JP2010139547A - Image forming method and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming method and an image forming apparatus for obtaining an image having excellent transfer efficiency, low-temperature fixability and offset resistance without occurrence of problems such as fog, low density, uniformity in solid image, dropping of a toner, uneven image, filming, fusion of the toner and inorganic fine powder to a latent image support and a developer support surface and fusion thereof to a layer thickness regulating member, and cleaning failure even in a long time use, and in use in a low-temperature and low humidity environment and a high-temperature and high humidity environment. <P>SOLUTION: In the image forming method, a toner layer is formed on a toner support by a regulating member for forming a thin layer of the toner, and the toner is developed by the toner support for developing in non-contact or in contact with a photoreceptor to thereby obtain a toner image on the photoreceptor. A coefficient μd of friction of the toner support is 1.35-2.00, and the toner is one-component development toner at least including binder resin, toner particles containing coloring agent and at least inorganic fine powder. In the state where a thin layer of toner is formed on the toner support, a coefficient of friction μt of the toner is 0.06-0.35. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an image forming method according to a recording method such as an electrophotographic method, an electrostatic recording method or a toner jet method, and an image forming apparatus using the same.

  In recent years, in the electrophotographic industry, the image resolution of printers and the like has been increased to 1200, 2400 dpi. Accordingly, the development method of the printer apparatus is also required to have higher definition. Also, copying machines are becoming more sophisticated, digitized, and full-color, and high resolution and high definition have been demanded as with printers.

  Further, as copiers and printers using electrophotography are widely used in general homes and the like, there is an increasing demand for making copiers and printers inexpensive and small.

  In response to the above requirements, it has been demanded to enable a design with simpler components. In addition, it is required to have high image quality even when designed with simpler components or for a long period of use.

  In response to such demands, there is a method of obtaining an image having good resolution and gradation by sharpening the particle size distribution by a polymerization method. There are suspension polymerization, emulsion aggregation and the like as a method for obtaining a toner by a polymerization method, but any method can obtain a polymer toner having a very sharp particle size distribution in a high yield. Further, this polymerized toner has a spherical shape as compared with the toner obtained by the pulverization method, and exhibits good developability and transferability. Furthermore, since it is easy to contain a release agent such as wax in the toner and to control the dispersion state in the toner, it is easy to achieve both developability and fixability, which also simplifies the fixing device. The merit that it is easy to deal with arises. In addition, by setting the molecular weight of the polymerization initiator and the polymerization reaction temperature within a certain range, the initial printing quality is improved, the image quality in continuous printing is excellent, and the occurrence of filming on the photoreceptor can be suppressed ( For example, see Patent Document 1).

  However, in recent years, the use environment and applications have been diversified due to the spread of copying machines and printers. For this reason, stable image characteristics and environmental characteristics are required even for long-term use, and this method is insufficient to satisfy these requirements. In particular, when an image with a low printing rate is printed over a long period of time in a high-temperature and high-humidity environment, the toner is fused to the developer carrier and the developing blade, and density unevenness is particularly observed in a low-density halftone image in a low-temperature and low-humidity environment. A problem occurred.

  In addition, a toner is obtained by mixing a charge control resin, a colorant, and an organic solvent that dissolves the charge control resin, and polymerizing in an aqueous dispersion medium, so that transferability and transparency are excellent, fog is small, and sufficient. There is a method for obtaining a print density (see, for example, Patent Document 2).

  However, the toner obtained by this method is insufficient in terms of transferability and fog when used for a long period of time, and further causes a problem that the toner is fused to the developer carrying member and the developing blade. . Further, since the charge distribution becomes broad, there arises a problem that image unevenness occurs due to charge unevenness.

Furthermore, the toner has a specific circularity distribution and a specific weight average particle diameter, and the average particle diameter and shape factor of the external additive contained in the toner particles are set to a specific range, whereby fine dots are formed. There is a report to reproduce faithfully (for example, see Patent Document 3).

  However, the above prior art has a point to be further improved in terms of suppression of fog when performing contact development. In addition, there are some problems in achieving both low-temperature fixability and stress resistance.

  In addition, as the negatively charged toner, externally added spherical toner base particles include small negatively charged silica fine particles, large particle negatively charged spherical silica fine particles, titanium oxide fine particles, α-type alumina fine particles, and metal soap particles. In addition, by using a toner having a specific relationship between the work function of toner base particles, alumina fine particles, and titanium oxide fine particles, there is no fogging, toner scattering, and toner leakage even when used continuously for a long time. There is a report that the amount does not increase (see, for example, Patent Document 4).

  However, the above-described prior art has some problems in long-term use at a low printing rate, use in a low-temperature and low-humidity environment, and use in a high-temperature and high-humidity environment. Further, there are some problems in terms of fusion of toner to the toner carrier and the regulating member. Furthermore, there are some problems in terms of fixing properties during high-speed printing.

  In addition, external additives are added to the toner base particles by multi-stage treatment, and the release of silica particles or titanium oxide fine particles is controlled by adding particles of long-chain fatty acids or salts thereof at the final stage of the multi-stage treatment. There is a report that a toner that maintains chargeability for a long time and has excellent fluidity can be obtained (see, for example, Patent Document 5).

  However, the above-described prior art has some problems in long-term use at a low printing rate, use in a low-temperature and low-humidity environment, and use in a high-temperature and high-humidity environment. Further, there are some problems in terms of fusion of toner to the toner carrier and the regulating member.

  Further, by using a toner comprising a toner particle containing a binder resin having a specific acid value, a fluidity improver, and a fatty acid metal salt particle having a specific particle size distribution, toner particles can be used in addition to the depleting action of the fatty acid metal salt. In the image under normal temperature normal humidity environment, high temperature high humidity environment, low temperature low humidity environment due to the effect of improving the chargeability of the image, reducing the reverse polarity part of the charge distribution and improving the long-term stability of the chargeability There are reports that image quality such as omission, image density, and fog is excellent, and toner scattering, poor cleaning, and developer particle fusing on OPC are not observed (see, for example, Patent Document 6).

  However, the above-described prior art has some problems in long-term use at a low printing rate and use such as intermittent durability. Further, there are some problems in terms of fusion of toner to the toner carrier and the regulating member. Further, the effect as a positively chargeable toner was insufficient.

  In addition, by adding inorganic fine powder treated with fatty acid and / or fatty acid metal salt to the toner, the stress applied to the toner between the transfer body and the photoreceptor can be reduced, toner aggregation can be prevented, Since charging stability is obtained, even if a low melt sharp melt resin is used, it achieves both high translucency and offset resistance, and suppresses filming on the photoconductor with high density and low fog. There are reports that prevent toner fusion, transfer failure, and image disturbance to a toner carrier or toner layer regulating member (see, for example, Patent Document 7).

  However, the above prior art has some problems in long-term use at a low printing rate and use in a high-temperature and high-humidity environment.

  In addition, by adjusting the ratio of the fatty acid metal salt liberation rate, environmental stability improvement, transferability improvement, charging stability improvement, and cleaning property improvement can be achieved, preventing the occurrence of photoconductor filming, There are reports that there are no fluctuations in image unevenness, and that there is no burying of external additives due to stirring of the developer during use, and that environmental stability, transferability, charging properties, and cleaning properties have little change over time (for example, patents) Reference 8).

  However, the above prior art has some problems in long-term use at a low printing rate. In particular, the non-magnetic one-component development system has some problems in terms of initial image density when the toner is fused to the toner layer regulating member and the toner carrier and used in a low temperature and low humidity environment.

  In addition, there is a report that the toner is prevented from being contaminated by adjusting the average circularity, the weight average particle diameter, and the dynamic friction coefficient of the toner, and has a good cleaning property (see, for example, Patent Document 9).

  However, the above prior art has some problems in long-term use at a low printing rate. In particular, the non-magnetic one-component development system has some problems in terms of image density unevenness when the toner is fused or fogged on the toner layer regulating member and the toner carrier and used in a low temperature and low humidity environment.

  Also, in response to the demand for a copying machine or printer that uses electrophotography to be inexpensive and compact, the two-component development system uses a carrier and requires a mechanism that controls the mixing ratio of the carrier and toner. Therefore, a one-component development system is preferable. However, in the one-component development system, since there is no carrier assistance, the toner is frictionally charged in the contact nip region between the toner carrier and the toner layer regulating member. Therefore, it is disadvantageous in the chargeability and durability of the toner. There is a report that the problem can be suppressed by lowering the developing roller and the dynamic friction coefficient (see, for example, Patent Documents 10 and 11).

  However, the above prior art has some problems in long-term use at a low printing rate and use in a high-temperature and high-humidity environment.

  Further, a charge uniformizing member is provided between the developer regulating member and the development area, and the coefficient of friction between the charge uniformizing member and the developer, the coefficient of friction between the developers, and the developer carrying member and the developer There is a report that all the developer can be uniformly charged by adjusting the magnitude relationship of the friction coefficient between the two, thereby obtaining a high-quality image (see, for example, Patent Document 12).

  However, in the above prior art, the toner layer on the developer carrying member is stressed by both the developer regulating member and the charge uniformizing member in long-term use at a low printing rate or in a high-temperature and high-humidity environment. Since it is added, it has some problems in terms of durability.

  In addition, in non-magnetic one-component contact development, there is a report that a driving torque is reduced by setting the dynamic friction coefficient of the developing roller with respect to the surface of the photosensitive member within a certain range, and a good image can be obtained (see, for example, Patent Document 13).

However, although the above prior arts are effective with respect to toner dust and image density, durability and solid image uniformity in long-term use at a low printing rate and in a high-temperature and high-humidity environment. There are some problems.
Japanese Patent Laid-Open No. 10-020548 JP 2002-108011 A European Patent Publication No. 0886187 JP 2007-148198 A JP 2004-246257 A Japanese Patent No. 03605983 JP 2003-043733 A JP 2007-108622 A JP 2005-164873 A JP 2000-112225 A JP 2001-051495 A JP 2000-275964 A JP 09-152769 A

  An object of the present invention is to provide an image forming method and an image forming apparatus that solve the above-mentioned problems. That is, the object of the present invention is to provide a latent image carrier of fogging, thin density, image unevenness, filming, toner or inorganic fine powder even in long-term use, use in a low temperature and low humidity environment, and use in a high temperature and high humidity environment. In addition, there is no problem of member contamination and poor cleaning such as fusion to the surface of the developer carrying member and adhesion to the layer thickness regulating member, and an image excellent in transfer efficiency, low-temperature fixability, and offset resistance can be obtained. An object is to provide an image forming method and an image forming apparatus.

The inventors of the present invention have made researches to solve the above problems, and found that the problems can be solved by making the friction coefficient of the toner carrier and the toner to be used constant, thereby completing the invention. That is, in the present invention, a toner layer is formed by a regulating member for forming a thin layer of toner on a toner carrier, and the toner is developed by a toner carrier that is developed in a non-contact manner or in contact with the photoreceptor. An image forming method for obtaining a toner image on the top,
The friction coefficient μd of the toner carrier is 1.35 to 2.00,
The toner is a one-component developing toner having at least a binder resin, a toner particle containing a colorant, and at least an inorganic fine powder;
The present invention relates to an image forming method, wherein a friction coefficient μt of the toner satisfies a relationship of 0.06 to 0.35 in a state where a thin layer of toner is formed on the toner carrier.

  The image forming method and the image forming apparatus of the present invention adjust the friction coefficient of the toner carrier and the friction coefficient μt of the toner in a state where a thin layer of toner is formed on the toner carrier to a specific range. In long-term use, use in low-temperature and low-humidity environments, and high-temperature and high-humidity environments, fogging, low density, image unevenness, filming, and melting of toner and inorganic fine powder onto the latent image carrier and developer carrier surface An image forming method capable of suppressing the occurrence of problems such as member contamination and poor cleaning, such as adhesion and adhesion to a layer thickness regulating member, and obtaining an image excellent in initial image density, transfer efficiency, low-temperature fixability, and offset resistance, and An image forming apparatus can be provided.

An image forming method and an image forming apparatus according to the present invention include a toner carrier that forms a toner layer on a toner carrier by a regulating member for forming a thin layer of toner, and that develops in a non-contact or contact manner with a photoreceptor. An image forming method for developing a toner to obtain a toner image on a photoreceptor,
The friction coefficient μd of the toner carrier is 1.35 to 2.00,
The toner is a one-component developing toner having at least a binder resin, a toner particle containing a colorant, and at least an inorganic fine powder;
When the friction coefficient μt of the toner satisfies the relationship of 0.06 to 0.35 in a state where a thin layer of toner is formed on the toner carrier, the following effects can be obtained.

  An image forming method using a toner carrier having a high friction coefficient is generally excellent in terms of image density and solid image uniformity because the toner formed on the toner carrier is quickly and sufficiently charged by friction. ing. However, since the friction energy is large, the stress on the toner is large. Therefore, when used over a long period of time, it is impossible to maintain excellent image quality in terms of image density and solid image uniformity. Furthermore, fogging, low density, image unevenness, filming, fusing of toner and inorganic fine powder to the surface of latent image carrier and developer carrier, fusing to layer thickness regulating member, etc., member contamination, poor cleaning and transfer The image quality also decreases in terms of efficiency reduction. As a method of solving these problems, there is a method of reducing the linear pressure between the toner carrier and the toner layer regulating member. However, the linear pressure is simply lowered to a level that does not cause degradation in image quality due to fog, fusion of toner or inorganic fine powder to the latent image carrier and developer carrier surface, and fusion to the layer thickness regulating member. When the device is used in a high temperature and high humidity environment, it will drop. In addition, the toner carrier is simply reduced to a level at which image quality deterioration due to fog, fusion of toner or inorganic fine powder to the surface of the latent image carrier and developer carrier, and fusion to the layer thickness regulating member does not occur. In the case of the method of reducing the friction coefficient, the image quality is lowered in terms of image density and solid image uniformity, which is not desirable.

