropsch wax and derivatives thereof by the Fischer-Tropsch method; polyolefin waxes and derivatives thereof such as polyethylene wax and polypropylene wax. Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Further examples include hydrogenated castor oil and derivatives thereof, vegetable waxes and animal waxes. These wax components may be used alone or in combination of two or more.

  Among these, when the hydrocarbon wax by the Fischer-Tropsch method is used, the high temperature offset resistance can be maintained well while maintaining the developability particularly in the contact development over a long period of time. These hydrocarbon waxes may contain an antioxidant within a range that does not affect the chargeability of the toner.

  As the dispersion stabilizer used when preparing the aqueous medium, known inorganic and organic dispersion stabilizers can be used.

Specifically, the following are mentioned as an example of an inorganic dispersion stabilizer. Tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina .
Moreover, the following are mentioned as an organic type dispersing agent. Polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, starch.

  Commercially available nonionic, anionic and cationic surfactants can also be used. Examples of such surfactants include the following. Sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate.

  As the dispersion stabilizer, an inorganic poorly water-soluble dispersion stabilizer is preferable, and a poorly water-soluble inorganic dispersion stabilizer that is soluble in an acid is preferably used.

  In the present invention, when preparing an aqueous medium using a hardly water-soluble inorganic dispersion stabilizer, the amount of these dispersion stabilizers used is 0.2 mass relative to 100 parts by mass of the polymerizable monomer. It is preferable that it is at least 2.0 parts by mass. Moreover, in this invention, it is preferable to prepare an aqueous medium using 300 to 3000 mass parts of water with respect to 100 mass parts of polymerizable monomer compositions.

  In the present invention, when preparing an aqueous medium in which the above poorly water-soluble inorganic dispersion stabilizer is dispersed, a commercially available dispersion stabilizer may be used as it is. In order to obtain particles of a dispersion stabilizer having a fine uniform particle size, an aqueous medium may be prepared by generating a poorly water-soluble inorganic dispersion stabilizer in a liquid medium such as water under high-speed stirring. For example, when tricalcium phosphate is used as a dispersion stabilizer, a preferred dispersion stabilizer can be obtained by mixing sodium phosphate aqueous solution and calcium chloride aqueous solution under high speed stirring to form fine particles of tricalcium phosphate. Can do.

  In the toner of the present invention, a charge control agent can be mixed with toner particles and used as necessary. By adding a charge control agent, the charge characteristics can be stabilized, and the optimum triboelectric charge amount can be controlled according to the development system.

  As the charge control agent, a known one can be used, and a charge control agent that has a high charging speed and can stably maintain a constant charge amount is particularly preferable. Further, when the toner particles are produced by a direct polymerization method, a charge control agent having a low polymerization inhibition property and substantially free from a solubilized product in an aqueous medium is particularly preferable.

  Examples of the charge control agent that control the toner to be negatively charged include the following. Organic metal compounds and chelate compounds are effective, and monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds. Other examples include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides, esters, and phenol derivatives such as bisphenol. Further examples include urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, and resin charge control agents.

  Examples of the charge control agent that controls the toner to be positively charged include the following. Nigrosine-modified products such as nigrosine and fatty acid metal salts; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and the like Onium salts such as phosphonium salts and lake pigments thereof; triphenylmethane dyes and lake pigments thereof. Gallic acid, ferricyanide, ferrocyanide, etc.); metal salt of higher fatty acid; resin charge control agent.

  The toner of the present invention can contain these charge control agents alone or in combination of two or more.

  Among these charge control agents, a salicylic acid-based compound containing a metal is preferable in order to fully exhibit the effects of the present invention, and the metal is particularly preferably aluminum or zirconium. The most preferred charge control agent is an aluminum 3,5-di-tert-butylsalicylate compound.

  A preferable blending amount of the charge control agent is 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer or the binder resin. . However, it is not essential to add a charge control agent to the toner of the present invention, and the toner does not necessarily contain a charge control agent by actively utilizing frictional charging with the toner layer thickness regulating member or the toner carrier. There is no need to let it.

  In addition to the silica fine powder described in the present invention, other inorganic fine powder can be added to the toner particles of the present invention as a fluidity improver.

  Examples of the inorganic fine powder to be added to the toner particles of the present invention include fine powder such as silica fine powder, titanium oxide fine powder, alumina fine powder, or double oxide fine powder thereof. Among the inorganic fine powders, silica fine powder and titanium oxide fine powder are preferable.

Examples of the silica fine powder include dry silica or fumed silica produced by vapor phase oxidation of silicon halide, and wet silica produced from water glass. As the inorganic fine powder, dry silica having less silanol groups on the surface and inside the silica fine powder and less Na ₂ O and SO ₃ ²⁻ is preferable. The dry silica may be a composite fine powder of silica and another metal oxide produced by using a metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound in the production process.

  The inorganic fine powder is preferably externally added to the toner particles in order to improve the fluidity of the toner and make the toner particles uniformly charged. By hydrophobizing the inorganic fine powder, it is possible to adjust the charge amount of the toner, improve the environmental stability, and improve the characteristics in a high-humidity environment. More preferably, it is used. When the inorganic fine powder added to the toner absorbs moisture, the charge amount as the toner is reduced, and the developability and transferability are easily lowered.

  As treatment agents for the hydrophobic treatment of inorganic fine powder, unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, organotitanium Compounds. These treatment agents may be used alone or in combination.

  The image forming method of the present invention is not limited as long as it is an image forming method having the step, but an example is shown below.

  FIG. 5 is a cross-sectional view showing a schematic configuration of an image forming apparatus using a process cartridge including a toner and a toner carrier used in the present invention. The image forming apparatus shown in FIG. 5 includes a developing device 10 including a toner carrier 6, a toner application member 7, a toner 8 and a toner regulating member 9, an electrostatic latent image carrier (photosensitive drum) 5, a cleaning blade 14, a waste An all-in-one process cartridge 4 comprising a toner container 13 and a charging member 12 is detachably mounted. The photosensitive drum 5 rotates in the direction of the arrow, is uniformly charged by a charging member 12 for charging the photosensitive drum 5, and the surface thereof is exposed by laser light 11 which is an exposure means for writing an electrostatic latent image on the photosensitive drum 5. An electrostatic latent image is formed. The electrostatic latent image is developed by being applied with toner by the developing device 10 disposed in contact with the photosensitive drum 5, and is visualized as a toner image.

  The visualized toner image on the photosensitive drum 5 is transferred to a paper 22 as a recording medium by a transfer roller 17 as a transfer member. The paper 22 to which the toner image has been transferred is subjected to fixing processing by the fixing device 15 and is discharged out of the device, thus completing the printing operation.

  On the other hand, the untransferred toner remaining on the photosensitive drum 5 without being transferred is scraped off by a cleaning blade 14 which is a cleaning member for cleaning the surface of the photosensitive member and stored in a waste toner container 13 to be cleaned. The drum 5 repeats the above action.

  The developing device 10 includes a developing container containing the toner 8, a toner carrier 6 positioned in an opening extending in the longitudinal direction in the developing container and facing the photosensitive drum 5, and a toner regulating member 9. The electrostatic latent image on the photosensitive drum 5 is developed and visualized.

  The developing process in the developing device 10 will be described below. The toner is applied onto the toner carrier 6 by the toner application member 7 that is rotatably supported. The toner applied on the toner carrier 6 is rubbed against the toner regulating member 9 by the rotation of the toner carrier 6. The toner carrier 6 is in contact with the photosensitive drum 5 while rotating, and an electrostatic latent image formed on the photosensitive drum 5 is developed with toner coated on the toner carrier 6 to form an image.

  In the image forming method of the present invention, it is preferable to apply a bias to the toner regulating member 9 in order to make the coatability of the toner on the toner carrier uniform. The polarity of the applied bias is the same as the charging polarity of the toner, and the voltage is generally several tens to several hundreds V higher than the developing bias. When a bias is applied to the toner regulating member 9 as described above, the toner regulating member 9 is preferably conductive, and more preferably a metal such as phosphor bronze or stainless steel.

  The measurement methods for the toner carrier used in the present invention are shown below.

<Measurement Method of Distortion Rsk of Roughness Curve of Surface Roughness of Toner Carrier>
The skewness Rsk of the roughness curve of the surface roughness of the toner carrier in the present invention was measured according to JIS B0601-2001. A specific measurement method is shown below.

  The toner carrier is allowed to stand for 24 hours or more in an environment of 23 ° C./55% Rh, and toner is measured using a contact surface roughness meter SE-3500 (manufactured by Kosaka Laboratory) in a measurement environment of 23 ° C./55% Rh. The degree of distortion Rsk of the roughness curve of the surface roughness was measured with respect to the carrier axis direction. As shown below, a total of 12 positions of 3 positions in the axial direction × 4 positions in the circumferential direction are measured, and the average value of these 12 points is the skewness Rsk of the roughness curve of the surface roughness of the toner carrier. Value. The measurement position and measurement conditions are shown below. A total of 12 points at a central portion in the axial direction and 30 mm positions inside from both ends in the axial direction are measured in the circumferential direction in increments of 90 ° in the circumferential direction and measured in the axial direction of the toner carrier. Of Rsk. The measurement conditions are shown below.