  On the other hand, the friction coefficient μt of the toner carrier is 1.35 to 2.00, and the friction coefficient μt of the toner is 0.06 to 0.00 when the toner thin layer is formed on the toner carrier. Only when the relationship 35 is satisfied, good results can be obtained in the above-described problem. That is, when the friction coefficient μt of the toner is less than 0.06 in a state where a thin layer of toner is formed on the toner carrier, the toner is not triboelectrically charged even if the friction coefficient μd of the toner carrier is adjusted. This is not only insufficient in terms of fog and image density, but also is not sufficiently regulated by the toner layer thickness regulating member, resulting in non-uniform frictional charging of the toner and insufficient image uniformity. In addition, it is not desirable in terms of the occurrence of dripping. This phenomenon becomes more prominent when μt is less than 0.06 and μd is less than 1.35.

  On the other hand, when the toner friction coefficient μt is more than 0.35 in a state where a toner thin layer is formed on the toner carrier, the stress caused by friction on the toner even if the friction coefficient μd of the toner carrier is adjusted. However, it becomes excessive in long-term use, and therefore, it is not desirable in terms of fog, fusion of toner or inorganic fine powder to the surface of the latent image carrier and developer carrier, and fusion to a layer thickness regulating member. This phenomenon becomes more conspicuous when μt exceeds 0.35 and μd exceeds 2.00.

  Even if μt is 0.06 to 0.35, if μd is less than 1.35, the image density or the image density may be deteriorated due to deterioration of the toner carrier due to contamination or wear by toner or inorganic fine powder in long-term use. This is not desirable in terms of solid image uniformity. Further, even if μt is 0.06 to 0.35, if μd is more than 2.00, stress due to friction with respect to the toner becomes excessive, so that the latent image carrier of fog and toner or inorganic fine powder and This is not desirable in terms of fusion to the developer carrier surface, fusion to a layer thickness regulating member, and the like.

  When the friction coefficient μd of the toner carrier in the present invention is 1.35 to 1.70, stress due to friction with respect to the toner is reduced, so that fog and the latent image carrier of toner or inorganic fine powder and development are used in long-term use. It is more desirable in terms of fusion to the surface of the agent carrier or fusion to the layer thickness regulating member. Further, in the present invention, if the friction coefficient μt of the toner is 0.06 to 0.20, stress due to friction on the toner is reduced. Therefore, the latent image carrier and development of fog, toner, and inorganic fine powder are used for a long period of use. It is more desirable in terms of fusion to the surface of the agent carrier or fusion to the layer thickness regulating member.

  In the present invention, it is more desirable that μt / μd = 0.04 to 0.17 and Δμt = 0.01 to 0.06. This is because if the μt / μd is 0.17 or less, the effect of reducing the frictional force of the toner with respect to the friction of the toner carrier becomes more sufficient, and therefore, in terms of image density and solid image uniformity due to the high μd. The stress due to friction on the toner can be sufficiently reduced in a state where the advantages are fully utilized. Thereby, even in long-term use, it is more desirable in terms of fusing of fog, toner, and inorganic fine powder to the surface of the latent image carrier and developer carrier, and to the layer thickness regulating member.

  The friction coefficient μd of the toner carrier is caused by the friction of only the surface of the toner carrier with respect to the PET film, whereas the friction coefficient μt of the toner is (i) the friction between the toner and the PET film, and (ii) the PET film side. This is due to the friction between the toner in contact with the toner and the toner in contact with the surface of the toner carrier, and (iii) the friction between the toner and the toner carrier. Especially regarding (ii) the friction between the toner in contact with the PET film side and the toner in contact with the surface of the toner carrier, the toner itself is not fixed by an adhesive tape or the like, It becomes friction. On the other hand, (iii) friction between the toner and the toner carrier is affected by μd. Accordingly, when μt is considerably small although μd is large, that is, when the difference between μt and μd is large, (i) friction between toner and PET film, (ii) toner and toner carrier in contact with the PET film side The friction with the toner in contact with the surface is small. Therefore, it is desirable that μt / μd is 0.04 or more because it is advantageous in terms of frictional charging between the toners and frictional charging between the toner layer regulating member and the toner.

  Further, Δμt is the fluctuation range of the friction coefficient in the measurement range of the friction coefficient of the toner in a state where a thin layer of toner is formed on the toner carrier. That is, it represents the uniformity of the state where the toner is coated on the toner carrier. Therefore, when Δμt = 0.01 to 0.06, there is no unevenness in the stress applied to the toner coated on the toner carrier, and there is no unevenness in the chargeability of the toner, and the charge distribution becomes sharp. . Therefore, even in long-term use, the image density, solid image uniformity, fog, and fusion of toner and inorganic fine powder to the surface of the latent image carrier and developer carrier, and to the layer thickness regulating member, etc. More desirable.

  In the present invention, the friction coefficients μt and Δμt of the toner in a state where a thin layer of toner is formed on the toner carrier on which the friction coefficients μd and μd of the toner carrier were measured were measured by the following methods.

The friction coefficients μd and μt and Δμt were determined using the apparatus shown in FIG. First, when measuring μd, a PET film 34 having a width of 3.0 cm and a thickness of 0.10 mm, in which a weight 31 is loaded on the other end and the other end is set on the digital force gauge 32, is applied to the surface of the developing roller 8. The angle θ in FIG. 3 was set to 90 degrees. The digital force gauge 32 is adjusted to a zero value when there is no load when neither the weight 31 nor the PET film 34 is added. After the value of the digital force gauge 32 is stabilized, the developing roller 8 is rotated in the direction of arrow R8 in FIG. 11 at 60 rpm, and the rubbing force between the developing roller 8 and the PET film 34 at this time is measured with the digital force gauge 32. To do. The measured value is analog output from the digital force gauge 32, sampled at a frequency of 10 Hz using a recorder, and the sampled data is calculated by the computer 33 according to the following equation (1). Further, as shown in FIG. In addition, the average value of data corresponding to a measurement distance of 500 mm from (a) after the first rise of the friction coefficient immediately after the start of measurement was defined as μd. As a PET film to be used, # 100 of type S10 which is a standard grade of a general industrial film “Lumirror” manufactured by Toray Industries, Inc. was used.

The coefficient of friction μt is measured using a developing device, and a toner is coated on the toner carrier measured with the above μd so that the applied amount is 0.4 to 0.5 mg / cm ^2, and the development is performed at the time of μd measurement. The friction coefficient was similarly measured by setting in the same manner as the roller 8. The measured value is obtained by sampling the analog output value from the digital force gauge 32 with a recorder at a frequency of 10 Hz, and calculating the sampling data with the computer 33 according to the following equation (1).
As shown in FIG. 1, the average value for the data for the measurement distance of 500 mm from (a) after the rise of the friction coefficient immediately after the start of measurement was defined as μt. Δμt was calculated as the difference between the maximum value and the minimum value of the friction coefficient in the data for the measurement distance of 500 mm as shown in FIG.

μ = (1 / θ) · ln (F / W) (1)
Where μ is the friction coefficient,
θ: W shown in FIG. 11: Total value of W1 and W2 (100.0 g)
W1: Weight of weight W2: Weight of PET film F: Measured value of a digital force gauge.

  The reason why the friction coefficient μd of the toner carrier and the friction coefficient μt of the toner in the state where the toner thin layer is formed on the toner carrier is measured with respect to the PET film 34 is as follows. Although there is an example in which paper or the like is used instead of the member corresponding to 34, there is paper having a rough surface or smooth paper depending on the paper type, and the coefficient of friction cannot be uniquely determined. Further, since the toner carrier used in the present invention has a high coefficient of friction, measurement of the friction coefficient cannot be performed stably unless the rotation number of the toner carrier is reduced to 60 rpm. On the other hand, in actual use, a metal toner layer regulating member is brought into contact with the toner carrying member. Therefore, when the number of rotations of the toner carrying member at the time of measurement is as large as that in actual use, Although it is appropriate to calculate the friction coefficient, it is not appropriate when the rotation number of the toner carrier is as small as 60 rpm. Therefore, as a result of the examination, it was determined that the use of the PET film 34 is an appropriate condition.

  Setting the friction coefficients μd and μt within the range of the present invention can be realized by adjusting the type, Tg, and molecular weight of the resin used for the surface layer of the toner carrier. Regarding μt, the toner strength is adjusted, the average circularity is adjusted, the fatty acid metal salt is contained, the liberation rate and particle size distribution of the fatty acid metal salt are adjusted, and the toner particles contain a crystalline polyester. This can be realized by adjusting the type and content of the polyester resin, the type and content of the wax, or changing the method for producing the toner particles.

  The surface roughness of the developing roller 8 is preferably 0.10 to 10.00 μm, more preferably 0.30 to 7.00 μm in terms of the ten-point average roughness Rz, although it depends on the particle size of the toner used. 0.30 to 3.00 μm is more preferable, and 0.30 to 1.00 μm is more preferable. When the toner particle size is smaller, it is preferable to make the ten-point average roughness Rz slightly smaller. When the ten-point average roughness Rz is less than 0.1 μm, a sufficient toner conveying force cannot be obtained and the density tends to be insufficient. On the other hand, if the thickness is 10.0 μm or more, the toner cannot be sufficiently charged, which may cause a problem in terms of fog.

  The ten-point average roughness Rz was defined according to JIS B0601, and a surface roughness tester “SE-30H” manufactured by Kosaka Laboratory was used for measurement.

The toner used in the present invention is a toner having a fatty acid metal salt in the toner particles. The toner particles have a number average particle diameter (D1) of Dt (μm) and a fatty acid metal salt volume-based median diameter (D50). When Df (μm),
0.022 ≦ Df / Dt ≦ 0.270
3.00 ≦ Dt ≦ 8.00
0.15 ≦ Df ≦ 1.00
It is desirable to satisfy the relationship.

  The fatty acid metal salt generally has an effect as a lubricant, and has an effect of reducing stress on the toner. In the case of the toner used in the present invention, the friction coefficient can be controlled. However, in order to maintain the effect in long-term use, the fatty acid metal salt needs to adhere to the toner particle surface firmly to some extent. This is because when fatty acid metal salts are easily released from the surface of the toner particles, most of the released fatty acid metal salts adhere to the toner carrier or latent image carrier as soon as they are supplied, and are effective as a lubricant. To do. In this case, since the effect of reducing the stress due to the friction between the toners is large in the portion where the effect is exerted by the fatty acid metal salt attached to the toner, the free fatty acid metal salt has a small effect for reducing the stress due to the friction between the toners. Further, when used for a long period of time, the fatty acid metal salt is consumed from the surface of the toner carrier or latent image carrier and the effect is not maintained, which is not desirable. On the other hand, in a toner containing a fatty acid metal salt, the fatty acid metal salt is less likely to be released from the toner particles as its particle size is smaller. However, if the particle diameter of the fatty acid metal salt is too small, it will be buried in the toner particle surface, and the effect will not be exhibited. That is, the particle diameter of the fatty acid metal salt is preferably a particle diameter having a certain ratio with respect to the particle diameter of the toner particles. In order to achieve high image quality, it is preferable that the particle diameter of the toner particles be small to some extent. Specifically, in order to achieve high image quality, the number average particle diameter Dt (μm) of the toner particles is preferably set to Dt ≦ 8.00. However, if Dt <3.00, the specific surface area of the toner is large and the contact area is large, so that the effect of the fatty acid metal salt tends to be insufficient in terms of stress resistance. Moreover, it is not desirable in terms of poor cleaning.

  Of the factors affecting the adhesion between the fatty acid metal salt and the toner particles, the particle size factor of the toner particles is preferably 3.00 ≦ Dt ≦ 8.00, whereas the fatty acid metal salt is based on volume. The median diameter Df of the toner satisfies 0.15 ≦ Df ≦ 1.00 and satisfies 0.022 ≦ Df / Dt ≦ 0.270. It is preferable because the fatty acid metal salt is not easily released from the particle surface. In addition, the fatty acid metal salt is not buried on the surface of the toner particles, and the above-described effects can be obtained.

  If Df <0.15 or Df / Dt <0.022, the fatty acid metal salt is embedded in the toner surface, so that the effect as the lubricant possessed by the fatty acid metal salt cannot be exhibited. In addition, as a result of embedding the fatty acid metal salt on the toner surface, the chargeability of the toner is also lowered, which is undesirable in terms of fog and image density during long-term use.

  On the other hand, when Df / Dt> 0.270, since the fatty acid metal salt is easily released from the toner surface, the effect as a lubricant is difficult to be sustained. Further, it is not desirable from the viewpoint of fusion of toner or inorganic fine powder to the latent image carrier and developer carrier surface and fusion to a layer thickness regulating member. In addition, it affects the chargeability of the toner, which is undesirable particularly in terms of initial image density.

  Next, how the adhesion between the fatty acid metal salt and the toner particles affects the effect of the toner of the present invention will be described below. As an effect of the fatty acid metal salt, there is an action as a lubricant. As a method for efficiently obtaining this effect, there is a method in which an external additive is added to the toner base particles by multistage treatment, and particles comprising a long chain fatty acid or a metal salt thereof are added in the final stage of the multistage treatment. However, in practice, particles composed of long-chain fatty acids or their metal salts are released from the toner particles, and the effect is insufficient. As another method, there is a method in which the toner contains an inorganic fine powder treated with a fatty acid and / or a fatty acid metal salt. It will be enough.

  On the other hand, even if the fatty acid metal salt is liberated from the toner, if it is in contact with the toner, the effect as a lubricant is exhibited. However, if there is a mixture of free fatty acid metal salts, toners with attached fatty acid metal salts, and toners without attached fatty acid metal salts, there is a difference in chargeability and fluidity between them. In this case, the toner charge distribution becomes broad. Further, the fluidity is uneven. Therefore, the use of toner for a short period of time or in a normal environment does not cause a noticeable difference in the durability of the toner. It produces undesirable results when used in a high temperature and high humidity environment.

  In the process of toner consumption during image formation, the free fatty acid metal salt is not consumed at the same speed as the toner due to differences in chargeability and fluidity. Therefore, during long-term use, the composition of the toner, including the free fatty acid metal salt in the developing container, changes between the initial use and the late use. As a result, the chargeability and fluidity of the toner change between the early stage of use and the late stage of use, which is undesirable because the image quality is not stable during long-term use. Therefore, by using a toner that does not liberate the fatty acid metal salt even during long-term use and has excellent adhesion between the fatty acid metal salt and the toner particles, the above-described use in a long-term use or in a high-temperature and high-humidity environment. Since the effect of this is acquired, it is preferable.