(Measurement position)
Axial direction: central part in the axial direction of the toner carrier and three points at 30 mm inward from both ends in the axial direction.

(Measurement condition)
Measurement direction: Toner carrier axial cut-off: 0.8 mm
Filter: 2CR
Evaluation length: 4mm
Measurement speed: 1mm / sec

<Method for Measuring Volume Particle Size Distribution of Particles Contained in Surface Layer of Toner Carrier>
First, the surface layer was cut from the toner carrier. The cut surface layer is torn and broken by an appropriate method, and the fractured surface is observed with an optical magnification observation means such as a video microscope. The observation magnification is preferably 500 to 2000 times.

  From the observed fractured surface, only 1000 particles whose particle outlines are all observable are selected. For each of the selected particles, an area equivalent diameter (diameter of a circle having an area equal to the projected area): R (μm) is obtained.

The particles used in the present invention are preferably spherical, and the volume of each particle: Vn (μm ³ ) can be calculated by equation (4).

  For each of the 1000 particles selected, the particle volume: Vn (n is an integer from 1 to 1000) is determined.

  From Vn obtained by the above operation, a histogram is created in which the horizontal axis is indicated by the particle diameter (μm) and the vertical axis is indicated by the volume fraction. The histogram is created as follows.

  First, the horizontal axis of the histogram is the particle area equivalent diameter: R (μm). In the hierarchy of the histogram, a section with a diameter of 1.59 μm to 64 μm is divided into 32 by a geometric series.

  That is, the class value (class separation value): Xm (μm) of the histogram is expressed by Expression (5).

ヒストグラムの各階級に属する粒子の体積の総和を、
１０００個の粒子の体積の総和：

Sum of the volume of particles belonging to each class of the histogram,
Total volume of 1000 particles:

で除した値を、その階級におけるヒストグラムの縦軸の値とする。

The value divided by is taken as the value of the vertical axis of the histogram in that class.

  As described above, the volume particle size distribution of 1000 particles is shown as a histogram.

  In the histogram, the particle size of each class: RSj (μm) (where j is an integer of 1 to 32) is obtained according to Equation (6), and RSj is defined as the representative particle size in that class. That is, the vertical axis of the histogram is the volume fraction of particles with a certain representative particle size in all particles.

From the histogram showing the volume particle size distribution, the peak positions D _P (A) and D _P (B) and the peak height D _H (A) of the volume particle size distribution of the particles contained in the toner carrier surface layer in the present invention. And D _H (B) were determined.

<Method for measuring thickness of surface layer of toner carrier>
Using a sharp razor blade, the surface layer of the toner carrier is cut out into a semi-cylindrical shape together with the elastic layer from a total of three points 30 mm from the center and both ends of the toner carrier. Three were obtained. In each of the three obtained samples, the thickness of the five-point surface layer was measured by changing the measurement position, and the average value of the measurement results of a total of 15 points was defined as the surface layer thickness of the toner carrier. Here, as a means for measuring the thickness of the surface layer, a video microscope (manufactured by Keyence Corporation, magnification 2000 times) was used.

<Method for measuring surface hardness of toner carrier>
Using a micro rubber hardness meter MD-1 type A (manufactured by Kobunshi Keiki Co., Ltd.), the surface hardness of the toner carrier was measured. The measurement points were 12 points similar to the measurement points of the skewness Rsk of the roughness curve in the toner carrier surface roughness, and the average value was defined as the surface hardness of the toner carrier.

<Method for Measuring Weight Average Particle Diameters D ₄ (A) and D ₄ (B) of Particle A and Particle B on the Surface Layer of Toner Carrier>
The weight average particle diameters D ₄ (A) and D ₄ (B) of the particles A and B on the surface layer of the toner carrier were calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube by a pore electrical resistance method was used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) was used. The measurement was performed with 25,000 effective measurement channels.

  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, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software was set as follows.

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and the Kd value is “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

  In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 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 exclusively for Multisizer 3, set on a sample stand, and the stirrer rod was stirred counterclockwise at 24 rotations / second. The dirt and air bubbles in the aperture tube were removed using the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic solution was placed in a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting the solution with ion exchange water about 3 times by mass.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. A predetermined amount of ion-exchanged water was placed in the water tank of the ultrasonic disperser, and about 2 ml of the contamination N was added to the 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 liquid surface of the electrolytic aqueous solution 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 (D ₄ ) was calculated. The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D ₄ ).

  Hereinafter, various measurement methods for the toner of the present invention will be described.

<Method for Measuring Toner Weight Average Particle Size D ₄ (T)>
The weight average particle diameter D ₄ (T) of the toner is the same as the above <Method for measuring weight average particle diameters D ₄ (A) and D ₄ (B) of particles A and B on the surface layer of the toner carrier>. went.

<Measurement Method of Toner Viscosity at 100 ° C.>
The viscosity of the toner at 100 ° C. was measured according to a manual attached to the apparatus using a constant load extrusion type capillary rheometer “Flow Characteristic Evaluation Apparatus Flow Tester CFT-500D” (manufactured by Shimadzu Corporation). In this device, while applying a constant load from the top of the measurement sample with the piston, the measurement sample filled in the cylinder is heated and melted, and the molten measurement sample is pushed out from the die at the bottom of the cylinder, and the piston drop amount at this time A flow curve showing the relationship between temperature and temperature can be obtained. In the present invention, the viscosity (Pa · s) of the toner at 50 ° C. to 200 ° C. was measured to obtain the viscosity (Pa · s) at 100 ° C.

  As a measurement sample, about 1.0 g of toner is compression-molded at about 10 MPa using a tablet molding compressor (for example, NT-100H, manufactured by NPA System) in an environment of 25 ° C. for about 60 seconds. A cylindrical shape having a diameter of about 8 mm is used.

The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising start temperature: 50 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

<Method of measuring molecular weight distribution and molecular weight by toner gel and permeation chromatography (GPC) of tetrahydrofuran (THF) soluble content of toner material>
The molecular weight distribution and molecular weight of the THF-soluble component of the toner of the present invention and the toner material were measured by gel permeation chromatography (GPC) as follows.

First, the toner was dissolved in tetrahydrofuran (THF) at room temperature over 24 hours. The obtained solution is 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 is adjusted so that the concentration of the component soluble in THF is 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: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml

  In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name “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.

<Measurement method of maximum endothermic peak temperature in DSC endothermic curve at the time of temperature rise measured by differential scanning calorimetry (DSC) apparatus of wax component>
The measurement of the maximum endothermic peak temperature in the DSC endothermic curve at the time of temperature rise measured by the DSC apparatus of the wax component is measured according to ASTM D3418-82 using a differential scanning calorimeter analyzer “Q1000” (manufactured by TA Instruments). did.

  For the temperature correction of the device detector, the melting points of indium and zinc were used, and for the correction of heat quantity, the heat of fusion of indium was used.

  Specifically, about 10 mg of toner is precisely weighed, put in an aluminum pan, and an empty aluminum pan is used as a reference. Measurements were made at ° C / min. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 30 ° C., and then the temperature is raised again. The maximum endothermic peak of the DSC curve in the temperature range of 30 ° C. to 200 ° C. in the second temperature rising process was defined as the maximum endothermic peak of the endothermic curve in the DSC measurement of the toner of the present invention.

  Each measuring method is shown below about the silica fine powder used for this invention.

<Measurement method of BET specific surface area of silica fine powder>
The BET specific surface area of the toner is measured according to JIS Z8830 (2001). A specific measurement method is as follows.

  As the measuring device, an “automatic specific surface area / pore distribution measuring device TriStar 3000 (manufactured by Shimadzu Corporation)” which employs a gas adsorption method by a constant volume method as a measuring method is used. Setting of measurement conditions and analysis of measurement data are performed using dedicated software “TriStar3000 Version 4.00” attached to the apparatus, and a vacuum pump, a nitrogen gas pipe, and a helium gas pipe are connected to the apparatus. The value calculated by the BET multipoint method using nitrogen gas as the adsorption gas is defined as the BET specific surface area in the present invention.

  The BET specific surface area is calculated as follows.

First, nitrogen gas is adsorbed to the toner, and then the equilibrium pressure P (Pa) in the sample cell and the nitrogen adsorption amount Va (mol · g ⁻¹ ) of the toner are measured. The relative pressure Pr, which is a value obtained by dividing the equilibrium pressure P (Pa) in the sample cell by the saturated vapor pressure Po (Pa) of nitrogen, is plotted on the horizontal axis, and the nitrogen adsorption amount Va (mol · g ⁻¹ ) is plotted on the vertical axis. The adsorption isotherm is obtained. Next, a monomolecular layer adsorption amount Vm (mol · g ⁻¹ ), which is an adsorption amount necessary for forming a monomolecular layer on the surface of the toner, is obtained by applying the following BET equation.
Pr / Va (1-Pr) = 1 / (Vm * C) + (C-1) * Pr / (Vm * C)
(Here, C is a BET parameter, which is a variable that varies depending on the measurement sample type, adsorbed gas type, and adsorption temperature.)

The BET equation is interpreted as a straight line with an inclination of (C-1) / (Vm × C) and an intercept of 1 / (Vm × C), where Pr is X axis and Pr / Va (1-Pr) is Y axis. Yes (this line is called a BET plot).
Straight line slope = (C-1) / (Vm × C)
Straight line intercept = 1 / (Vm × C)

  When the measured value of Pr and the measured value of Pr / Va (1-Pr) are plotted on a graph and a straight line is drawn by the least square method, the slope and intercept value of the straight line can be calculated. Vm and C can be calculated by solving the above slope and intercept simultaneous equations using these values.

Further, the BET specific surface area S (m ² · g ⁻¹ ) of the toner is calculated from the calculated Vm and the molecular occupation cross-sectional area of the nitrogen molecule (0.162 nm ² ) based on the following formula.
S = Vm × N × 0.162 × 10 ⁻¹⁸
(N is Avogadro's number (mole- ¹ ).)

  The measurement using this apparatus follows the “TriStar 3000 Instruction Manual V4.0” attached to the apparatus, and specifically, the measurement is performed according to the following procedure.

  Thoroughly weigh the tare of a dedicated glass sample cell (stem diameter 3/8 inch, volume about 5 ml) that has been thoroughly cleaned and dried. Then, about 1.5 g of toner is put into the sample cell using a funnel.

  The sample cell containing the toner is set in a “pretreatment device Bacuprep 061 (manufactured by Shimadzu Corporation)” connected with a vacuum pump and a nitrogen gas pipe, and vacuum degassing is continued at 23 ° C. for about 10 hours. During vacuum deaeration, the toner is gradually deaerated while adjusting the valve so that the toner is not sucked into the vacuum pump. The pressure in the cell gradually decreases with deaeration and finally becomes about 0.4 Pa (about 3 mTorr). After completion of vacuum degassing, nitrogen gas is gradually injected to return the inside of the sample cell to atmospheric pressure, and the sample cell is removed from the pretreatment device. Then, the mass of the sample cell is precisely weighed, and the accurate toner mass is calculated from the difference from the tare. At this time, the sample cell is covered with a rubber stopper during weighing so that the toner in the sample cell is not contaminated by moisture in the atmosphere.

  Next, a dedicated “isothermal jacket” is attached to the stem portion of the sample cell containing the toner. Then, a dedicated filler rod is inserted into the sample cell, and the sample cell is set in the analysis port of the apparatus. The isothermal jacket is a cylindrical member having an inner surface made of a porous material and an outer surface made of an impermeable material capable of sucking liquid nitrogen to a certain level by capillary action.

  Subsequently, the free space of the sample cell including the connection tool is measured. The free space is measured by measuring the volume of the sample cell with helium gas at 23 ° C., and subsequently measuring the volume of the sample cell after cooling the sample cell with liquid nitrogen using helium gas. Calculated from the difference in volume. The saturated vapor pressure Po (Pa) of nitrogen is automatically measured separately using a Po tube built in the apparatus.

  Next, after performing vacuum deaeration in the sample cell, the sample cell is cooled with liquid nitrogen while continuing the vacuum deaeration. Thereafter, nitrogen gas is gradually introduced into the sample cell to adsorb nitrogen molecules to the toner. At this time, the adsorption isotherm is obtained by measuring the equilibrium pressure P (Pa) as needed, and the adsorption isotherm is converted into a BET plot. Note that the points of the relative pressure Pr for collecting data are set to a total of 6 points of 0.05, 0.10, 0.15, 0.20, 0.25, and 0.30. A straight line is drawn from the obtained measurement data by the least square method, and Vm is calculated from the slope and intercept of the straight line. Further, using the value of Vm, the BET specific surface area of the toner is calculated as described above.

<Method for measuring carbon content (C content) of silica fine powder>
After pyrolyzing a hydrophobic group chemically bonded to the surface of the silica fine powder in an oxygen atmosphere at a temperature of 1100 ° C. into CO ₂ , the inclusion of the silica fine powder by a trace carbon analyzer (“EMIA-110” manufactured by Horiba) The carbon content was determined. In addition, the effective number of carbon content seen from the reproducibility of the hydrophobization reaction is 0.1 mass%.

  Hereinafter, the present invention will be specifically described with reference to production examples and examples, but this does not limit the present invention in any way.

<Example 1>
<< Toner Carrier No. 1 Production Example >>
[Formation of elastic layer]
As a shaft core, a SUS 8 mm core metal made of SUS was nickel-plated, and a primer DY35-051 (trade name, manufactured by Toray Dow Corning Silicone) was applied and baked. Next, the shaft core is arranged concentrically with a cylindrical mold having an inner diameter of 16 mm, and carbon black talker is used for 100 parts by mass of liquid silicone rubber material SE6724A / B (trade name, manufactured by Toray Dow Corning Silicone). An addition type silicone rubber composition in which 35 parts by mass of black # 7360SB (trade name, manufactured by Tokai Carbon Co., Ltd.), 0.2 parts by mass of silica powder as a heat resistance imparting agent, and 0.1 parts by mass of platinum catalyst are mixed. Injection into a cavity formed in the mold. Subsequently, the mold was heated to vulcanize and cure the silicone rubber at 150 ° C. for 15 minutes, demolded, and further heated at 200 ° C. for 2 hours to complete the curing reaction, and the elastic layer having a thickness of 4 mm was formed as the shaft core. It was provided on the outer periphery.

[Polyol synthesis]
As a binder resin component for the surface layer, 100 parts by mass of polytetramethylene glycol PTG1000SN (trade name, manufactured by Hodogaya Chemical Co., Ltd.) and 20 parts by mass of isocyanate compound Millionate MT (trade name, manufactured by Nippon Polyurethane Industry Co., Ltd.) in the MEK solvent. Then, the mixture was reacted at 80 ° C. for 7 hours under a nitrogen atmosphere to prepare a polyether polyol having a hydroxyl value of 20.

[Synthesis of isocyanate]
Under a nitrogen atmosphere, with respect to 100 parts by mass of polypropylene glycol having a number average molecular weight of 500, 57 parts by mass of crude MDI was heated at 90 ° C. for 2 hours, and then butyl cellosolve was added to a solid content of 70%. Of 5.0% was obtained. Thereafter, 22 parts by mass of MEK oxime was added dropwise under a reaction temperature of 50 ° C. to obtain block polyisocyanate A.

[Preparation of paint for surface layer]
Block polyisocyanate A is mixed with the polyol prepared as described above so that the NCO / OH group ratio is 1.4, and carbon black (trade name: MA100 is used with respect to 100 parts by mass of the binder resin solid content. , Mitsubishi Chemical Co., Ph = 3.5) 20 parts by mass are mixed, dissolved and mixed in MEK so that the total solid content ratio is 35% by mass, and glass beads having a particle diameter of 1.5 mm are used. Dispersion 1 was prepared by dispersing for 4 hours using a sand mill. Thereafter, 24 parts by mass of spherical urethane resin particle Art Pearl C800 transparent (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle size 7.3 μm) in MEK of the same amount as the solid content of the binder resin component in the dispersion. 6 parts by mass of urethane resin particle Art Pearl C400 transparent (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle size 14.0 μm) was added and ultrasonically dispersed to obtain a spherical urethane resin particle dispersion. The obtained spherical urethane resin particle dispersion was added to dispersion 1 and further dispersed for 30 minutes using a sand mill to obtain a coating material for the surface layer.

[Formation of surface layer on elastic layer]
The surface layer paint obtained as described above is dip-coated on the elastic layer using an overflow dip coating apparatus, dried, and heat-treated at 150 ° C. for 2 hours for elasticity. A surface layer (resin layer) having a thickness of 10 μm is provided on the surface of the toner layer. 1 was obtained. Toner carrier No. The physical properties of 1 are shown in Table 1.

<< Silica Fine Powder No. 1 Production Example >>
In an outer flame formed by an oxygen-hydrogen flame, octamethylcyclotetrasiloxane is burnt and oxidized in an oxyhydrogen flame to obtain a raw silica fine particle having a specific surface area of 135 m ² / g and an average primary particle diameter of 16 nm. It was. Care was taken not to perform any operation such as mixing on the raw silica fine particles to promote contact between the fine particles.

  The raw silica fine particles were put into a mixer, and stirring was started under conditions where the temperature in the mixer was 250 ° C., the peripheral speed was 94 m / s, and the mixing degree for 1 minute was 98%, and nitrogen was circulated. This was maintained for 30 minutes to dry the raw silica fine particles. By this operation, the water content of the raw silica fine particles became 0.1% or less.