  Further, when considering the fluidity and chargeability of the toner, there is a particle size distribution of the toner particles as an influential factor. In general, a toner having a small particle size has high chargeability, and a toner having a large particle size has low chargeability. Therefore, in order to obtain a toner having a sharp charge distribution, it is necessary to lower the chargeability of the toner on the smaller particle diameter side and increase the chargeability of the toner on the larger particle diameter side. The reason why the toner on the larger particle diameter side has low chargeability is that the specific surface area is small and the fluidity is poor, and that the toner surface is not particularly smooth during long-term use. On the other hand, since the fatty acid metal salt adheres to the toner particles without being released to the toner particles, the toner used in the present invention has a large particle size and the lubricant action of the fatty acid metal salt even when the toner surface is not smooth. Improves fluidity. For this reason, the amount of toner with low chargeability is reduced even during long-term use. This is desirable because the toner charge distribution remains sharp.

  In particular, in the non-magnetic one-component development system, the toner is charged by friction between the toners. Therefore, a decrease in the toner having a low chargeability results in a decrease in the toner having a low chargeability and a toner that is frictionally charged. Usually, in a non-magnetic one-component development system, a low-charge toner and a friction-charged toner have a high charge. Therefore, the highly charged toner also decreases due to the phenomenon of the toner having low chargeability. This is particularly desirable because the toner on both the highly charged side and the lowly charged side is reduced, and the effect of sharpening the charge distribution of the toner becomes remarkable. The toner used in the present invention is desirable because the fatty acid metal salt is less liberated from the toner particles and the charge distribution of the toner is kept sharp for a long period of time.

  The volume-based median diameter Df (μm) of the fatty acid metal salt is preferably 0.15 ≦ Df ≦ 1.00, more preferably 0.15 ≦ Df ≦ 0.75, and 0.30 ≦ It is particularly desirable that Df ≦ 0.65. Setting the volume-based median diameter Df of the fatty acid metal salt within the above range is realized by adjusting the type, concentration, reaction time of raw materials charged during the production of the fatty acid metal salt, and adjusting the pulverization conditions and the classification process. can do.

Further, the span value B defined by the following formula (1) of the fatty acid metal salt is desirably 1.75 or less, more desirably 1.50 or less, and particularly desirably 1.00 or less.
Span value B = (D95s−D5s) / D50s (1)
D5s: 5% integrated diameter based on volume D50s: median diameter based on volume (D50)
D95s: 95% integrated diameter on a volume basis

  As can be understood from the above definition, the span value indicates that the smaller the value, the narrower the particle size distribution, and the larger the value, the wider the particle size distribution. In the present invention, when the span value is within the above range, it is desirable that the fatty acid metal salt has a smaller particle size in terms of adhesion to toner particles. Setting the span value of the fatty acid metal salt in the above range can be realized by adjusting the type and concentration of the raw material charged during the production of the fatty acid metal salt, the reaction time, and adjusting the pulverization conditions and the classification process. .

  In the toner used in the present invention, the liberation rate of the fatty acid metal salt in the toner is preferably 1.0% or more and 30.0% or less, more preferably 1.0% or more and 25.0% or less. It is particularly desirable to be 0% or more and 20.0% or less.

In order to make a toner having a liberation rate of fatty acid metal salt of less than 1.0%, a strong force must be applied to adhere the fatty acid metal salt to toner particles. As a result, the toner is damaged and stress resistance is lowered, which is not desirable. In particular, when the toner has a viscosity at 100 ° C. of 65,000 Pa · s or less in a flow tester, the influence becomes remarkable. Further, even if the liberation rate of the fatty acid metal salt in the toner can be less than 1.0% without damaging the toner during the production of the toner, it is desirable that it is 1.0% or more. This is because the fatty acid metal salt liberated from the toner is appropriately adhered to the latent image carrier to suppress heat generation due to friction of the latent image carrier with the toner carrier and the cleaning member. As a result, thermal damage to the toner during long-term use can be suppressed, and stable image quality can be obtained for a long time. If the liberation rate of the fatty acid metal salt is more than 30.0%, the effect as a lubricant is lowered, and filming on the latent image carrier tends to be undesirable.
The release rate of the fatty acid metal salt in the toner can be achieved by adjusting the type of the fatty acid metal salt, the median diameter, the span value, the Df / Dt value, and the external addition conditions. .

  The toner particles used in the present invention preferably have a number average particle diameter (D1), that is, Dt of 3.0 μm or more and 8.0 μm or less, and more preferably 4.0 μm or more and 7.8 μm or less. It is particularly desirable that it is 0 μm or more and 6.5 μm or less. When the number average particle diameter Dt is less than 3.0 μm, the specific surface area of the toner is large, so that problems are likely to occur in durability and heat resistance during long-term use, and defective cleaning is likely to occur. When the number average particle diameter Dt exceeds 8.0 μm, it is not desirable because it is inferior in terms of toner coloring power, image resolution, and fine line reproducibility. The toner particles of the present invention preferably have 10 to 40% by number of particles of 4 μm or less. This is because if the number of particles of 4 μm or less is 10% by number or more, it is desirable in terms of toner coloring power and image resolution, and if it is 40% by number or less, it is desirable in terms of durability and heat resistance in long-term use. The number average particle diameter of the toner particles can be set in the above range by adjusting the hardness and pulverization conditions of the toner in the case of pulverized toner, or by using means such as classification and sieving, In the case of polymerized toner, the type and amount of the dispersion stabilizer used in the production of the toner particles, the stirring conditions, the pH of the aqueous layer are adjusted, and the produced toner particles are dried and then used for classification or sieving. Can be realized.

<Measurement method of volume-based median diameter (D50) and span value B of fatty acid metal salt>
The volume-based median diameter (D50) of the fatty acid metal salt used in the present invention is measured according to JIS.
Although it is measured according to Z8825-1 (2001), it is specifically as follows.

As a measuring device, a laser diffraction / scattering particle size distribution measuring device “LA-920” (manufactured by Horiba, Ltd.) is used. The dedicated software “HORIBA LA-920 for Windows WET (LA-920) Ver. 2.02” attached to LA-920 is used for setting measurement conditions and analyzing measurement data. As the measurement solvent, ion-exchanged water from which impure solids are removed in advance is used. The measurement procedure is as follows.
(1) A batch type cell holder is attached to LA-920.
(2) A predetermined amount of ion-exchanged water is put into a batch type cell, and the batch type cell is set in a batch type cell holder.
(3) The inside of the batch cell is stirred using a dedicated stirrer chip.
(4) Press the “refractive index” button on the “display condition setting” screen and select the file “110A000I” (relative refractive index 1.10).
(5) In the “display condition setting” screen, the particle diameter reference is set as the volume reference.
(6) After performing warm-up operation for 1 hour or more, the optical axis is adjusted, the optical axis is finely adjusted, and blank measurement is performed.
(7) Put about 60 ml of ion-exchanged water in a glass 100 ml flat bottom beaker. Among them, as a dispersant, “Contaminone N” (a nonionic surfactant, an anionic surfactant, a 10% by weight aqueous solution of a neutral detergent for washing a pH 7 precision measuring instrument comprising an organic builder, Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting the product (manufactured) with ion exchange water about 3 times by mass is added.
(8) 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. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.
(9) The beaker of (7) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the aqueous solution in a beaker may become the maximum.
(10) In a state where the aqueous solution in the beaker of (9) is irradiated with ultrasonic waves, about 1 mg of a fatty acid metal salt is added to the aqueous solution in the beaker little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In this case, the fatty acid metal salt may solidify and float on the liquid surface. In this case, ultrasonic dispersion is performed for 60 seconds after the mass is submerged by shaking the beaker. Moreover, in ultrasonic dispersion, it adjusts suitably so that the water temperature of a water tank may become 10 to 40 degreeC.
(11) The aqueous solution in which the fatty acid metal salt prepared in the above (10) is dispersed is immediately added little by little to a batch type cell, taking care not to enter bubbles, and the transmittance of the tungsten lamp is 90% to 95%. Adjust so that Then, the particle size distribution is measured. Based on the obtained volume-based particle size distribution data, the volume-based median diameter (D50) and span value B are calculated. Moreover, the span value B here is a value obtained by the following equation.
Span value B = (D95s−D5s) / D50s (1) Formula D5s: 5% integrated diameter on volume basis D50s: median diameter on volume basis (D50)
D95s: 95% integrated diameter on a volume basis

<Measurement method of liberation rate of fatty acid metal salt>
The liberation rate of the fatty acid metal salt in the toner according to the present invention is determined using a powder tester (manufactured by Hosokawa Micron) having a digital vibrometer (Digivibro Model 1332), an X-ray fluorescence analyzer Axios (manufactured by PANallytical), and measurement condition setting and measurement. The liberation rate of the fatty acid metal salt was determined from the intensity difference of fluorescent X-rays using the attached dedicated software “SuperQ ver. 4.0F” (manufactured by PANalytical) for data analysis.

As a specific measuring method, this sieve having a mesh size of 25 μm (635 mesh) is set on a powder tester shaking table. 5 g of accurately weighed sample is added on a sieve having a mesh size of 25 μm (635 mesh), the amplitude of the digital vibrometer is adjusted to about 0.60 mm, and vibration is applied for about 2 minutes. The above operation is repeated two more times, and the sample is passed through a 25 μm (635 mesh) sieve a total of three times. Next, about 4 g of the obtained sample is placed on an aluminum ring having a diameter of 40 mm, and compressed by a press machine at 150 kN to prepare a sample. The obtained sample was measured with a fluorescent X-ray analyzer (Axios). Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 27 mm, and the measurement time is 10 seconds. Further, when measuring a light element, it is detected by a proportional counter (PC), and when measuring a heavy element, it is detected by a scintillation counter (SC). The liberation rate of the fatty acid metal salt in the present invention was determined from the following formula by measuring the Kα ray net intensity (KCPS) of the metal element of the fatty acid metal salt before and after the sieve.
Liberation rate = {(Kα ray net intensity of metal element of fatty acid metal salt before sieving) − (Kα ray net intensity of metal element of fatty acid metal salt after sieving)} / (of metal element of fatty acid metal salt before sieving) Kα ray net intensity)

<Method for Measuring Toner and Number Average Particle Size (D1) of Toner Particles>
The number average particle diameter (D1) of the toner and toner particles is 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.) using a pore electrical resistance method equipped with a 100 μm aperture tube is 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.) is used. Note that the measurement is 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, dedicated software was set up as follows.
On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman The value obtained using Coulter Co.) is set. By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1,600 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 aqueous solution is put in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rotations / second. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put into 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 3) with ion-exchanged water is added.
(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 is placed in a water tank of an ultrasonic disperser, and about 2 ml of the contamination N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) About 10 mg of toner or toner particles are added to the electrolytic aqueous solution little by little in a state where ultrasonic waves are applied to the electrolytic aqueous solution in the beaker of (4). Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the number average particle diameter (D1) is calculated. When the graph / volume% is set with the dedicated software, the “average diameter” on the “Analysis / volume statistics (arithmetic average)” screen is the weight average particle diameter (D4), and the graph / number% is set. The “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

  A toner carrier that is particularly preferably used in the present invention will be described. The toner carrier preferably used in the present invention has an elastic layer and a surface layer around the core, the surface layer contains resins A and B, and the resin A is a polypropylene glycol or polytetramethylene glycol skeleton. The resin B is an acrylic resin having a Tg of 30 ° C. or more and 70 ° C. or less and a weight average molecular weight of 30,000 or more and 100,000 or less.

  First, the polyether polyurethane resin of resin A will be described. The polarity and mechanical properties of urethane resins vary depending on the type of resin introduced as the main skeleton. Among them, urethane resins having a polypropylene glycol unit or polytetramethylene glycol unit as the main skeleton are excellent in flexibility, and are generally relatively low polarity among urethane resins that are generally highly polar, and have good compatibility with acrylic resins. , Phase separation of the acrylic component and extreme surface unevenness are less likely to occur.

  Next, the acrylic resin of resin B will be described. Acrylic resins are generally less polar than urethane resins. Therefore, it tends to cause phase separation and extreme surface localization with a highly polar urethane resin. However, when used as a surface layer of a toner carrier, it is possible to avoid various increases in film hardness and decrease in substrate adhesion, and satisfy various performances at a high level. In particular, tackiness is improved, toner regulating member adhesion is suppressed, and development streaks are suppressed. Stabilization of development under high humidity and high temperature can be obtained.

A toner carrier suitably used in the present invention will be described below with reference to the drawings.
As shown in FIG. 12, the toner carrier used in the image forming apparatus of the present invention has an elastic layer 2 on the outer periphery of the conductive shaft core 1 and further has a surface layer 3. The conductive shaft core 1 functions as an electrode and a support member of a conductive member, and is a metal or alloy such as aluminum, copper alloy, or stainless steel; iron plated with chromium or nickel; It is made of a conductive material such as synthetic resin. The outer diameter of the shaft core is usually in the range of 4 to 10 mm.

The elastic layer 2 has such hardness and elasticity that it can be pressed against the photoconductor with an appropriate nip width and nip pressure so that the toner can be supplied to the electrostatic latent image formed on the photoconductor surface without excess or deficiency. It is given to the developing roller. This elastic layer is usually formed of a molded body of rubber material. As the rubber material, various rubber materials conventionally used for conductive rubber rollers can be used. Examples of the rubber used for the rubber material include the following. Ethylene-propylene-diene copolymer rubber (EPDM), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), natural rubber (NR), isoprene rubber (IR), styrene-butadiene rubber (SBR), fluorine rubber, Silicone rubber, epichlorohydrin rubber, NBR hydride, urethane rubber. These can be used alone or in admixture of two or more. Among these, it is preferable to use silicone rubber from the viewpoint of setting performance. Examples of the silicone rubber include polydimethylsiloxane, polymethyltrifluoropropylsiloxane, polymethylvinylsiloxane, polyphenylvinylsiloxane, and copolymers of these polysiloxanes.