  Subsequently, stirring of the mixer is continued under the same conditions, and 20 parts by mass of dimethyl silicone oil (viscosity 50 cSt) is sprayed with 100 parts by mass of the original silica fine particles using a two-fluid nozzle to adhere to the active silica fine particles. It was.

  Furthermore, stirring of the mixer was continued under the same conditions, held for 60 minutes, and cooled. Subsequently, the silica fine particles No. 1 were subjected to crushing treatment with a pulverizer (manufactured by Hosokawa Micron Corporation) and surface-treated with silicone oil. 1 was obtained. The obtained silica fine particles No. The physical properties of 1 are shown in Table 2.

<< Toner No. 1 Production Example >>
With respect to 100 parts by mass of the styrene monomer, C.I. I. 16.5 parts by mass of Pigment Blue 15: 3 and 3.0 parts by mass of an aluminum compound of di-tertiary butylsalicylic acid [Bontron E88 (manufactured by Orient Chemical Co., Ltd.)] were prepared. These were introduced into an attritor (manufactured by Mitsui Mining Co., Ltd.), and stirred at 200 rpm at 25 ° C. for 180 minutes using zirconia beads (140 parts by mass) with a radius of 1.25 mm to prepare a master batch dispersion 1. .

On the other hand, after adding 450 parts by mass of 0.1 M Na ₃ PO ₄ aqueous solution to 710 parts by mass of ion-exchanged water and heating to 60 ° C., 67.7 parts by mass of 1.0 M CaCl ₂ aqueous solution was gradually added. An aqueous medium containing a calcium phosphate compound was obtained.
Master batch dispersion 1 40 parts by mass Styrene monomer 52 parts by mass n-butyl acrylate monomer 19 parts by mass Low molecular weight polystyrene 15 parts by mass (Mw = 3,000, Mn = 1,050, Tg = 55 ° C)
Hydrocarbon wax 9 parts by mass (Fischer-Tropsch wax, maximum endothermic peak = 78 ° C., Mw = 750)
Polyester resin 5 parts by mass (terephthalic acid: isophthalic acid: propylene oxide modified bisphenol A (2 mol adduct): ethylene oxide modified bisphenol A (2 mol adduct) = 30: 30: 30: 10 polycondensate, acid No. 11, Tg = 74 ° C., Mw = 11,000, Mn = 4,000)
The above material was heated to 63 ° C., and uniformly dissolved and dispersed at 5,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). In this, 7.0 parts by mass of a 70% toluene solution of a polymerization initiator 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate was dissolved to prepare a polymerizable monomer composition.

The polymerizable monomer composition is charged into the aqueous medium, and stirred at 12,000 rpm for 10 minutes with a TK homomixer at a temperature of 65 ° C. and in an N ₂ atmosphere to prepare the polymerizable monomer composition. Then, the temperature was raised to 66 ° C. while stirring with a paddle stirring blade, and when the polymerization conversion of the polymerizable vinyl monomer reached 90%, a 0.1 mol / liter sodium hydroxide aqueous solution was added. The pH of the aqueous dispersion medium was adjusted to 9 by addition. Furthermore, it heated up at 80 degreeC with the temperature increase rate of 40 degreeC / h, and was made to react for 4 hours. After completion of the polymerization reaction, the residual monomer in the toner particles was distilled off under reduced pressure. After cooling the aqueous medium, hydrochloric acid was added to adjust the pH to 1.4, and the mixture was stirred for 6 hours to dissolve the calcium phosphate salt. The toner particles were filtered off and washed with water, and then dried at a temperature of 40 ° C. for 48 hours. 1 was obtained.

  This toner particle No. 1 Silica fine powder No. 1 per 100 parts by mass. 1.9 parts by mass of 1 and 0.15 parts by mass of rutile titanium oxide fine powder (number average primary particle size: 30 nm) were dry-mixed for 5 minutes with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). . 1 was obtained. Toner No. The physical properties of 1 are shown in Table 2.

《Image evaluation》
Canon printer LBP5300 remodeling machine (8μm thick SUS blade is used as the toner regulating member, and the blade bias is modified so that a blade bias of −200V with respect to the developing bias can be applied to the toner regulating member). Images were evaluated in each environment. In the evaluation, the toner carrier of the image output cartridge is referred to as the toner carrier No. 1 described above. 1 and the toner no. An image was evaluated by attaching 160 g of 1 to the cyan station and attaching a dummy cartridge to the others.

  The image evaluation was performed in each environment of 23 ° C./55% Rh (normal temperature and normal humidity environment) and 30 ° C./80% Rh (high temperature and high humidity environment). After 50 images having a printing rate of 1% were output continuously, the image was paused for 5 hours, and the occurrence of development streaks was confirmed every time the output number reached 500. Finally, 15000 images were output, and development streaks and fogging were evaluated by the following methods. The evaluation results are shown in Table 3.

(1) Evaluation of development streaks To confirm the occurrence of development streaks, repeat the pause for 5 hours after outputting 50 sheets, and output a solid image and a halftone image every time the number of output sheets reaches 500 sheets. Judgment was made by visual observation of the image, and durability evaluation was performed up to 15000 sheets. The slower the development streak generation number, the better the development streak characteristics, and it was judged that the development streak generation start number was 12,000 or less. A, B, and C are levels that do not cause a problem in use, while D and E are levels that cause a problem in use.
A: Up to 15000 sheets, no development streak B: 14001 to 15000 sheets, development streak generation C: 12001 to 14000 sheets, development streak generation D: 10001 to 12000 sheets, development streak generation E: before 10,000 sheets, Development streaks

(2) Image fog evaluation 15,000 sheets of images having a white background portion were output at the end of the durability evaluation, and the whiteness of the white background portion of the printout image measured by “REFLECTMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku) ( The fog density (%) (= Dr (%) − Ds (%)) is calculated from the difference between the reflectance Ds (%)) and the whiteness of the transfer paper (average reflectance Dr (%)), and the durability evaluation is completed. The image fog of the time was evaluated. An amberlite filter was used as the filter. A, B, and C are levels that do not cause a problem in use, while D and E are levels that cause a problem in use.
A: Less than 0.5% B: 0.5% or more and less than 1.0% C: 1.0% or more and less than 1.5% D: 1.5% or more and less than 5.0% E: 5.0% or more

<Example 2>
The following toner carrier No. The procedure was the same as in Example 1 except that 2. The evaluation results are shown in Table 3.

<< Toner Carrier No. Production example 2
Toner carrier No. In the production example of Example 1, toner carrier No. 1 was changed except that the spherical urethane resin particles to be added were prepared as follows. In the same manner as in Production Example 1, toner carrier No. 2 was produced. Toner carrier No. The physical properties of 2 are shown in Table 1.
・ Classifying spherical urethane resin particle Art Pearl C800 transparent as follows: 26 parts by mass Classification of spherical urethane resin particle Art Pearl C800 transparent (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle size 7.3 μm) Fine powder and coarse powder were removed using Turboflex 100ATP (manufactured by Hosokawa Micron Corporation), and the volume average particle diameter was adjusted to 7.5 μm.
・ Classifying spherical urethane resin particle Art Pearl C400 transparent as follows: 4 parts by mass Classification of spherical urethane resin particle Art Pearl C400 transparent (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle diameter 14.0 μm) Fine powder and coarse powder were removed using Turboflex 100ATP (manufactured by Hosokawa Micron Corporation), and the volume average particle diameter was adjusted to 14.8 μm.

<Example 3>
The following toner carrier No. The procedure was the same as in Example 1 except that 3 was used. The evaluation results are shown in Table 3.

<< Toner Carrier No. Production example 3>
Toner carrier No. 1 except that the amount of spherical urethane resin particles to be added is changed as follows. In the same manner as in Production Example 1, toner carrier No. 3 was created. Toner carrier No. The physical properties of 3 are shown in Table 1.
・ Spherical urethane resin particle Art Pearl C800 transparent ... 22 parts by mass (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle size 7.3 μm)
-Spherical urethane resin particle Art Pearl C400 transparent ... 8 parts by mass (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle size 14.0 μm)

<Example 4>
The following toner carrier No. The procedure was the same as Example 1 except that 4 was used. The evaluation results are shown in Table 3.

<< Toner Carrier No. Production example 4
Toner carrier No. In the production example of Example 1, toner carrier No. 1 was changed except that the spherical urethane resin particles to be added were prepared as follows. In the same manner as in Production Example 1, toner carrier No. 4 was produced. Toner carrier No. The physical properties of 4 are shown in Table 1.
・ Spherical urethane resin particle Art Pearl C600 transparent is classified as follows: 14 parts by mass Spherical urethane resin particle Art Pearl C600 transparent (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle size 10.3 μm) is classified. Coarse powder was removed using Turboflex 100ATP (manufactured by Hosokawa Micron Corporation), and the volume average particle diameter was adjusted to 9.3 μm.
・ Classifying spherical urethane resin particle Art Pearl C300 transparent as follows: 6 parts by mass Spherical urethane resin particle Art Pearl C300 transparent (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle size 21.5 μm) is classified. Coarse powder was removed using Turboflex 100ATP (manufactured by Hosokawa Micron Corporation), and the volume average particle diameter was adjusted to 19.3 μm.