  The elastic layer 2 contains a conductivity-imparting agent, and various additives such as a non-conductive filler, a crosslinking agent, and a catalyst are appropriately blended. As the conductivity-imparting agent, fine particles of conductive metal such as graphite, carbon black, aluminum, and copper; conductive metal oxide such as zinc oxide, tin oxide, and titanium oxide can be used. Of these, carbon black is preferred because it is relatively easily available and provides good chargeability. Non-conductive fillers include silica, quartz powder, titanium oxide, zinc oxide or calcium carbonate. Examples of the crosslinking agent include di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and dicumyl peroxide.

The volume resistivity value of the elastic layer 2 is preferably in the range of 10 ^{3 to} 10 ⁸ Ω · cm when a DC voltage of 100 V is applied. For example, when carbon black is used as the conductivity-imparting agent, 15 to 80 parts by mass is blended with 100 parts by mass of rubber in the rubber material. The thickness of the elastic layer 2 is preferably in the range of 2.0 to 6.0 mm, and more preferably in the range of 3.0 to 5.0 mm.

  The resin A preferably contained in the surface layer 3 is preferably a urethane resin excellent in flexibility having a polypropylene glycol unit or a polytetramethylene glycol unit as a main skeleton. Considering the compatibility with the acrylic resin, the SP value is preferably 8.4 or more and 8.9 or less. On the other hand, polyethylene glycol tends to have a higher polarity than polypropylene glycol and polytetramethylene glycol, and also has increased hydrophilicity, so that the sticking resistance may increase due to changes in physical properties in a high temperature and high humidity environment.

  Such a polyether polyurethane resin is obtained by reacting a polyether polyol or a urethanized polyether polyol with an isocyanate, but the content of the polyether component is adjusted so as not to reduce the mechanical strength by adjusting the content of urethane bonds. By increasing the content, it becomes possible to make it more flexible and low in polarity. Specifically, when the content of the polypropylene glycol skeleton and / or the polytetramethylene glycol skeleton is 60% by mass or more and 85% by mass or less, the urethane resin is more flexible and excellent in compatibility with the acrylic resin component.

  Although it does not specifically limit as an isocyanate compound as a crosslinking agent made to react with a polyol component, The following are mentioned. Aliphatic polyisocyanates such as ethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI); cycloaliphatic polyisocyanates such as isophorone diisocyanate (IPDI), cyclohexane 1,3-diisocyanate, cyclohexane 1,4-diisocyanate; 2,4 -Tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate (MDI), copolymers thereof, and block bodies thereof are used.

Moreover, the acrylic resin of the resin B preferably contained in the surface layer 3 can obtain more stable developability by strictly controlling the polarity difference, Tg and molecular weight between the polyurethane raw material and the acrylic resin. The Tg of the acrylic resin is preferably 30 ° C. or higher and 70 ° C. or lower. When Tg is less than 30 ° C., the adhesion resistance to the toner in a high-temperature and high-humidity environment is reduced regardless of the content of the acrylic resin, and toner fusion may easily occur during image formation. On the other hand, when Tg exceeds 70 ° C., the surface hardness of the developing roller increases, fogging occurs, and the durability of a large number of sheets may be reduced.

  The SP value of the acrylic resin is preferably 7.5 or more and 8.6 or less. The polarity of the acrylic resin can be easily controlled by selecting the monomer species. Those containing monomer units having a long-chain alkyl group at a high ratio greatly reduce the Tg, and since the SP value is low, the polarity difference from the urethane resin component suitable as a developing roller is increased, and the layer In some cases, the appearance may be poor due to separation, or the adhesiveness may be lowered with a low-polarity elastic layer such as silicone rubber. The acrylic resin preferably has a weight average molecular weight (Mw) of 30,000 or more and 100,000 or less. If the Mw is less than 30,000, it is difficult to obtain sufficient toner adhesion resistance in a high-temperature and high-humidity environment even if the Tg and SP values are in an appropriate range, and if the Mw exceeds 100,000, sufficient durability is obtained. Sexuality may not be obtained.

  In order to bring the various physical properties of the acrylic resin into a preferable range for such a developing roller, it is important to select the monomer species. Specifically, methyl methacrylate (MMA), ethyl methacrylate (EMA), styrene, 2-ethylhexyl methacrylate (EHMA), hydroxyethyl methacrylate (HEMA), acrylonitrile, and acrylamide can be preferably used. As described above, a monomer having a long-chain alkyl group, a monomer having fluorine or a silicone component may significantly lower the Tg and SP values of the acrylic resin. Methyl methacrylate (MMA), 2-ethylhexyl methacrylate (EHMA), and styrene are particularly preferable for obtaining an appropriate physical property range of the acrylic resin. In addition, an acrylic resin that does not contain a monomer unit containing a hydroxyl group such as HEMA is more preferable because it does not react with isocyanate during the crosslinking reaction of the urethane resin, and thus hardly raises the hardness of the film.

  In the present invention, the difference between the SP value of the polyurethane raw material before the crosslinking reaction of the (A) polyether polyurethane resin and the SP value of the (B) acrylic resin is 0.1 or more and 0.9 or less, and the total resin It is preferable that the content rate of (B) acrylic resin in a component is 0.1 mass% or more and 5.0 mass% or less. The difference in SP value between (A) polyether polyurethane resin and (B) acrylic resin in the present invention is [(A) SP value of polyurethane raw material before crosslinking reaction of polyether polyurethane resin]-[(B) acrylic resin SP value]. When the difference between the SP value of the polyurethane raw material before the crosslinking reaction of the urethane resin and the SP value of the acrylic resin exceeds 0.9, the adhesion of the substrate is reduced due to poor appearance due to layer separation or uneven distribution at the extreme interface There is. Further, when there is no SP difference, there is a case where toner is fused or fixed to another member. When the SP value of the acrylic resin is larger, an appearance defect may occur due to incompatibility.

  Regarding the content of the acrylic resin, if the content of the resin (B) in all the resin components is less than 0.1% by mass, the effect of adding the acrylic resin may not be sufficiently obtained. There is a risk of causing an increase in hardness and a decrease in adhesion to the elastic layer.

  The surface layer 3 preferably contains a conductivity imparting agent in order to impart conductivity. As the conductivity imparting agent, carbon black is preferable. The content of the carbon black in the surface layer 3 is 10 to 50% by mass with respect to 100 parts by mass of the base resin forming the surface layer, so that the conductivity as the developing roller can be in a preferable range. Therefore, it is preferable. The number average particle diameter and DBP oil absorption of carbon black to be used are not particularly limited, but from the viewpoint of film strength and conductivity imparting, the number average primary particle diameter is 15 to 50 nm and the DBP oil absorption is 70 to 150 ml / It is preferable that it is 100 g.

  Fine particles may be added to the surface layer 3 in order to control the surface roughness of the developing roller. The fine particles for roughness control preferably have a volume average particle size of 3 to 20 μm. The amount of particles added to the surface layer is preferably 1 to 50% by mass with respect to 100% by mass of the resin solid content of the surface layer. Furthermore, polyurethane resin, polyester resin, polyether resin, polyamide resin, acrylic resin, and polycarbonate resin can be used as the component of the fine particles for controlling roughness.

  Examples of the fatty acid constituting the fatty acid metal salt preferably contained in the toner particles of the present invention include monovalent saturated fatty acids such as butyric acid, valeric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and montanic acid, adipic acid, Examples include polyvalent saturated fatty acids such as pimelic acid, suberic acid, azelaic acid and sebacic acid, monovalent unsaturated fatty acids such as crotonic acid and oleic acid, and polyunsaturated fatty acids such as maleic acid and citraconic acid. It is desirable to have a fatty acid having 12 to 30 carbon atoms, and it is more desirable to have a fatty acid having 18 to 24 carbon atoms. This is because the fatty acid metal salt has a fatty acid having 12 or more carbon atoms because the fatty acid metal salt has higher chargeability and a higher electrostatic adhesion effect, and has a fatty acid having 18 or more carbon atoms. This is because the effect is further increased. Moreover, when a C12 or more fatty acid is used, it is easy to suppress a free fatty acid, and it is used preferably. Furthermore, it is desirable that the fatty acid contained in the fatty acid metal salt is a fatty acid having 30 or less carbon atoms, since the charge distribution of the toner becomes sharp. A fatty acid having a carbon number of 24 or less is particularly desirable because the effect becomes more remarkable. In particular, when the fatty acid metal salt is a stearic acid metal salt, the rise of charge is quick and the effect is most desirable.

  The fatty acid metal salt desirably has a free fatty acid content of 0.20% or less. This is because the effect of the fatty acid metal salt is reduced when the free fatty acid exceeds 0.20%.

<Method for measuring free fatty acid content of fatty acid metal salt>
The amount of free fatty acid of the fatty acid metal salt is precisely weighed 1 g of a sample, dissolved in a 1: 1 mixture of ethanol and ethyl ether, neutralized and titrated with an aqueous potassium hydroxide solution using phenolphthalein as an indicator. The content was expressed as a percentage by mass of stearic acid.

  The melting point of the fatty acid metal salt is desirably 122.0 ° C or higher and lower than 130.0 ° C. This is because when the melting point of the fatty acid metal salt is less than 122.0 ° C., the toner adheres to the vicinity of the bearing of the toner agitating blade and the developing roller in the developing container and the fatty acid metal salt is fused to the mixing blade at the time of manufacture. This is because it tends to be easy. In general, such a fatty acid metal salt having a low melting point has a low purity of the fatty acid raw material constituting the fatty acid and tends to contain other low-molecular components as impurities. On the other hand, a melting point of the fatty acid metal salt of 130.0 ° C. or higher is not preferable because toner filming on the toner conveying member may occur.

<Measuring method of melting point>
The melting point is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments). The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
Specifically, about 10 mg of a sample is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measurement is performed at ° C / min. In addition, melting | fusing point of fatty acid was made into melting | fusing point with the endothermic peak temperature of the obtained measurement result. The measurement was performed by 1ST scan.

The amount of the fatty acid metal salt added to 100 parts by mass of toner particles is preferably 0.02 parts by mass to 1.00 parts by mass, and more preferably 0.05 parts by mass or more and 0.50 parts by mass. . This is because if the amount of the fatty acid metal salt is less than 0.02 parts by mass, the effect of preventing toner filming on the toner conveying member tends not to be obtained. Further, when the amount of the fatty acid metal salt is 1.00 parts by mass or more, the toner tends to easily fall out in the developing container.

  Many fatty acids existing in nature exist as a mixture of acid components having different carbon numbers. Taking stearic acid obtained as a natural product as an example, stearic acid having 18 carbon atoms as a main component and further containing a trace amount of fatty acid components such as 14 carbon atoms, 16 carbon atoms, 20 carbon atoms and 22 carbon atoms. Usually, a product obtained by increasing the purity of the fatty acid component through a purification process to some extent is commercially available. Furthermore, as a high-purity product, there are Japanese Pharmacopoeia grade products and the like, but it is preferable to use these to obtain the effect. When stearic acid is used as the fatty acid, the purity of stearic acid is preferably 90.0% by mass or more, more preferably 99.9% by mass or more and 95.0% by mass or less of the whole. If the purity of stearic acid is less than 90.0% by mass, the heat resistance of the stearic acid metal salt particles is deteriorated, and solidification in the raw material container and handling become difficult during production, which is not preferable. Further, it is not preferable to set the purity of stearic acid to 99.9% by mass or more because of the purification cost. Here, the purity of the fatty acid is the purity of the stearic acid component, and fatty acids having carbon numbers other than 18 and other organic and inorganic substances are considered as impurities.

  As the main metal species forming the salt, lithium, sodium, potassium, copper, rubinium, silver, zinc, magnesium, calcium, strontium, aluminum, iron, cobalt, nickel and the like can be used. Furthermore, it is preferable to use zinc and calcium in order to keep the chargeability of the toner within an appropriate range throughout the durability. In addition to the main metal species, other metal species may be included. At this time, it is preferable that the element ratio of the main metal species and the other metal species group (the other metal ratio in the whole) is less than 30%.

  The most preferable fatty acid metal salt composition is zinc stearate and calcium stearate.

<Method for producing fatty acid metal salt>
Examples of typical fatty acid metal salt production methods currently in use include a method in which a solution of an inorganic metal compound is dropped into a solution of an alkali metal salt of a fatty acid (reaction method), or a fatty acid and an inorganic salt. A method (melting method) in which a metal compound is kneaded and reacted at a high temperature is exemplified. For the fatty acid metal salt used in the present invention, there is little variation among the particles of the fatty acid metal salt, and a preferred production method is a wet method, and among them, a metathesis method is preferred. The manufacturing process includes a step of dropping the solution of the inorganic metal compound into the solution of the alkali metal salt of the fatty acid to replace the alkali metal of the fatty acid with the metal of the inorganic metal compound.

In the toner used in the present invention, in a micro-compression test for a toner, the particle diameter of the toner to be measured is D (μm), and a load of 9.8 × 10 ⁻⁵ N / sec is applied to one particle of the toner at a load of 9.8 × 10. The maximum displacement when ^-4 N is loaded is X ₁₀₀ (μm), the maximum displacement when the load is 9.8 × 10 ⁻⁵ N / sec and the load is 2.0 × 10 ⁻⁴ N. when was _{20 (μm),}
D1 + 0.20 ≧ D ≧ D1−0.20 (D1: number average particle diameter of toner)
0.40 ≦ X ₁₀₀ /D≦0.80
0.020 ≦ X ₂₀ /D≦0.060
It is desirable to satisfy.

When the toner load speed is 9.8 × 10 ⁻⁵ N / sec and the load is 9.8 × 10 ⁻⁴ N, the maximum displacement / toner particle diameter (X ₁₀₀ / D) is less than 0.40. The concentration and resolution are likely to decrease due to the liberation of external additives. On the other hand, when it exceeds 0.80, development streaks occur even if the microhardness of the surface of the toner carrier is an appropriate value. Further, when the toner load speed is 9.8 × 10 ⁻⁵ N / sec and the load amount is 2.0 × 10 ⁻⁴ N, the amount of displacement / toner particle diameter (X ₂₀ / D) is smaller than 0.020. Sufficient fixability cannot be obtained. On the other hand, if it exceeds 0.060, the stress resistance is lowered and filming on the toner carrier occurs.

It should be noted that setting X ₁₀₀ / D and X ₂₀ / D of the toner within the above range means that the toner production method, the type and amount of the crosslinking agent added at the time of toner particle production, the type of wax or polyester contained in the toner, It can be realized by adjusting the amount. In particular, the toner can contain crystalline polyester or amorphous polyester, and the content can be adjusted, and by using a polyester having an unsaturated double bond, it can be further adjusted to an appropriate range and realized. it can.

<Toner micro-compression measurement method>
The micro-compression test in the present invention was performed using “Ultra micro hardness meter ENT1100” (manufactured by Elionix). This device obtains a load load-indentation depth curve by measuring the load applied to the indenter and the indentation depth from the time of loading to the time of unloading when the indenter is pushed into the sample. Data such as hardness and elastic modulus is obtained. The measurement method using the apparatus is described in the “ENT1100 operation manual” attached to the apparatus, and is specifically as follows.
As the indenter, a flat indenter having a contact surface of 20 μm square was used, and measurement was performed in an environment of a temperature of 27 ° C. and a humidity of 60% RH. The maximum load was set to 9.8 × 10 ⁻⁴ N, and the load was increased at a rate of 9.8 × 10 ⁻⁵ N / sec starting from a load of 0 N / sec. At this time, the displacement when the load reached 2.0 × 10 ⁻⁴ N was defined as X ₂₀ (μm). Further, after reaching the maximum load (9.8 × 10 ⁻⁴ N), the load was held for 0.1 sec, and the displacement after the holding was defined as the maximum displacement X ₁₀₀ (μm).
In actual measurement, after applying the toner on the ceramic cell, weak air is blown so that the toner is dispersed on the cell, the cell is set in the apparatus, and the measurement is performed as follows.
As the particles to be measured, the one having toner particles alone on the measurement screen is selected while looking through the microscope attached to the apparatus (the external additive may be attached to the toner particle surface). However, in order to eliminate the displacement error as much as possible, a particle diameter (D) in the range of ± 0.20 μm of the number average particle diameter (D1) (D1 + 0.20 ≧ D ≧ D1−0.20) is selected. . The major axis and minor axis of the toner particles were measured using software attached to the ultra-micro hardness meter ENT1100, and the aspect ratio [(major axis + minor axis) / 2] determined therefrom was defined as the particle diameter D (μm). . Further, the number average particle diameter (D1) of the toner particles was separately calculated by the method described above.
In measurement, 100 arbitrary toner particles having a particle diameter D (μm) satisfying the above conditions are selected and measured. Of the 100 data, the remaining 80 toner particles excluding the toner particles giving 10 data from the maximum value side and the minimum value side of the obtained maximum displacement amount X ₁₀₀ (μm), respectively. Were used as valid data. Using the obtained data, for each of the 80 selected toner particles, a calculated value obtained by dividing X ₂₀ and the maximum displacement X ₁₀₀ (μm) by the particle diameter D (μm) is obtained, and 80 calculated values are obtained. The arithmetic average value in the particles was obtained, and the average value was defined as X ₂₀ / D and X ₁₀₀ / D.

The toner used in the present invention preferably has a viscosity at 100 ° C. of 8,000 to 80,000 Pa · s, more preferably 15,000 to 65,000 Pa · s, as measured by a flow tester, and 15,000 to More preferably, it is 55,000 Pa · s, more preferably 15,000 to 42,000 Pa · s, and 20,000 to 42,000 P.
a · s is even more desirable. When the viscosity at 100 ° C. is 8,000 Pa · s or more, the storage stability is excellent. In addition, since contamination due to fusion and adhesion of the toner to the toner supply member and the toner regulating member is suppressed, it is desirable in that the toner is sufficiently frictionally charged even in long-term use. It is desirable for the viscosity to be 80,000 Pa · s or less because of excellent fixability at low temperatures. Further, since the inorganic fine powder is difficult to peel off from the toner particles in the frictional charging between the toner supply member, the toner regulating member and the toner, the effect of the present invention can be sufficiently obtained, and the toner supply member and the toner regulating member made of the inorganic fine powder are obtained. It is desirable because contamination of the latent image carrier can be suppressed.

The viscosity of the toner is determined as follows.
<Measurement Method of Toner Viscosity at 100 ° C.>
The viscosity of the toner at 100 ° C. is measured using a constant-load extrusion type capillary rheometer “Flow Characteristic Evaluation Apparatus Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the apparatus. In this device, while applying a constant load from the top of the measurement sample by the piston, the measurement sample filled in the cylinder is heated and melted, and the molten measurement sample is extruded from the die at the bottom of the cylinder, and the temperature at this time And measure the relationship between the amount of piston descent.

  In the present invention, measurement is performed from 50 ° C. to 200 ° C., and the apparent viscosity calculated at 100 ° C. is defined as the viscosity (Pa · s) of the toner at 100 ° C. The apparent viscosity η (Pa · s) at 100 ° C. is calculated as follows.

First, the flow rate Q (cm ³ / s) is calculated from the following formula (1). In the equation, the cross-sectional area of the piston is A (cm ² ), and the time required for the piston to descend between 0.10 mm above and below (0.20 mm as the interval) with respect to the position of the piston at 100 ° C. is Δ Let t (seconds).
Q = (0.20 × A) / (10 × Δt) (1)
Then, the apparent viscosity η at 100 ° C. is calculated from the following formula (2) using the obtained flow rate Q. In the formula, the piston load is P (Pa), the diameter of the hole of the die is B (mm), and the length of the die is L (mm).
η = (π × B4 × P) / (128,000 × L × Q) (2)
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

The average circularity of the toner used in the present invention is desirably 0.940 or more and 0.995 or less, more desirably 0.950 or more and 0.995 or less, and further desirably 0.960 or more and 0.995 or less. Desirably, 0.970 or more and 0.990 or less is particularly desirable. This is because when the average circularity of the toner is less than 0.940, the chargeability and fluidity of the toner tend to be inferior, and when it exceeds 0.995, the cleaning property tends to be inferior. In particular, 0.970 or more is desirable because a high-quality image can be obtained.

<Measurement of average circularity of toner>
Measurement was performed using a flow type particle image measuring apparatus “FPIA-2100 type” (manufactured by Toa Medical Electronics Co., Ltd.), and the calculation was performed using the following formula.

  Here, the “particle projected area” is the area of the binarized toner particle image, and the “peripheral length of the particle projected image” is the length of the contour line obtained by connecting the edge points of the toner particle image. Define. The degree of circularity is an index indicating the degree of unevenness of the toner particles, and is 1.000 when the toner particles are completely spherical, and the degree of circularity becomes smaller as the surface shape becomes more complicated.

  As a specific measuring method, first, 10 ml of ion-exchanged water from which impure solids are removed in advance is prepared in a container. After adding a surfactant, preferably an alkyl benzene sulfonate, as a dispersant, 0.02 g of a measurement sample was further added and dispersed uniformly. As a means for dispersion, an ultrasonic disperser “Tetora 150 type” (manufactured by Nikka Ki Bios) was used for dispersion treatment for 2 minutes to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of this dispersion may not be 40 degreeC or more. In order to suppress variation in circularity, the installation environment of the apparatus is controlled at 23 ° C. ± 0.5 ° C. so that the temperature inside the flow type particle image analyzer FPIA-2100 is 26 to 27 ° C. Preferably, autofocusing was performed using 2 μm latex particles every 2 hours. To measure the circularity of the toner, the flow type particle image measuring device is used, the concentration of the dispersion is readjusted so that the toner concentration at the time of measurement is 3,000 to 10,000 / μl, Measure more than 000. After the measurement, using this data, data having an equivalent circle diameter of less than 2 μm was cut to determine the average circularity of the toner.

  The toner used in the present invention preferably has a toner ratio of 2.0 μm or less of 2.0 to 20.0% by number, more preferably 2.0 to 10.0% by number, and 1% of the toner. It is desirable that the ratio of the toner of 0.0 μm or less is 1.0 to 6.0% by number. This is desirable in terms of contamination and fusion to the toner carrier and toner regulating member, and is because a higher quality image can be obtained over a long period of use.

  As a method for controlling the average circularity of the toner, a method of producing in an aqueous medium is desirable in the present invention. In particular, production by suspension polymerization is desirable. In this case, it is particularly desirable for the toner of the present invention to contain a polar resin during the production of the toner and adjust the acid value, composition and content of the polar resin.

  Next, the toner used in the present invention preferably contains a crystalline polyester. This is because both the fixability and durability are achieved at a high level due to the sharp melt property of the crystalline polyester.

The crystalline polyester can be obtained by reacting a divalent or higher polyvalent carboxylic acid with a diol. Among these, a polyester mainly composed of an aliphatic diol and an aliphatic dicarboxylic acid is preferable because of its high crystallinity. Only one type of crystalline polyester may be used, or a plurality of types may be used in combination. Furthermore, in addition to the crystalline polyester, an amorphous polyester may be included in the toner. In the present invention, the crystalline polyester means a polyester having an endothermic peak at the time of temperature rise in differential scanning calorimetry (DSC) and an exothermic peak at the time of temperature fall, and the measurement is performed according to “ASTM D 3417-99”.

  Examples of alcohol monomers for obtaining such a crystalline polyester include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, trimethylene glycol, and tetramethylene. Examples include glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, neopentyl glycol, 1,4-butadiene glycol and the like.

  In the present invention, the alcohol monomer as described above is used as a main component. In addition to the above components, polyoxyethylenated bisphenol A, polyoxypropylenated bisphenol A, 1,4-cyclohexanedimethanol, etc. Divalent alcohol, aromatic alcohol such as 1,3,5-trihydroxymethylbenzene, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, Trivalent alcohols such as glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, and trimethylolpropane may be used.

  Examples of the carboxylic acid monomer for obtaining the crystalline polyester include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, peric acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, Decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, isophthalic acid, terephthalic acid, n-dodecyl succinic acid, n-dedecenyl succinic acid, cyclohexanedicarboxylic acid, these Examples include acid anhydrides and lower alkyl esters.

  In the present invention, the carboxylic acid monomer as described above is used as a main component, but a trivalent or higher polyvalent carboxylic acid may be used in addition to the above components.

  Trivalent or higher polyvalent carboxylic acid components include trimellitic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid, 1,2,4-butanetricarboxylic acid, Examples thereof include 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, and derivatives such as acid anhydrides or lower alkyl esters thereof.

  Particularly preferable crystalline polyesters include polyesters obtained by reacting 1,4-cyclohexanedimethanol and adipic acid, polyesters obtained by reacting tetramethylene glycol and ethylene glycol and adipic acid, hexamethylene glycol and sebacine. Polyester obtained by reacting acid, polyester obtained by reacting ethylene glycol and succinic acid, polyester obtained by reacting ethylene glycol and sebacic acid, obtained by reacting tetramethylene glycol and succinic acid And polyester obtained by reacting diethylene glycol and decanedicarboxylic acid. More preferably, the crystalline polyester is a saturated polyester. This is because, compared with the case where the crystalline polyester has an unsaturated portion, a crosslinking reaction does not occur in the reaction with the polymerization initiator, which is advantageous in terms of the solubility of the crystalline polyester.

The crystalline polyester resin used in the present invention can be produced by an ordinary polyester synthesis method. For example, it can be obtained by subjecting a dicarboxylic acid component and a dial alcohol component to an esterification reaction or a transesterification reaction, and then performing a polycondensation reaction under reduced pressure or by introducing nitrogen gas according to a conventional method.

  In the esterification or transesterification reaction, a normal esterification catalyst or a transesterification catalyst such as sulfuric acid, tertiary butyl titanium butoxide, dibutyl tin oxide, manganese acetate, magnesium acetate can be used as necessary. As for polymerization, conventional polymerization catalysts such as tertiary butyl titanium butoxide, dibutyl tin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide and the like can be used. . The polymerization temperature and the amount of catalyst are not particularly limited, and may be arbitrarily selected as necessary. As the catalyst, a titanium catalyst is preferably used, and a chelate-type titanium catalyst is more preferable. This is because the reactivity of the titanium catalyst is appropriate, and a polyester having a desirable molecular weight distribution can be obtained in the present invention, and the crystalline polyester produced using the titanium catalyst is incorporated into the polyester during production. This is because the produced titanium or titanium catalyst is excellent in terms of chargeability of the toner. This is because the chelate-type titanium catalyst has large effects and improves the durability of the toner.

  In order to adjust the relationship between the acid value and the hydroxyl value of the crystalline polyester, this relationship can be adjusted by the amount of alcohol monomer used.

  That is, the ratio of the alcohol monomer to the carboxylic acid monomer can be adjusted to 1.01 to 1.10: 1 in molar ratio by using a large amount of alcohol monomer. . Regarding the adjustment of the acid value itself, the reaction may be traced over time, and the polyesterification may be terminated when the acid value falls within an appropriate range.

  The melting point of the crystalline polyester is preferably 60 to 110 ° C. When the melting point of the crystalline polyester is lower than 60 ° C., the toner is likely to be blocked, and the storage stability may be lowered. On the other hand, if the melting point of the crystalline polyester is higher than 110 ° C., the low-temperature fixability is impaired, which is not preferable. In the case where the toner is obtained by suspension polymerization, which is a preferred toner production method in the present invention, the solubility of the crystalline polyester in the polymerizable monomer is likely to deteriorate, and a colorant, crystalline polyester, etc. As a result, the dispersibility of the toner constituting material deteriorates, resulting in an increase in fog. It is preferable that the crystalline polyester has a melting point of 60 to 110 ° C. because the storage stability and fixability can be maintained, and when the toner particles are produced by a polymerization method, the solubility in the polymerizable monomer is increased. The melting point of the crystalline polyester can be measured by differential scanning calorimetry (DSC). The melting point of the crystalline polyester can be adjusted by the kind of alcohol monomer or carboxylic acid monomer used, the degree of polymerization, and the like.

  The number average molecular weight of the crystalline polyester is preferably 2,000 to 10,000. A crystalline polyester having a number average molecular weight in the range of 2,000 to 10,000 is desirable because the dispersibility of the crystalline polyester is improved and durability stability is improved in the obtained toner particles.

  When the number average molecular weight of the crystalline polyester is less than 2,000, the density of the crystalline polyester is lowered, and the durability stability may not be improved. On the other hand, when the number average molecular weight of the crystalline polyester exceeds 10,000, it takes time to melt the crystalline polyester and the dispersion state becomes non-uniform, so that the effect of improving the development stability is lowered. Sometimes. The number average molecular weight of the crystalline polyester can be adjusted by the type of alcohol monomer or carboxylic acid monomer used, the polymerization time, the polymerization temperature, and the like.