<Example 5>
The following toner carrier No. The procedure was the same as in Example 1 except that 5 was used. The evaluation results are shown in Table 3.

<< Toner Carrier No. Example 5
Toner carrier No. In the production example of Example 1, toner carrier No. 1 was changed except that the spherical urethane resin particles to be added were prepared as follows. In the same manner as in Production Example 1, toner carrier No. 5 was created. Toner carrier No. The physical properties of 5 are shown in Table 1.
・ Classifying spherical urethane resin particle art pearl C800 transparent as follows: 25 parts by mass Spherical urethane resin particle art pearl C800 transparent (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle size 7.3 μm) is classified. Coarse powder is removed using Turboflex 100ATP (manufactured by Hosokawa Micron Corporation), and the volume average particle diameter is adjusted to 6.0 μm.
-Spherical urethane resin particle Art Pearl C600 transparent ... 6 parts by mass (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle size 10.3 μm)

<Example 6>
The following toner carrier No. The same procedure as in Example 1 was performed except that 6 was used. The evaluation results are shown in Table 3.

<< Toner Carrier No. Production example 6
Toner carrier No. In the production example of Example 1, toner carrier No. 1 was changed except that the spherical urethane resin particles to be added were prepared as follows. In the same manner as in Production Example 1, toner carrier No. 6 was created. Toner carrier No. The physical properties of 6 are shown in Table 1.
-Spherical urethane resin particle Art Pearl C300 transparent ... 12 parts by mass (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle diameter 21.5 μm)
・ Classifying spherical urethane resin particle art pearl C200 transparent as follows: 3 parts by mass Spherical urethane resin particle art pearl C200 transparent (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle size 30.5 μm) is classified. Coarse powder was removed using Turboflex 100ATP (manufactured by Hosokawa Micron Corporation), and the volume average particle diameter was adjusted to 26.5 μm.

<Example 7>
The following toner carrier No. The procedure was the same as in Example 1 except that 7. The evaluation results are shown in Table 3.

<< Toner Carrier No. 7 Production Example >>
Toner carrier No. In the production example of Example 1, toner carrier No. 1 was changed except that the spherical urethane resin particles to be added were prepared as follows. In the same manner as in Production Example 1, toner carrier No. 7 was created. Toner carrier No. The physical properties of 7 are shown in Table 1.
・ Classifying spherical urethane resin particle Art Pearl C400 transparent as follows: 12 parts by mass Spherical urethane resin particle Art Pearl C400 transparent (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle size 14.0 μm) is classified. Fine powder was removed using Turboflex 100ATP (manufactured by Hosokawa Micron Corporation), and the volume average particle diameter was adjusted to 15.3 μm.
・ Classifying spherical urethane resin particle art pearl C200 transparent as follows: 3 parts by mass Spherical urethane resin particle art pearl C200 transparent (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle size 30.5 μm) is classified. Coarse powder was removed using Turboflex 100ATP (manufactured by Hosokawa Micron Corporation), and the volume average particle diameter was adjusted to 26.5 μm.

<Example 8>
The following toner carrier No. The procedure was the same as in Example 1 except that 8 was used. The evaluation results are shown in Table 3.

<< Toner Carrier No. 8 Production Examples >>
Toner carrier No. 1 except that the amount of spherical urethane resin particles to be added is changed as follows. In the same manner as in Production Example 1, toner carrier No. 8 was created. Toner carrier No. The physical properties of 8 are shown in Table 1.
・ Spherical urethane resin particle Art Pearl C800 transparent 35 parts by mass (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle size 7.3 μm)
-Spherical urethane resin particle Art Pearl C400 transparent ... 4 parts by mass (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle size 14.0 μm)

<Example 9>
Toner carrier No. 2 and the following toner No. The procedure was the same as in Example 1 except that 2 was used. The evaluation results are shown in Table 3.

<< Toner No. Production example 2
Toner No. In the production example 1, polymerization was started with 40 parts by mass of styrene monomer other than that used in Masterbatch Dispersion 1, 21 parts by mass of n-butyl acrylate monomer, and 20 parts by mass of low molecular weight polystyrene. Except for changing the 70% toluene solution of the agent 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate to 9.0 parts by mass, the toner no. In the same manner as in the production example 1, the toner No. 2 was produced. Toner No. The physical properties of 2 are shown in Table 2.

<Example 10>
Toner carrier No. 2 and the following toner No. The procedure was the same as in Example 1 except that 3 was used. The evaluation results are shown in Table 3.

<< Toner No. Production example 3>
Toner No. In Production Example 1, polymerization was started with 69 parts by mass of styrene monomer other than that used in Masterbatch Dispersion 1, 17 parts by mass of n-butyl acrylate monomer, and 10 parts by mass of low molecular weight polystyrene. Except for changing the 70% toluene solution of the agent 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate to 8.5 parts by mass, the toner No. In the same manner as in the production example 1, the toner No. 3 was produced. Toner No. The physical properties of 3 are shown in Table 2.

<Example 11>
Toner carrier No. 2 and the following toner No. The procedure was the same as in Example 1 except that 4 was used. The evaluation results are shown in Table 3.

<< Silica Fine Powder No. Production example 2
Silica fine powder no. 1 except that the dimethyl silicone oil (viscosity 50 cSt) is changed to 22 parts by mass with respect to 100 parts by mass of the raw silica fine particles. In the same manner as in Production Example 1, the silica fine powder No. 1 was used. 2 was produced. Silica fine powder no. The physical properties of 2 are shown in Table 2.

<< Toner No. Production example 4
Toner No. In the production example 1, the silica fine powder No. 1 was used. Toner No. 2 except that the toner No. 2 is used. In the same manner as in the production example 1, the toner No. 4 was produced. Toner No. The physical properties of 4 are shown in Table 2.

<Example 12>
Toner carrier No. 2 and the following toner No. The procedure was the same as in Example 1 except that 5 was used. The evaluation results are shown in Table 3.

<< Silica Fine Powder No. Production example 3>
Silica fine powder no. 1 except that the dimethyl silicone oil (viscosity 50 cSt) is changed to 18 parts by mass with respect to 100 parts by mass of the raw silica fine particles. In the same manner as in Production Example 1, the silica fine powder No. 1 was used. 3 was produced. Silica fine powder no. The physical properties of 3 are shown in Table 2.

<< Toner No. Production example 5>
Toner No. In the production example 1, the silica fine powder No. 1 was used. 3 except that the toner No. 3 is used. In the same manner as in the production example 1, the toner No. 5 was produced. Toner No. The physical properties of 5 are shown in Table 2.

<Example 13>
Toner carrier No. 2 and the following toner No. The procedure was the same as in Example 1 except that 6 was used. The evaluation results are shown in Table 3.

<< Silica Fine Powder No. Production example 4
Silica fine powder no. 1 except that the dimethyl silicone oil (viscosity 50 cSt) is changed to 15 parts by mass with respect to 100 parts by mass of the raw silica fine particles. In the same manner as in Production Example 1, the silica fine powder No. 1 was used. 4 was produced. Silica fine powder no. The physical properties of 4 are shown in Table 2.

<< Toner No. Production example 6
Toner No. In the production example 1, the silica fine powder No. 1 was used. 4 except that the toner No. 4 is used. In the same manner as in the production example 1, the toner No. 6 was produced. Toner No. The physical properties of 6 are shown in Table 2.

<Example 14>
Toner carrier No. 2 and the following toner No. The procedure was the same as in Example 1 except that 7 was used. The evaluation results are shown in Table 3.

<< Silica Fine Powder No. Example 5
Silica fine powder no. In one production example, oxygen - in the hydrogen flame outer flame formed of, by controlling the lower the temperature at which burning oxidation of octamethylcyclotetrasiloxane at an oxyhydrogen flame, a specific surface area of 140 m ² / g, Raw silica fine particles having an average primary particle diameter of 12 nm were obtained. Subsequent operations were performed with silica fine powder No. In the same manner as in Production Example 1, the silica fine powder No. 1 was used. 5 was produced. Silica fine powder no. The physical properties of 5 are shown in Table 2.

<< Toner No. 7 Production Example >>
Toner No. In the production example 1, the silica fine powder No. 1 was used. Toner No. 5 is used except that the toner No. 5 is changed. In the same manner as in the production example 1, the toner No. 7 was produced. Toner No. The physical properties of 7 are shown in Table 2.

<Example 15>
Toner carrier No. 2 and the following toner No. The procedure was the same as in Example 1 except that 8 was used. The evaluation results are shown in Table 3.