  The acid value (AV) of the crystalline polyester is preferably 0.0 to 20.0 mgKOH / g, more preferably 0.1 to 20.0 mgKOH / g, and 1.0 to 20.0 mgKOH / g. It is particularly desirable to have it. By reducing the acid value, the adhesion between the toner and paper during image formation is improved. Further, when the toner particles are produced by a polymerization method, if the acid value (AV) of the crystalline polyester is 20.0 mgKOH / g or less, the toner particles tend not to agglomerate with each other. Since the distribution state of the crystalline polyester is less likely to be biased, charging stability and durability stability are improved, which is desirable. In particular, when the acid value of the crystalline polyester is 1.0 or more, the distribution of the crystalline polyester in the toner is not concentrated in the core portion, and is distributed at a certain ratio or more in the middle and in the vicinity of the surface layer. From the viewpoints of adhesion, anti-fogging and fogging, transferability, fusion to a toner layer regulating member and toner carrier.

  Although the measuring method of the acid value of crystalline polyester is not specifically limited, For example, the method shown by JISK0070-1992 can be mentioned. Moreover, the hydroxyl value of crystallized polyester can be measured by said method.

  The xylene-insoluble content of the crystalline polyester is desirably 0.1 to 5.0% by mass, and more desirably 0.1 to 2.0% by mass. This is because 0.1 mass% or more is desirable in terms of durability and heat resistance, and 5.0 mass% or less is desirable in terms of solubility.

The method for measuring the proportion of xylene insolubles in the crystalline polyester resin is as follows.
For sample preparation, 10.00 g of resin was dispersed in 1000.0 g of xylene and allowed to stand for 72 hours, and then centrifuged using a centrifuge to remove the supernatant, followed by vacuum drying at 40 ° C. for 8 hours. A xylene-insoluble matter was obtained.
Proportion of xylene insoluble matter in the crystalline polyester resin = (weight of xylene insoluble matter obtained / 10.00) × 100 (wt%)
Calculated as
The conditions for centrifugation are as follows.
Centrifuge: H-9R (manufactured by Kokusan Co., Ltd.)
Rotation speed: 15000rpm
Rotation time: 10 minutes Temperature: 15 ° C

  The toner of the present invention preferably contains 3.0 to 30.0% by mass of crystalline polyester, more preferably 3.0 to 25.0% by mass, more preferably 3.0 to 3.0% by mass with respect to the binder resin. It is particularly preferable to contain ~ 20.0 mass%. When the content of the crystalline polyester is 3.0% by mass or more, the fixability is better, and it is more desirable from the viewpoint of suppressing the decrease in the rubbing concentration. Further, since the crystalline polyester easily absorbs moisture, if its content is more than 30% by mass with respect to the binder resin, the uniformity of charging of the toner is liable to be impaired, resulting in an increase in fog and the like. In particular, it is desirable for the chargeability of the toner to be 20% by mass or less.

  On the other hand, when the content of the crystalline polyester is greater than 30 parts by mass, the presence of excess crystalline polyester is likely to cause compatibility with the binder resin, resulting in a decrease in melt viscosity and an offset. There is a problem that makes it easier to do. Further, the polymerized toner is not desirable because the smoothness of the surface shape of the toner particles is reduced, which may reduce the charging characteristics and the image density.

The toner used in the present invention preferably has a BET specific surface area of 1.5 to 3.5 (m ² / g), more preferably 1.7 to 3.5 (m ² / g), and more preferably 1.7. It is especially desirable that it is -3.0 (m < ² > / g). When the BET specific surface area is 1.5 (m ² / g) or more, the toner can obtain sufficient fluidity over a long period of time, and when it is 3.5 (m ² / g) or less, the toner regulating member and latent This is desirable because it has excellent performance against image carrier contamination and poor cleaning.

<Measurement method of BET specific surface area>
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.
Furthermore, 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 (mol-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 using helium gas at 23 ° C., and then measuring the volume of the sample cell after cooling the sample cell with liquid nitrogen using helium gas. It is calculated by converting from the difference in volume. Further, 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.

  The toner used in the present invention has a polar resin, and the polar resin is preferably an amorphous polyester resin polymerized using at least a titanium catalyst. This is because the toner is excellent in chargeability and durability. This is because a polyester resin produced using a chelate-type titanium catalyst is particularly excellent in terms of heat resistance.

  In particular, when the toner is produced in an aqueous medium, the content of the amorphous polyester resin is preferably 0.50 to 20.0% by mass, more preferably 0.50 to 15.0% by mass, and still more preferably 1 It is 0.0-10.0 mass part, and it is especially desirable in it being 1.0-8.0 mass part. When the content is 0.50% by mass or more, the amorphous polyester layer has a sufficient thickness and covers the entire surface of the toner, and is particularly effective in terms of mechanical characteristics and chargeability. In addition, since the wax is sufficiently encapsulated, it is desirable because it is excellent in developability and durability. When the content is 20.0% by mass or less, the toner is excellent in terms of low-temperature fixability, and further, a release layer can be quickly formed with wax, which is desirable in terms of offset resistance. Further, it is desirable that the particle size distribution is sharp and the charge distribution is sharp, and that the influence of humidity on the toner is small and the toner has excellent charging stability. Further, the acid value of the amorphous polyester resin is preferably 3.0 to 25.0 mgKOH / g, more preferably 4.0 to 20.0 mgKOH / g, and 4.0 to 15.0 mgKOH / g. It is even more desirable if it is 4.0 to 10.0 mg KOH / g, and it is particularly desirable. When the acid value is 3.0 mgKOH / g or more, the amorphous polyester is desirable in that it forms a uniform layer on the toner surface. When the acid value is 25.0 mgKOH / g or less, the amorphous polyester is less affected by humidity when converted into a toner and has stable charging stability. Desirable in terms. In addition, since the amorphous polyester resin has an intermediate polarity between the toner and the aqueous medium, it can act as a dispersion stabilizing component during the production of toner particles, but has an acid value of 3.0 mgKOH / g or more and 25.0 mgKOH. / G or less is desirable because it is uniformly distributed in a stable state on the surface of the toner, and the effect is great, the generation of irregularly shaped particles is suppressed, and the toner charge distribution is uniform.

  In the toner of the present invention, the acid value of the amorphous polyester is desirably higher than the acid value of the crystalline polyester. This is because when the acid value of the crystalline polyester is higher than the acid value of the amorphous polyester, the interaction between the crystalline polyester and the wax decreases.

  The acid value of the polyester resin is determined as follows. Basic operation conforms to JIS-K0070-1992.

  The number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids, etc. contained in 1 g of a sample is called the acid value, and the test is conducted as follows.

(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95 vol%), and ion exchanged water is added to make 100 ml to obtain a phenolphthalein solution. 7 g of special grade potassium hydroxide is dissolved in 5 ml of water, and ethyl alcohol (95 vol%) is added to make 1 l. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.1 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. Determined from the amount of potassium solution. As the 0.1 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

(2) Operation (A) Main test 2.0 g of the pulverized binder resin sample is precisely weighed into a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene / ethanol (2: 1) is added and dissolved over 5 hours. . Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).

(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (ml) of a potassium hydroxide solution in a blank test, C: addition amount (ml) of a potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

  The xylene-insoluble content in the amorphous polyester resin is desirably 5.00% by mass or less, and more desirably 2.50% by mass. If the xylene-insoluble content is 5.00% by mass or less, it is difficult to produce irregularly shaped particles, which is desirable in terms of chargeability and durability. In particular, it is desirable in terms of fog and filming.

The measuring method of the ratio of xylene insolubles in the amorphous polyester resin is as follows.
For sample preparation, 10.00 g of resin was dispersed in 1,000.0 g of xylene and allowed to stand for 72 hours, then centrifuged with a centrifuge to remove the supernatant and then vacuum at 40 ° C. for 8 hours. It was dried to obtain xylene-insoluble matter.
Ratio of xylene insoluble matter in polyester resin = (weight of xylene insoluble matter obtained / 10.00) × 100 (wt%)
Calculated as The conditions for centrifugation are as follows.
Centrifuge: H-9R (manufactured by Kokusan Co., Ltd.)
Rotation speed: 15000rpm
Rotation time: 10 minutes Temperature: 15 ° C

The amorphous polyester resin has a glass transition point (Tg) of 50 to 80 ° C., preferably 60 to 80 ° C. More preferably, it is 65 to 80 ° C., and still more preferably 70
It is thru | or 76 degreeC. Particularly preferred is 73 to 76 ° C. When the glass transition point is less than 50 ° C., the toner has low blocking resistance and durability. When the glass transition point exceeds 80 ° C., the fixing property at low temperature and the low temperature offset resistance of the toner are deteriorated. Tg represents a value obtained by the midpoint method.

  The amorphous polyester resin preferably has a weight average molecular weight (Mw) of 6,000 to 100,000, more preferably 6,500 to 85,000, still more preferably 6,500 to 45,000. is there.

  When the amorphous polyester resin has a weight average molecular weight of less than 6,000, the external additive on the toner surface is likely to be buried due to durability in continuous image output, and transferability is likely to be lowered. On the contrary, when the weight average molecular weight exceeds 100,000, it takes much time to dissolve the amorphous polyester resin in the polymerizable monomer. Further, the viscosity of the polymerizable monomer composition increases, and it becomes difficult to obtain a toner having a small particle size and a uniform particle size distribution.

  The amorphous polyester resin preferably has a number average molecular weight (Mn) of 3,000 to 80,000, more preferably 3,500 to 60,000, still more preferably 3,500 to 12,000. is there. The amorphous polyester resin has a molecular weight distribution main peak value (Mp) in a gel permeation chromatogram (GPC) in the region of a molecular weight of 4,500 to 40,000, more preferably a molecular weight of 6,000 to 30,000. It is good to exist in the area. A region having a molecular weight of 6,000 to 20,000 is more preferable. When it is out of the above range, the same tendency as in the case of the weight average molecular weight is exhibited.

  The amorphous polyester resin has a Mw / Mn of 1.2 to 3.0, more preferably 1.5 to 2.5. When Mw / Mn is 1.2 or more, it is desirable from the viewpoint of durability of a large number of toner sheets and offset resistance, and when it is 3.0 or less, it is desirable from the viewpoint of low-temperature fixability.

  Examples of the method for producing the amorphous polyester resin include a method using a dehydration condensation reaction from a carboxylic acid compound and an alcohol compound, and a transesterification reaction. The catalyst may be a general acidic or alkaline catalyst used in the esterification reaction, such as zinc acetate or a titanium compound. A titanium compound is preferably used. Thereafter, it may be highly purified by a recrystallization method, a distillation method or the like.

  A particularly preferred production method is a dehydration condensation reaction from a carboxylic acid compound and an alcohol compound because of the diversity of raw materials and the ease of reaction.

  The composition of the polyester when polyester is used as the condensation resin will be described below.

  It is preferable that 43-57 mol% of polyester is an alcohol component and 57-43 mol% is an acid component among all the components.

で示されるジオールの如きジオール類が挙げられる。 As alcohol components, ethyl glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexane Diol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, the following formula (I)

Diols such as the diol represented by

  Divalent carboxylic acids include phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, diphenyl-P · P′-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, diphenylmethane Benzenedicarboxylic acids such as P · P'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, 1,2-diphenoxyethane-P · P'-dicarboxylic acid or anhydrides thereof; succinic acid, adipic acid, sebacin Acids, azelaic acid, glutaric acid, cyclohexanedicarboxylic acid, triethylenedicarboxylic acid, alkyldicarboxylic acids such as malonic acid or anhydrides thereof, and succinic acid substituted with an alkyl group or alkenyl group having 6 to 18 carbon atoms or its Anhydrides such as fumaric acid, maleic acid, citraconic acid, itaconic acid Saturated dicarboxylic acid or an anhydride thereof.

  A particularly preferred alcohol component is a bisphenol derivative represented by the above formula (I), and an acid component is phthalic acid, terephthalic acid, isophthalic acid or its anhydride, succinic acid, n-dodecenyl succinic acid, or its anhydride. And dicarboxylic acids such as fumaric acid, maleic acid and maleic anhydride.

  The polyester unit can be obtained by synthesizing from a divalent dicarboxylic acid and a divalent diol, but in some cases, a tricarboxylic or higher polycarboxylic acid or polyol may not be adversely affected by the present invention. May be used in small quantities.

  Trivalent or higher polycarboxylic acids include trimellitic acid, pyromellitic acid, cyclohexanetricarboxylic acids, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid Acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropane, 1,3-dicarboxyl-2-methyl-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2 , 7,8-octanetetracarboxylic acid and their anhydrides.

Examples of the trivalent or higher polyol include sulfitol, 1,2,3,6-hexanetetol,
1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-methanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, Examples include trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene.

  The amorphous polyester resin is preferably an aromatic saturated polyester. This is because the toner has excellent chargeability, durability, and fixability, and the physical properties of the toner and polyester can be easily controlled. In particular, the chargeability is excellent due to the interaction of aromatic π electrons. In addition, when the unsaturated polyester is contained, the unsaturated portion reacts when the toner is produced, and the toner is hardened by cross-linking.

  The glass transition point of the toner and the polyester resin and the melting point of the wax are determined by DSC measurement.

  In DSC measurement, from the measurement principle, it is preferable to measure with a differential scanning calorimeter of high accuracy internal heat type input compensation type. For example, DSC-7 manufactured by Perkin Elmer and DSC-2920 manufactured by TA Instruments Japan can be used.

In the present invention, the measurement is performed using DSC-2920 manufactured by TA Instruments Japan.
The measurement method is performed according to ASTM D3418-82. 10 mg of the measurement sample is precisely weighed. It is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rising rate of 10 ° C./min within a measurement range of 30 to 200 ° C. A specific heat change is obtained in the temperature range of 40 ° C. to 100 ° C. during this temperature raising process. At this time, the point of intersection between the midpoint of the baseline before and after the change in specific heat and the differential heat curve is defined as the glass transition point. Moreover, the maximum endothermic peak temperature of the wax component is obtained from the obtained DSC curve at the time of temperature increase.

  The toner used in the present invention preferably contains a resin having a sulfonic acid group or a sulfonic acid group or a sulfonic acid ester group. This is because the chargeability of the toner is stable during long-term use.

  Furthermore, the glass transition temperature of the resin having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group is preferably 50 to 100 ° C, more preferably 50 to 80 ° C. This is because if the glass transition temperature is 100 ° C. or higher, the toner fixability is lowered, and if it is lower than 50 ° C., the storage stability is poor, and it is not desirable because it easily causes member contamination in the image forming process.

  The resin having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group preferably has a certain acid value, and generally in combination with a colorant often having basicity, Since the base of the colorant is distributed so as to be bonded, the charge leakage site of the pigment is covered with the resin, so that the toner has excellent chargeability, which is preferable.

  Examples of the monomer used for producing the resin having a sulfonic acid group or a sulfonic acid group or a sulfonic acid ester group include styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and 2-methacrylamide-2. -Methylpropane sulfonic acid vinyl sulfonic acid, methacryl sulfonic acid, or maleic acid amide derivatives, maleimide derivatives and styrene derivatives having the following structure. Preferred is (meth) acrylamide containing a sulfonic acid group.

  The resin having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group may be a homopolymer of the monomer, but may be a copolymer of the monomer and another monomer. Preferably there is. As the monomer that forms a copolymer with the above monomer, polymerizable monomers such as vinyl aromatic hydrocarbons and (meth) acrylic acid esters are preferably used. More specifically, monomers as exemplified below can be used.

Monofunctional polymerizable monomers include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p -Styrene derivatives such as phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2 -Ethylhexyl acrylate Acrylates such as methyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; , Ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n -Nonyl methacrylate, benzyl methacrylate, diethylphosphine Methacrylic acid esters such as ethyl acetate and dibutyl phosphate ethyl methacrylate; Methylene aliphatic monocarboxylic acid esters; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and vinyl formate; Vinyl methyl ether, vinyl Examples thereof include vinyl ethers such as ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, 2,2′-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (methacryloxy-diethoxy) phenyl) propane, Examples include 2,2′-bis (4- (methacryloxypolyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylol methanetoteramethacrylate, divinylbenzene, divinylnaphthalene, and divinyl ether.

  The resin having a sulfonic acid group or a sulfonic acid group or a sulfonic acid ester group may contain 0.01 to 20% by mass of a unit derived from a monomer having the sulfonic acid group or the sulfonic acid group or sulfonic acid ester group. The content is preferably 0.05 to 10% by mass, more preferably 0.1 to 7% by mass. When the amount is less than 0.01% by mass, the effect of adding the resin having the sulfonic acid group, sulfonate group, or sulfonic acid ester group cannot be sufficiently obtained. In this case, the compatibility with the binder resin tends to deteriorate, which is not desirable for controlling the toner shape. In addition, it is not desirable because impurities are likely to remain because moisture and counter ions are easily retained due to increased hygroscopicity during production.

  The resin having a sulfonic acid group or a sulfonic acid group or a sulfonic acid ester group has a monomer unit having an ionic group, a nonionic electron donating group, and an aromatic group having no electron withdrawing group as a substituent in the side chain. The content is preferably 0.01 to 10% by mass, and more preferably 0.10 to 5.0% by mass, since the dispersion state in the toner becomes better. In particular, in the case of an acrylic ester or methacrylic ester monomer unit, the effect is great.

  The method for producing a resin having a sulfonic acid group or a sulfonic acid group or a sulfonic acid ester group includes bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, ionic polymerization, etc., but solution polymerization is preferable from the viewpoint of operability. preferable.

Resin having the sulfonic acid group or sulfonic acid group, sulfonic acid ester group,
X (SO ₃ ⁻ ) n · mY ^{k +}
(X represents a polymer site derived from the polymerizable monomer, Y + represents a counter ion,
k is the valence of the counter ion, m and n are integers, and n = k × m. )
It has the following structure. Counter ions are preferably hydrogen ions, sodium ions, potassium ions, calcium ions, and ammonium ions, and more preferably hydrogen ions.

  The acid value (mgKOH / g) of the resin having a sulfonic acid group or a sulfonic acid group or a sulfonic acid ester group is preferably 3 to 80, more preferably 5 to 40, and still more preferably 10 to 30.

  When the acid value is less than 3, it is difficult to obtain a sufficient charge control action, and the environmental stability tends to be inferior. On the other hand, when the acid value exceeds 80, when particles are produced by suspension polymerization using a composition containing such a resin, the toner particles have an irregular shape and the circularity is low. The release agent contained in the toner appears on the toner surface and tends to cause a decrease in developability.

  The resin having a sulfonic acid group or a sulfonic acid group or a sulfonic acid ester group is preferably contained in an amount of 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the binder resin. Is good.

  When the content of the monomer having a sulfonic acid group or a sulfonic acid group or a sulfonic acid ester group is less than 0.01 parts by mass, it is difficult to obtain a sufficient charge control action. When granulation is performed in a medium, the granulation property is lowered, and developability and transferability are lowered.

  Furthermore, in the present invention, it is preferable to contain a unit derived from a monomer having a sulfonic acid group or a sulfonic acid group or a sulfonic acid ester group in an amount of 0.001 to 3 parts by mass per 100 parts by mass of the binder resin. Further, 0.005 to 2 parts by mass, particularly 0.01 to 1.5 parts by mass is preferable.

  The content of the resin having a sulfonic acid group or a sulfonic acid group or a sulfonic acid ester group in the toner is measured by an arbitrary method such as X-ray photoelectron spectroscopy. Moreover, it can also measure using capillary electrophoresis etc.

  The resin having a sulfonic acid group or a sulfonic acid group or a sulfonic acid ester group preferably has a weight average molecular weight (Mw) of 500 to 100,000. More preferably, it is 1,000 to 70,000, and still more preferably 5,000 to 50,000. When the weight average molecular weight (Mw) is less than 500, it is likely to cause member contamination. When the weight average molecular weight (Mw) exceeds 100,000, it takes time to dissolve in the monomer. Due to the decrease in compatibility, the toner is not uniformly dispersed in the toner, the effect on the chargeability of the toner is not sufficiently obtained, and further, the effect of improving the dispersibility of the pigment is reduced, and the coloring power of the toner is lowered. .

  In addition, in obtaining the physical properties as described above, the extraction method is not particularly limited when extraction from a toner having a sulfonic acid group or a sulfonic acid group or a sulfonic acid ester group is required. Can be handled.

It is desirable that the toner has at least a peak or a shoulder between 2,000 and 5,000 in the weight average molecular weight (Mw) measured by gel permeation chromatography of tetrahydrofuran (THF) soluble content of the toner. . This is because the toner has excellent low-temperature fixability, offset resistance, and durability.

  The molecular weight and molecular weight distribution of the resin having toner, sulfonic acid or sulfonate group, and sulfonic acid ester are measured by GPC under the following conditions.

  The molecular weight and molecular weight distribution by GPC of a resin having a binder resin, a sulfonic acid group or a sulfonic acid group, and a sulfonic acid ester group are measured by the following method.

Using a GPC measuring device (HLC-8120GPC manufactured by Tosoh Corporation), measurement can be performed under the following measurement conditions.
<Measurement conditions>
Column (manufactured by Showa Denko KK): Shodex GPC KF-801, Shodex GPC KF-802, Shodex GPC KF-803, Shodex GPC KF-804, Shodex GPC KF-805, Shodex GPC KF-806, G 807 (diameter 8.0mm, length 30cm) 7 stations ・ Temperature: 40 ℃
・ Flow rate: 1.0 ml / min
・ Eluent: Tetrahydrofuran (THF)
・ Detector: RI
・ Sample injection amount: 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) are used.

  The sample is prepared as follows.

  Place the sample in tetrahydrofuran (THF) and let it stand for several hours, then shake well and mix well with THF (until the sample is no longer united), and let stand for more than 12 hours. At this time, the standing time in THF is set to be 24 hours or longer. 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. Measurement is performed using this sample solution.

  In the present invention, the acid value (AV1) of the amorphous polyester resin and the acid value (AV2) of the resin having a sulfonic acid group or a sulfonic acid group or a sulfonic acid ester group are AV1 <AV2 <3.5. XAV1 is desirable, AV1 <AV2 <2.5 × AV1 is more preferable, and AV1 <AV2 <2.0 × AV1 is more preferable. In this case, in the granulation step at the time of production of toner particles by a wet method, a resin having a sulfonic acid group or a sulfonic acid group or a sulfonic acid ester group coexists with an amorphous polyester resin in an aqueous medium. Since the ratio of uneven distribution on the outermost surface of the droplets increases, the charging ability of the toner is preferable because the charging performance of a resin having a sulfonic acid group or a sulfonic acid group or a sulfonic acid ester group can be effectively exhibited. In the present invention, particularly in the case of AV1 <AV2 <2.0 × AV1, the existence state of the resin having a sulfonic acid group or a sulfonic acid group or a sulfonic acid ester group and an amorphous polyester resin is optimized. Therefore, heat conduction during fixing is performed uniformly and quickly from any toner surface, which is desirable in terms of fixability.

  This effect is remarkable when the wax contained in the toner is a polymethylene wax such as paraffin wax, polyolefin wax, microcrystalline wax, and Fischer-Tropsch wax. This is because the polymethylene wax is less polar and less distributed in the vicinity of the toner surface than the ester wax and the like, and as a result, the resin having a sulfonic acid group or a sulfonic acid group or a sulfonic acid ester group is non-crystalline. This is because the influence of the presence state of the polyester resin is increased. At this time, the method for measuring the acid value of the resin having a sulfonic acid group or a sulfonic acid group or a sulfonic acid ester group is the same as the method for measuring the acid value of the amorphous polyester resin.

  It is desirable that the toner has at least a peak or a shoulder between 2,000 and 5,000 in the weight average molecular weight (Mw) measured by gel permeation chromatography of tetrahydrofuran (THF) soluble content of the toner. . This is because the toner has excellent low-temperature fixability, offset resistance, and durability.

  The wax preferably has a weight average molecular weight (Mw) of 350 to 4,000 and a number average molecular weight (Mn) of 200 to 4,000, more preferably Mw of 400 to 3,500 and Mn of 250 to 4,000. 3,500. When Mw is less than 350 and Mn is less than 200, the blocking resistance of the toner tends to decrease. When Mw exceeds 4,000 and Mn exceeds 4,000, the crystallinity of the wax itself. And the transparency of the OHP fixed image tends to decrease.

The molecular weight and molecular weight distribution of the wax are measured by gel permeation chromatography (GPC) as follows.
To o-dichlorobenzene for gel chromatography, special grade 2,6-di-t-butyl-4-methylphenol (BHT) is added so that the concentration becomes 0.10 wt / vol%, and dissolved at room temperature. The wax and o-dichlorobenzene to which the above BHT is added are put into a sample bottle and heated on a hot plate set at 150 ° C. to dissolve the wax. Once the wax has melted, place it in a preheated filter unit and place it on the body. The sample that has passed through the filter unit is used as a GPC sample. The sample solution is adjusted so that the concentration is about 0.15% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
Detector: RI for high temperature
Column: TSKgel GMHHR-H HT 2 series (manufactured by Tosoh Corporation)
Temperature: 135.0 ° C
Solvent: o-dichlorobenzene for gel chromatography (BHT added at 0.10 wt / vol%)
Flow rate: 1.0 ml / min
Injection volume: 0.4ml
In calculating the molecular weight of the wax, 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) are used.

  In the toner of the present invention, a low softening point material, so-called wax, can be used as necessary.

At least one of the waxes used in the present invention has a melting point (temperature corresponding to the maximum endothermic peak of the DSC endothermic curve in the temperature range of 20 to 200 ° C.) of 30 to 120 ° C., preferably 50 to 100 ° C. . A solid wax that is solid at room temperature is preferable, and a solid wax having a melting point of 50 to 100 ° C. is particularly preferable in terms of toner blocking resistance, durability of a large number of sheets, low-temperature fixability, and offset resistance.

  Examples of the wax component that functions as a release agent used in the toner of the present invention include plant waxes such as carnauba wax, rice wax, and candelilla wax, petroleum waxes such as paraffin wax, polyolefin wax, and microcrystalline wax, and Fischer tropical. Examples include polymethylene wax such as Schwax, polyethylene wax, polypropylene wax, amide wax, higher fatty acids, long chain alcohols, ketones, ethers, ester waxes and their graft compounds, and derivatives such as block compounds. It is preferable that the DSC endothermic curve from which the component is removed has a sharp maximum endothermic peak.

  Further, those obtained by removing impurities such as liquid fatty acid from these waxes in advance are also preferred.

  In addition, it is more desirable that these waxes have appropriate moisture resistance when used in a high temperature and high humidity environment.

  As the wax preferably used, at least one of the wax is advantageous for embedding in the toner and free wax is hardly generated, so that the developability of the toner is not hindered. Therefore, at least one of the wax is a paraffin wax, a polyolefin wax, a microcrystalline wax, a fisher Examples include polymethylene waxes such as Tropsch wax and ester waxes. Particularly preferred is Fischer-Tropsch wax. The effect of the toner of the present invention is particularly remarkable when it is Fischer-Tropsch wax or ester wax. Among these, the thing whose melting | fusing point is in the range of 60-100 degreeC is preferable. The ester wax is more preferably a polyfunctional ester compound formed from a trifunctional or higher polyhydric alcohol and a carboxylic acid.

  Examples of the trifunctional or higher polyhydric alcohol include aliphatic alcohols such as glycerin, pentaerythritol, and pentaglycerol; alicyclic alcohols such as phloroglucitol, quercitol, and inositol; and aromatics such as tris (hydroxymethyl) benzene. Alcohol; sugars such as D-erythrose, L-arabinose, D-mannose, D-galactose, D-fructose, L-rhamnose, saccharose, maltose, lactose; erythritol, D-trayt, L-arabit, adnit, xylit, etc. Sugar alcohols; and the like. Among these, pentaerythritol is preferable.