<< Silica Fine Powder No. Production example 6
Silica fine powder no. In one production example, by controlling the temperature at which combustion oxidation of octamethylcyclotetrasiloxane in an oxyhydrogen flame is increased in an outer flame formed by an oxygen-hydrogen flame, a specific surface area of 120 m ² / g, Raw material silica fine particles having an average primary particle diameter of 20 nm were obtained. Subsequent operations were performed with silica fine powder No. In the same manner as in Production Example 1, the silica fine powder No. 1 was used. 6 was produced. Silica fine powder no. The physical properties of 6 are shown in Table 2.

<< Toner No. 8 Production Examples >>
Toner No. In the production example 1, the silica fine powder No. 1 was used. Except for changing to using toner No. 6, Toner No. In the same manner as in the production example 1, the toner No. 8 was produced. Toner No. The physical properties of 8 are shown in Table 2.

<Example 16>
Toner carrier No. 2 and the following toner No. The procedure was the same as in Example 1 except that 9 was used. The evaluation results are shown in Table 3.

<< Toner No. Example 9
Toner No. In the production example 1, in the preparation of an aqueous medium containing a calcium phosphate compound, ion-exchanged water was added to 610 parts by mass, 0.1M-Na ₃ PO ₄ aqueous solution to 540 parts by mass, and 1.0M-CaCl ₂ aqueous solution to 81 Except for changing to the mass part, the toner No. In the same manner as in the production example 1, the toner No. 9 was produced. Toner No. The physical properties of 9 are shown in Table 2.

<Example 17>
Toner carrier No. 2 and the following toner No. The procedure was the same as in Example 1 except that 10 was used. The evaluation results are shown in Table 3.

<< Toner No. 10 production examples >>
Toner No. In the production example 1, in the preparation of an aqueous medium containing a calcium phosphate compound, 0.1M-Na ₃ PO ₄ aqueous solution was added to 810 parts by mass of ion-exchanged water and 550 parts by mass of 1.0M-CaCl ₂ aqueous solution was added to 55.5 masses. Toner No. In the same manner as in the production example 1, the toner No. 10 was produced. Toner No. The physical properties of 10 are shown in Table 2.

<Comparative Example 1>
The following toner carrier No. The same procedure as in Example 1 was performed except that 9 was used. The evaluation results are shown in Table 3.

<< Comparative toner carrier No. Example 9
Toner carrier No. In the production example 1, toner carrier No. 1 was used except that the spherical urethane resin particle Art Pearl C400 transparent was not added and the addition amount of the spherical urethane resin particle Art Pearl C800 transparent was changed to 30 parts by mass. In the same manner as in Production Example 1, the comparative toner carrier No. 9 was produced. Comparative toner carrier No. The physical properties of 9 are shown in Table 1.

<Comparative Example 2>
The following toner carrier No. The procedure was the same as in Example 1 except that 10 was used. The evaluation results are shown in Table 3.

<< Comparative toner carrier No. 10 production examples >>
Toner carrier No. In the production example of Example 1, toner carrier No. 1 was changed except that the spherical urethane resin particles to be added were prepared as follows. In the same manner as in Production Example 1, the comparative toner carrier No. 10 was produced. Comparative toner carrier No. The physical properties of 10 are shown in Table 1.
・ Classifying spherical urethane resin particle Art Pearl C800 transparent as follows: 25 parts by mass Classification of spherical urethane resin particle Art Pearl C800 transparent (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle size 7.3 μm) Coarse powder is removed using Turboflex 100ATP (manufactured by Hosokawa Micron Corporation), and the volume average particle diameter is adjusted to 6.0 μm.
・ Classifying spherical urethane resin particle art pearl C600 transparent as follows: 6 parts by mass Spherical urethane resin particle art pearl C600 transparent (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle size 10.3 μm) is classified. Coarse powder was removed using Turboflex 100ATP (manufactured by Hosokawa Micron Corporation), and the volume average particle diameter was adjusted to 9.3 μm.

<Comparative Example 3>
The following toner carrier No. The procedure was the same as Example 1 except that 11 was used. The evaluation results are shown in Table 3.

<< Comparative toner carrier No. 11 Production Examples >>
Toner carrier No. In the production example of Example 1, toner carrier No. 1 was changed except that the spherical urethane resin particles to be added were prepared as follows. In the same manner as in Production Example 1, the comparative toner carrier No. 11 was produced. Comparative toner carrier No. The physical properties of 11 are shown in Table 1.
Spherical urethane resin particle Art Pearl C800 transparent is classified as follows: 23 parts by mass Spherical urethane resin particle Art Pearl C800 transparent (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle size 7.3 μm) is classified. Fine powder and coarse powder were removed using Turboflex 100ATP (manufactured by Hosokawa Micron Corporation), and the volume average particle diameter was adjusted to 7.5 μm.
・ Classifying spherical urethane resin particle Art Pearl C400 transparent as follows: 6 parts by mass Classification of spherical urethane resin particle Art Pearl C400 transparent (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle diameter 14.0 μm) Fine powder and coarse powder were removed using Turboflex 100ATP (manufactured by Hosokawa Micron Corporation), and the volume average particle diameter was adjusted to 14.8 μm.

<Comparative example 4>
The following toner carrier No. The procedure was the same as in Example 1 except that 12 was used. The evaluation results are shown in Table 3.

<< Comparative toner carrier No. 12 Production Examples >>
Toner carrier No. In the production example 1, toner carrier No. 1 was changed except that the following were used as the spherical urethane resin particles to be added and the thickness of the surface layer was adjusted as shown in Table 1. In the same manner as in Production Example 1, the comparative toner carrier No. 12 was produced. Comparative toner carrier No. The physical properties of 12 are shown in Table 1.
-Spherical urethane resin particle Art Pearl C300 transparent ... 11 parts by mass (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle size 21.5 μm)
-Spherical urethane resin particle Art Pearl C200 transparent ... 4 parts by mass (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle size 30.5 μm)

<Comparative Example 5>
The following toner carrier No. The same procedure as in Example 1 was performed except that 13 was used. The evaluation results are shown in Table 3.

<< Comparative toner carrier No. 13 Production Examples >>
Toner carrier No. In the production example 1, toner carrier No. 1 was changed except that the following were used as the spherical urethane resin particles to be added. In the same manner as in Production Example 1, the comparative toner carrier No. 13 was produced. Comparative toner carrier No. The physical properties of 13 are shown in Table 1.
-Spherical urethane resin particle Art Pearl C600 transparent ... 20 parts by mass (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle size 10.3 μm)
-Spherical urethane resin particle Art Pearl C300 transparent ... 10 parts by mass (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle diameter 21.5 μm)

<Comparative Example 6>
The following toner carrier No. The procedure was the same as in Example 1 except that 14 was used. The evaluation results are shown in Table 3.

<< Comparative toner carrier No. 14 Production Examples >>
Toner carrier No. In the production example 1, toner carrier No. 1 was changed except that the following were used as the spherical urethane resin particles to be added and the thickness of the surface layer was adjusted as shown in Table 1. In the same manner as in Production Example 1, the comparative toner carrier No. 14 was produced. Comparative toner carrier No. The physical properties of 14 are shown in Table 1.
-Spherical urethane resin particle Art Pearl C800 transparent ... 29 parts by mass (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle size 7.3 μm)
-Spherical urethane resin particle Art Pearl C400 transparent ... 1 part by mass (trade name, manufactured by Negami Kogyo Co., Ltd., volume average particle diameter 14.0 μm)

<Comparative Example 7>
Toner carrier No. 2 and the following comparative toner No. The procedure was the same as in Example 1, except that 11 was used. The evaluation results are shown in Table 3.

<< Comparative Toner No. 11 Production Examples >>
Toner No. In one production example, in the preparation of an aqueous medium containing a calcium phosphate compound, ion-exchanged water was added to 610 parts by mass, 0.1M-Na ₃ PO ₄ aqueous solution to 540 parts by mass, and 1.0M-CaCl ₂ aqueous solution to 81 Except for changing the stirring with a TK homomixer when the polymerizable monomer composition is further introduced into the aqueous medium into the mass part at 10,000 rpm for 20 minutes, the toner no. In the same manner as in Production Example 1, the comparative toner No. 11 was produced. Comparative toner No. The physical properties of 11 are shown in Table 2.

<Comparative Example 8>
Toner carrier No. 2 and the following comparative toner No. The procedure was the same as in Example 1 except that 12 was used. The evaluation results are shown in Table 3.

<< Comparative Toner No. 12 production examples >>
Toner No. In the production example 1, in the preparation of an aqueous medium containing a calcium phosphate compound, ion-exchanged water was added to 810 parts by mass, 0.1M-Na ₃ PO ₄ aqueous solution to 370 parts by mass, and 1.0M-CaCl ₂ aqueous solution to 55 Toner No. 5 except that the stirring with a TK homomixer when the polymerizable monomer composition is further charged into an aqueous medium is changed to 30 parts by weight for 5 minutes. In the same manner as in Production Example 1, the comparative toner No. 12 was produced. Comparative toner No. The physical properties of 12 are shown in Table 2.

<Comparative Example 9>
Toner carrier No. 2 and the following comparative toner No. The procedure was the same as in Example 1 except that 13 was used. The evaluation results are shown in Table 3.

<< Silica Fine Powder No. 7 Production Example >>
Silica fine powder no. In one production example, by controlling the temperature at which combustion oxidation of octamethylcyclotetrasiloxane in an oxyhydrogen flame is controlled lower in an outer flame formed by an oxygen-hydrogen flame, a specific surface area of 140 m ² / g, Raw silica fine particles having an average primary particle diameter of 12 nm were obtained. Thereafter, except that the dimethyl silicone oil (viscosity 50 cSt) is changed to 15 parts by mass with respect to 100 parts by mass of the original silica fine particles, the silica fine powder No. In the same manner as in Production Example 1, the silica fine powder No. 1 was used. 7 was produced. Silica fine powder no. The physical properties of 7 are shown in Table 2.

<< Comparative Toner No. 13 Production Examples >>
Toner No. In the production example 1, the silica fine powder No. 1 was used. Except for changing to using toner No. 7, Toner No. In the same manner as in Production Example 1, the comparative toner No. 13 was created. Comparative toner No. The physical properties of 13 are shown in Table 2.

<Comparative Example 10>
Toner carrier No. 2 and the following comparative toner No. The same procedure as in Example 1 was performed except that 14 was used. The evaluation results are shown in Table 3.

<< Silica Fine Powder No. 8 Production Examples >>
Silica fine powder no. In one production example, a specific surface area of 130 m ² / r is obtained by controlling the temperature at which combustion oxidation of octamethylcyclotetrasiloxane is carried out in an oxyhydrogen flame in an outer flame formed by an oxygen-hydrogen flame. g, Raw silica fine particles having an average primary particle diameter of 18 nm were obtained. Thereafter, except that the dimethyl silicone oil (viscosity 50 cSt) was changed to 25 parts by mass with respect to 100 parts by mass of the raw silica fine particles, the silica fine powder No. In the same manner as in Production Example 1, the silica fine powder No. 1 was used. 8 was produced. Silica fine powder no. The physical properties of 8 are shown in Table 2.

<< Comparative Toner No. 14 Production Examples >>
Toner No. In the production example 1, the silica fine powder No. 1 was used. Except for changing to using toner No. 8, toner no. In the same manner as in Production Example 1, the comparative toner No. 14 was produced. Comparative toner No. The physical properties of 14 are shown in Table 2.

<Comparative Example 11>
Toner carrier No. 2 and the following comparative toner No. The procedure was the same as in Example 1 except that 15 was used. The evaluation results are shown in Table 3.

<< Silica Fine Powder No. Example 9
Silica fine powder no. In one production example, by controlling the temperature at which combustion and oxidation of octamethylcyclotetrasiloxane in an oxyhydrogen flame is increased in an outer flame formed by an oxygen-hydrogen flame, a specific surface area of 100 m ² / g, Raw material silica fine particles having an average primary particle diameter of 30 nm were obtained. Thereafter, except that the dimethyl silicone oil (viscosity 50 cSt) was changed to 22 parts by mass with respect to 100 parts by mass of the raw silica fine particles, the silica fine powder No. In the same manner as in Production Example 1, the silica fine powder No. 1 was used. 9 was produced. Silica fine powder no. The physical properties of 9 are shown in Table 2.

<< Comparative Toner No. 15 Production Examples >>
Toner No. In the production example 1, the silica fine powder No. 1 was used. Toner No. 9 is used except that the toner No. 9 is used. In the same manner as in Production Example 1, the comparative toner No. 15 was produced. Comparative toner No. The physical properties of 15 are shown in Table 2.

<Comparative Example 12>
Toner carrier No. 2 and the following comparative toner No. The procedure was the same as in Example 1 except that 16 was used. The evaluation results are shown in Table 3.

<< Silica Fine Powder No. 10 production examples >>
Silica fine powder no. In one production example, in the outer flame formed by an oxygen-hydrogen flame, by controlling the temperature at which octamethylcyclotetrasiloxane is burnt and oxidized in an oxyhydrogen flame, the specific surface area is 300 m ² / g, Raw silica fine particles having an average primary particle diameter of 8 nm were obtained. Thereafter, except that the dimethyl silicone oil (viscosity 50 cSt) was changed to 30 parts by mass with respect to 100 parts by mass of the raw silica fine particles, the silica fine powder No. In the same manner as in Production Example 1, the silica fine powder No. 1 was used. 10 was produced. Silica fine powder no. The physical properties of 10 are shown in Table 2.

<< Comparative Toner No. 16 Production Examples >>
Toner No. In the production example 1, the silica fine powder No. 1 was used. Toner No. 9 is used except that the toner No. 9 is used. In the same manner as in Production Example 1, the comparative toner No. 16 was produced. Comparative toner No. The physical properties of 16 are shown in Table 2.

<Comparative Example 13>
Toner carrier No. 2 and the following comparative toner No. The procedure was the same as in Example 1 except that 17 was used. The evaluation results are shown in Table 3.

<< Comparative Toner No. 17 Production Examples >>
Toner No. In the production example 1, the silica fine powder No. 1 was used. Toner No. 1 was changed except that 1 was changed to 3.0 parts by mass. In the same manner as in Production Example 1, the comparative toner No. 17 was produced. Comparative toner No. The physical properties of 17 are shown in Table 2.

<Comparative example 14>
Toner carrier No. 2 and the following comparative toner No. The procedure was the same as in Example 1 except that 18 was used. The evaluation results are shown in Table 3.

<< Silica Fine Powder No. 11 Production Examples >>
Silica fine powder no. In the production example of No. 1, silica fine powder No. 1 was used except that dimethyl silicone oil was changed to hexamethyldisilazane as a surface treatment agent. In the same manner as in Production Example 1, the silica fine powder No. 1 was used. 11 was produced. Silica fine powder no. The physical properties of 11 are shown in Table 2.

<< Comparative Toner No. 18 Production Examples >>
Toner No. In the production example 1, the silica fine powder No. 1 was used. No. 11 is used except that toner No. 11 is used. In the same manner as in Production Example 1, the comparative toner No. 18 was produced. Comparative toner No. The physical properties of 18 are shown in Table 2.

<Comparative Example 15>
Toner carrier No. 2 and the following comparative toner No. The procedure was the same as in Example 1 except that 19 was used. The evaluation results are shown in Table 3.

<< Comparative Toner No. 19 Production Examples >>
Toner No. 1 except that the silica fine powder 1 is not used. In the same manner as in Production Example 1, the comparative toner No. 19 was produced. Comparative toner No. The physical properties of 19 are shown in Table 2.

<Comparative Example 16>
Toner carrier No. 5 and toner no. The procedure was the same as in Example 1 except that 10 was used. The evaluation results are shown in Table 3.

<Example 18>
<< Toner No. 1-Y, toner no. 1-M and Toner No. 1-Bk Production Example >>
Toner No. In 1 production example, the colorants were “19.5 parts by weight CI Pigment Yellow 93”, “24 parts by weight CI Pigment Red 122”, and “22.5 parts by weight carbon black”, respectively. Toner no. In the same manner as in the production example 1, the toner No. 1-Y, toner no. 1-M and Toner No. 1-Bk was produced. Table 4 shows the physical properties of these toners.

《Image evaluation》
Canon printer LBP5300 remodeling machine (8μm thick SUS blade is used as the toner regulating member, and the blade bias is modified so that a blade bias of −200V with respect to the developing bias can be applied to the toner regulating member). Images were evaluated in each environment. In the evaluation, the toner carrier of the image output cartridge is designated as toner carrier No. The cyan toner No. 2 used in Example 1 was replaced. 1 and the yellow toner no. 1-Y, magenta toner no. 1-M, black toner no. A 1-Bk filled 160 g was mounted on each color station and a full color image evaluation was performed.

  In the evaluation of image fogging, the image evaluation method, evaluation conditions, and evaluation criteria were the same as in Example 1 except that an amber light filter, a green light filter, and a blue light filter were used as filters. The evaluation results are shown in Table 5.

FIG. 3 is a sectional view in the axial direction of a toner carrier used in the present invention. FIG. 3 is a conceptual diagram illustrating a state near the surface of a toner carrier used in the present invention. FIG. 5 is a conceptual diagram illustrating the degree of distortion of a roughness curve in the toner carrier surface roughness. 3 is a cross-sectional view of a volume particle size distribution of particles contained in a toner carrier surface layer. FIG. 1 is a schematic cross-sectional view of an image forming apparatus that can be used in the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Shaft core body of toner carrier 2 Elastic layer of toner carrier 3 Surface layer of toner carrier 4 Process cartridge 5 Photosensitive drum 6 Toner carrier 7 Toner applying member 8 Toner 9 Toner regulating member 10 Developing device 11 Laser beam 12 Charging Member 13 Waste toner container 14 Cleaning blade 15 Fixing device 16 Drive roller 17 Transfer roller 18 Bias power supply 19 Tension roller 20 Transfer conveyance belt 21 Drive roller 22 Paper 23 Feed roller 24 Adsorption roller 31 Relative in surface layer of toner carrier The relatively large particle 32 The relatively small particle G in the surface layer of the toner carrier The gap formed by the relatively large particle and the relatively small particle

Claims (24)

A charging step of charging the electrostatic latent image carrier with charging means, an exposure step of exposing the charged electrostatic latent image carrier to form an electrostatic latent image, and a toner on the toner carrier with a toner layer regulating member An image forming process including a step of regulating the electrostatic latent image carrier, a development step of developing the toner on the toner carrier with the toner on the toner carrier, and a transfer step of transferring the toner image to the transfer material with or without the intermediate transfer member In the method
The toner carrier is a toner carrier having an elastic layer on the outer periphery of the shaft core and a surface layer containing at least a binder resin and particles on the outer periphery.
The degree of distortion Rsk of the roughness curve of the toner carrier surface is 0.15 to 0.70,
The particles have two peaks in the volume particle size distribution, and each peak position is D _P (A) [μm] and D _P (B) [μm], and the peak heights are D _H (A) and D _H ( B) and the weight average particle diameter D ₄ (T) of the toner,
2.0 ≦ D _P (B) −D _P (A) ≦ 12.0
3.0 ≦ D ₄ (T) <D _P (A) <D _P (B) ≦ 30.0
1.0 ≦ D _H (A) / D _H (B) ≦ 8.0
And
The toner has toner particles containing at least a binder resin, a colorant, and a wax component, and silica fine powder,
In the particle size distribution of the toner, the weight average particle diameter D ₄ (T) is 3.0 to 8.0 μm,
At least one of the silica fine powders is a silica fine powder hydrophobized with silicone oil,
The amount of the silica fine powder with respect to 100 parts by mass of toner particles is 0.05 to 2.5 parts by mass,
The silica fine powder has a BET of 40 to 150 m ² / g,
When the amount of carbon of the silica fine powder is C amount (mass%) and the BET before the hydrophobic treatment of the silica fine powder is the base BET (m ² / g), the C amount / base BET = 0.020 to An image forming method, wherein the image forming method is 0.060. ^2. The image forming method according to claim 1, wherein the silica fine powder has a BET of 50 to 90 m ² / g. When the amount of carbon of the silica fine powder is C amount (mass%) and the BET before the hydrophobic treatment of the silica fine powder is the base BET (m ² / g), the amount of C / base BET = 0.030 to The image forming method according to claim 1, wherein the image forming method is 0.060. When the amount of carbon of the silica fine powder is C amount (% by mass) and the BET before the hydrophobic treatment of the silica fine powder is the base BET (m ² / g), the C amount / base BET = 0.035 to The image forming method according to claim 1, wherein the image forming method is 0.055. The image forming method according to claim 1, wherein the toner has a viscosity at 100 ° C. of 1.5 × 10 ^{4 to} 5.5 × 10 ⁴ Pa · s. In the toner carrier surface layer, when the blending amount of the particles with respect to 100 parts by mass of the binder resin is C [parts by mass] and the thickness of the surface layer is t [μm],
15.0 ≦ C ≦ 40.0
8.0 ≦ t ≦ 15.0
The image forming method according to claim 1, wherein the image forming method is an image forming method.   7. The image forming method according to claim 1, wherein the toner carrier has a surface hardness of 30.0 to 38.0.   8. The toner carrier surface layer, wherein the particles comprise A and B, and the mixing mass ratio of A and B is A: B = 60: 40 to 90:10. The image forming method according to one item.   9. The toner carrier surface layer according to claim 1, wherein the particles of the toner carrier surface layer are resin particles, and the binder resin and resin particles of the toner carrier surface layer are urethane resins. Image forming method. The particles of the toner carrier surface layer are composed of A and B, and the weight average particle diameter D ₄ (A) [μm] of A is 6.0 ≦ D ₄ (A) ≦ 10.0. The image forming method according to any one of claims 1 to 9. The particles of the surface layer of the toner carrier are composed of A and B, and the weight average particle diameter D ₄ (B) [μm] of B is 12.0 ≦ D ₄ (B) ≦ 20.0. The image forming method according to claim 1. The particles of the toner carrier surface layer are composed of A and B, and the weight average particle diameter D ₄ (A) [μm] of A and the weight average particle diameter D ₄ (B) [μm] of B are D ₄ ( The image forming method according to claim 1, wherein B) −D ₄ (A) ≧ 4.0. A charging step of charging the electrostatic latent image carrier with charging means, an exposure step of exposing the charged electrostatic latent image carrier to form an electrostatic latent image, and a toner on the toner carrier with a toner layer regulating member An image forming process including a step of regulating the electrostatic latent image carrier, a development step of developing the toner on the toner carrier with the toner on the toner carrier, and a transfer step of transferring the toner image to the transfer material with or without the intermediate transfer member Toner used in the method,
The toner carrier is a toner carrier having an elastic layer on the outer periphery of the shaft core and a surface layer containing at least a binder resin and particles on the outer periphery.
The degree of distortion Rsk of the roughness curve of the toner carrier surface is 0.15 to 0.70,
The particles have two peaks in the volume particle size distribution, and each peak position is D _P (A) [μm] and D _P (B) [μm], and the peak heights are D _H (A) and D _H ( B) and the weight average particle diameter D ₄ (T) of the toner,
2.0 ≦ D _P (B) −D _P (A) ≦ 12.0
3.0 ≦ D ₄ (T) <D _P (A) <D _P (B) ≦ 30.0
1.0 ≦ D _H (A) / D _H (B) ≦ 8.0
And
The toner has toner particles containing at least a binder resin, a colorant, and a wax component, and silica fine powder,
In the particle size distribution of the toner, the weight average particle diameter D ₄ (T) is 3.0 to 8.0 μm,
At least one of the silica fine powders is a silica fine powder hydrophobized with silicone oil,
The amount of the silica fine powder with respect to 100 parts by mass of toner particles is 0.05 to 2.5 parts by mass,
The silica fine powder has a BET of 40 to 150 m ² / g,
When the amount of carbon of the silica fine powder is C amount (mass%) and the BET before the hydrophobic treatment of the silica fine powder is the base BET (m ² / g), the C amount / base BET = 0.020 to A toner characterized by 0.060. The toner according to claim 13, wherein the silica fine powder has a BET of 50 to 90 m ² / g. When the amount of carbon of the silica fine powder is C amount (mass%) and the BET before the hydrophobic treatment of the silica fine powder is the base BET (m ² / g), the amount of C / base BET = 0.030 to The toner according to claim 13, wherein the toner is 0.060. When the amount of carbon of the silica fine powder is C amount (% by mass) and the BET before the hydrophobic treatment of the silica fine powder is the base BET (m ² / g), the C amount / base BET = 0.035 to The toner according to claim 13, wherein the toner is 0.055. The toner according to claim 13, wherein the toner has a viscosity at 100 ° C. of 1.5 × 10 ^{4 to} 5.5 × 10 ⁴ Pa · s. In the toner carrier surface layer, when the blending amount of the particles with respect to 100 parts by mass of the binder resin is C [parts by mass] and the thickness of the surface layer is t [μm],
15.0 ≦ C ≦ 40.0
8.0 ≦ t ≦ 15.0
The toner according to claim 13, wherein the toner is a toner.   The toner according to claim 13, wherein the toner carrier has a surface hardness of 30.0 to 38.0.   The particle of the toner carrier surface layer is composed of A and B, and the mixing mass ratio of A and B is A: B = 60: 40 to 90:10. The toner according to one item.   21. The toner carrier surface layer according to any one of claims 13 to 20, wherein the particles of the toner carrier surface layer are resin particles, and the binder resin and resin particles of the toner carrier surface layer are urethane resins. toner. The particles of the toner carrier surface layer are composed of A and B, and the weight average particle diameter D ₄ (A) [μm] of A is 6.0 ≦ D ₄ (A) ≦ 10.0. The toner according to any one of claims 13 to 21. The particles of the surface layer of the toner carrier are composed of A and B, and the weight average particle diameter D ₄ (B) [μm] of B is 12.0 ≦ D ₄ (B) ≦ 20.0. The toner according to any one of claims 13 to 22. The particles of the toner carrier surface layer are composed of A and B, and the weight average particle diameter D ₄ (A) [μm] of A and the weight average particle diameter D ₄ (B) [μm] of B are D ₄ ( The toner according to claim 13, wherein B) −D ₄ (A) ≧ 4.0.

Images