Examples of the carboxylic acid include acetic acid, butyric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, stearic acid, margaric acid, arachidic acid, serotic acid, melicic acid, Aliphatic carboxylic acids such as ericic acid, brassic acid, sorbic acid, linoleic acid, linolenic acid, behenic acid, tetrolic acid, ximenic acid; cyclohexanecarboxylic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 3, 4, 5, Alicyclic carboxylic acids such as 6-tetrahydrophthalic acid; aromatic carboxylic acids such as benzoic acid, toluic acid, cumic acid, phthalic acid, isophthalic acid, terephthalic acid, trimesic acid, trimellitic acid, hemimellitic acid; Can do. Among these, a carboxylic acid having preferably 10 to 30 carbon atoms, more preferably 13 to 25 carbon atoms is preferable, and an aliphatic carboxylic acid having the number of carbon atoms is more preferable. Of the aliphatic carboxylic acids, stearic acid and myristic acid are particularly preferable. As a polyfunctional ester compound,
Formula (I)

（ただし、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は、それぞれ独立にアルキル基またはフェニル基であり、アルキル基またはフェニル基の炭素原子数は、好ましくは１０〜３０個、より好ましくは１３〜２５個である。）で表される化合物が好ましい。

(However, R ¹ , R ² , R ³ , and R ⁴ are each independently an alkyl group or a phenyl group, and the alkyl group or the phenyl group preferably has 10 to 30 carbon atoms, more preferably 13 carbon atoms. To 25.) is preferred.

Specific examples of the polyfunctional ester compound include pentaerythritol tetrastearate (a compound in which R ¹ , R ² , R ³ , and R ⁴ are all CH ₃ (CH ₂ ) ₁₆ groups in formula (I)). , Pentaerythritol tetramyristate [a compound in which R ¹ , R ² , R ³ , and R ⁴ are all CH ₃ (CH ₂ ) ₁₂ groups in formula (I)], glycerol triaraquinic acid, etc. Can do. The polyfunctional ester compound is preferably one that dissolves easily in the polymerizable monomer.

  Among polyfunctional ester compounds, pentaerythritol esters such as pentaerythritol tetramyristate, pentaerythritol tetrapalmitate, pentaerythritol tetrastearate, and pentaerythritol tetralaurate; dipentaerythritol hexamyristate, dipentaerythritol hexapalmitate And dipentaerythritol esters such as dipentaerythritol hexalaurate are particularly preferred because they are excellent in polymerization stability, blocking resistance during storage of the polymerized toner, and low-temperature fixability. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Furthermore, an ester wax containing 50 to 95% by mass (based on wax) of an ester compound having the same total carbon number is particularly preferable. The content of the ester compound having the same total carbon number can be measured by a gas chromatography method (GC method) described below.

  GC-17A (manufactured by Shimadzu Corporation) is used for measuring the content of ester compounds having the same carbon number by gas chromatography (GC method). As a sample, 1 μl of a solution previously dissolved in toluene at a concentration of 1% by mass is injected into a GC apparatus equipped with an on-column injector. As the column, 0.5 mm diameter × 10 m long Ultra Alloy-1 (HT) is used. The column is initially 40 ° C. to 40 ° C./min. The temperature was increased to 200 ° C. at a temperature increase rate of 15 ° C./min. At 350 ° C. and then 7 ° C./min. The temperature is raised to 450 ° C. at a temperature raising speed of As the carrier gas, He gas is allowed to flow under a pressure condition of 50 kPa. The identification of the compound species is performed by separately injecting alkanes with known carbon numbers and comparing the same outflow times, or by introducing gasification components into mass spectrometry. The ester compound content is calculated by determining the ratio of the peak area to the total peak area of the chromatogram.

  When the toner is produced by the polymerization method, the wax is preferably blended in an amount of 1 to 40 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of the polymerizable monomer. The wax may be contained in an amount of 1 to 40 parts by weight, more preferably 10 to 30 parts by weight, per 100 parts by weight of the binder resin.

Compared with the dry toner manufacturing method, compared to the dry toner manufacturing method, it is easier to encapsulate a large amount of wax inside the toner with the polar resin in the toner manufacturing method using the polymerization method compared to the dry toner manufacturing method using the melt kneading pulverization method. Accordingly, the effect of preventing offset at the time of fixing is further improved.

  If the added amount of wax is less than the lower limit, the effect of preventing offset tends to be lowered. On the other hand, if the upper limit is exceeded, the anti-blocking effect is reduced and the anti-offset effect is likely to be adversely affected, and toner drum fusion and toner development sleeve fusion are likely to occur. Tends to produce toner with a wide particle size distribution.

  The wax used in the present invention preferably has a melt viscosity at 135 ° C. of 1 to 300 cPs, more preferably a wax having 3 to 50 cPs. When the melt viscosity is lower than 1 cPs, when the toner layer is thinly coated on the developing sleeve with a coating blade or the like by the non-magnetic one-component development method, the sleeve is likely to be contaminated by mechanical slippage. If the melt viscosity exceeds 300 cPs, the viscosity of the polymerizable monomer composition becomes high when a toner is produced using a polymerization method, and it is difficult to obtain a toner having a fine particle size with a sharp particle size distribution. It becomes.

  The melt viscosity of the wax can be measured using a cone plate rotor (PK-1) with VP-500 manufactured by HAAKE.

  Further, the penetration of the wax is 14 or less, preferably 4 or less, more preferably 3 or less. When the penetration exceeds 14, filming is likely to occur on the surface of the photosensitive drum. In addition, the measurement of penetration is according to JIS-K2235.

  In addition, when obtaining the physical properties as described above, when the wax needs to be extracted from the toner, the extraction method is not particularly limited, and any method can be used. For example, a predetermined amount of toner is Soxhlet extracted with toluene, and after removing the solvent from the obtained toluene-soluble component, a chloroform-insoluble component is obtained. Thereafter, identification analysis is performed by IR method or the like. In addition, quantitative analysis is performed by DSC or the like.

  The toner of the present invention may use a charge control agent. Examples of the charge control agent for controlling the toner to be negatively charged include the following substances. For example, organometallic compound, chelate compound, monoazo metal compound, acetylacetone metal compound, urea derivative, metal-containing salicylic acid compound, metal-containing naphthoic acid compound, quaternary ammonium salt, calixarene, silicon compound, nonmetal carboxylic acid compound And derivatives thereof. Among these, in the toner of the present invention, a charge control agent such as a metal-containing salicylic acid compound is preferably used. It is particularly preferred when the toner of the present invention is prepared by suspension polymerization.

  In addition, as the charge control agent for controlling the toner to be positively charged, there are the following substances. For example, modified products of nigrosine and fatty acid metal salts, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and phosphonium salts that are analogs thereof Onium salts and their lake pigments, triphenylmethane dyes and their lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, Ferrocyanide, etc.); diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; diorganotin oxides such as dibutyltin borate, dioctyltin borate, dicyclohexyltin borate Lugano tin borate compounds; can be used in combination singly or two or more kinds. Among these, a charge control agent such as a nigrosine-type quaternary ammonium salt is particularly preferably used.

  The charge control agent may be contained in an amount of 0.01 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the binder resin in the toner.

  The binder resin used in the present invention is not particularly limited, and a resin generally used as a toner resin can be used. Specifically, styrene such as polyester resin, polystyrene, polyvinyltoluene, and substituted homopolymers thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic. Acid methyl copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer Polymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, Styrene-vinylmethyl Styrene copolymers such as ton copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate , Polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin, epoxy resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, paraffin wax, Examples include carnauba wax. These can be used alone or in combination.

  In particular, the toner of the present invention may contain a resin having a viscosity of 2,000 ≦ Mw ≦ 6,000 so that the viscosity of the toner measured by a flow tester may be within a desired range. This is desirable because it is easy to achieve both compatibility and durability.

  The toner of the present invention contains a colorant. As the black colorant, carbon black, which is toned to black using the yellow / magenta / cyan colorant shown below, is used.

  As the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds are used as pigments. Specifically, C.I. I. Pigment Yellow 3, 7, 10, 12, 13, 14, 15, 17, 23, 24, 60, 62, 74, 75, 83, 93, 94, 95, 99, 100, 101, 104, 108, 109, 110 111,117,123,128,129,138,139,147,148,150,166,168,169,177,179,180,181,183,185,191: 1,191,192,193,199 Are preferably used. Examples of the dye system include C.I. l. solventYellow33, 56, 79, 82, 93, 112, 162, 163, C.I. I. disperse Yellow 42.64.2011.211.

  As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254, C.I. I. Pigment Bio Red 19 is particularly preferable.

As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment Blue 1,
7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 are particularly preferably used.

  These colorants can be used alone or in combination and further in the form of a solid solution. The colorant of the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The coloring agent is used in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

  When a toner is obtained by using the polymerization method in the present invention, it is necessary to pay attention to the polymerization inhibition property and water phase transfer property of the colorant. Preferably, surface modification of the colorant, for example, hydrophobic treatment with a substance that does not inhibit polymerization is performed. In particular, since dyes and carbon black often have polymerization inhibiting properties, care must be taken when using them. A preferable method for surface-treating the colorant includes a method of polymerizing a polymerizable monomer in the presence of these colorants in advance, and it is preferable to add the obtained colored polymer to the monomer composition. . In addition to carbon black, the carbon black may be grafted with a substance that reacts with the surface functional group of the carbon black, such as polyorganosiloxane.

  Next, a manufacturing method suitably used for the toner of the present invention will be described. As a production method suitably used for the toner of the present invention, suspension polymerization methods described in JP-B-36-10231, JP-A-59-53856, and JP-A-59-61842 are used. Toner by a method of directly producing toner using the toner; an emulsion polymerization method represented by a soap-free polymerization method in which the toner is directly polymerized in the presence of a water-soluble polymerization initiator in the presence of a water-soluble polymerization initiator Conversion to a toner by an interfacial polymerization method such as a microcapsule production method, an in situ polymerization method; a toner formation by a coacervation method; disclosed in JP-A-62-106473 and JP-A-63-186253 Toner formation by an associative polymerization method in which at least one kind of fine particles are aggregated to obtain particles having a desired particle size; Toner formation by a dispersion polymerization method characterized by monodispersion; Method of obtaining a toner by an emulsion dispersion method in which the toner in water was dissolved resins required water-soluble organic solvents.

  Of these, toner production by suspension polymerization, association polymerization, and emulsion dispersion is preferred. Even more preferably, a suspension polymerization method that can easily obtain a toner having a small particle diameter is desired. Furthermore, a seed polymerization method in which a monomer is further adsorbed to the obtained polymer particles and then polymerized using a polymerization initiator can be suitably used in the present invention. At this time, it is also possible to use a compound having polarity dispersed or dissolved in the monomer to be adsorbed.

  When suspension polymerization is used as a toner production method, the toner can be produced directly by the following production method. Dispersing and stabilizing a monomer composition that has been uniformly dissolved or dispersed with a homogenizer, ultrasonic disperser, etc., by adding a release agent, colorant, polymerization initiator, crosslinking agent, or other additives to the monomer The mixture is dispersed in an aqueous medium having an agent by an ordinary stirrer, homomixer, or homogenizer. Preferably, granulation is performed by adjusting the stirring speed and time so that the droplets of the monomer composition have a desired toner size. Thereafter, stirring may be performed to such an extent that the particle state is maintained by the action of the dispersion stabilizer and the sedimentation of the particles is prevented. The polymerization is carried out at a polymerization temperature of 40 ° C. or higher, usually 50 to 95 ° C. (preferably 55 to 85 ° C.). The temperature may be raised in the latter half of the polymerization reaction, and the pH may be changed as necessary. Further, in order to remove unreacted polymerizable monomers, by-products and the like that cause odor during fixing, a part of the aqueous medium may be distilled off in the latter half of the reaction or after the completion of the reaction. After completion of the reaction, the produced toner particles are collected by washing and filtration and dried.

The pH in the aqueous medium during granulation is not particularly limited, but preferably 4.5 to 13.0, more preferably 4.5 to 12.0, and particularly preferably 4.5 to 11.0. Most preferably, it is 4.5-7.5. When the pH is less than 4.5, a part of the dispersion stabilizer dissolves, making it difficult to stabilize the dispersion, and granulation may not be possible. On the other hand, when the pH exceeds 13.0, components added to the toner may be decomposed, and sufficient charging ability may not be exhibited. When granulation is performed in the acidic region, it is possible to suppress an excessive content of the metal derived from the dispersion stabilizer in the toner, and it is easy to obtain a toner that satisfies the provisions of the present invention. Become.

  The toner particles are preferably washed with an acid having a pH of 3 or less, more preferably 1.5 or less. By washing the toner particles with an acid, the dispersion stabilizer present on the surface of the toner particles can be reduced. The acid used for washing is not particularly limited, and inorganic acids such as hydrochloric acid and sulfuric acid can be used. As a result, the chargeability of the toner particles can be adjusted to a desired range.

  Examples of the dispersion stabilizer used in the present invention include magnesium phosphate, tricalcium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, and calcium metasilicate. , Calcium sulfate, barium sulfate, hydroxyapatide and the like.

  Further, as the dispersion stabilizer, those containing at least one of magnesium, calcium, barium, zinc, aluminum and phosphorus are used, but preferably one of magnesium, calcium, aluminum and phosphorus is contained. It is hoped that

  An organic compound such as polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, and starch may be used in combination with the dispersion stabilizer.

  These dispersion stabilizers are preferably used in an amount of 0.01 to 2.00 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  Furthermore, you may use together 0.001-0.100 mass% surfactant for refinement | miniaturization of these dispersion stabilizers. Specifically, commercially available nonionic, anionic and cationic surfactants can be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, and calcium oleate are preferably used.

  As the polymerizable monomer used when the toner of the present invention is produced by the polymerization method, a vinyl polymerizable monomer capable of radical polymerization is used.

As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. Monofunctional polymerizable monomers include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p -Styrene derivatives such as phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2 -Ethylhexyl acrylate , Acrylic polymerizable monomers such as n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-buty methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl Methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate Methacrylic polymerizable monomers such as dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid ester; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, And vinyl ethers such as vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, 2,2'-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (methacryloxy-diethoxy) phenyl) propane, Examples include 2,2'-bis (4- (methacryloxy-polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, and divinyl ether.

  In the present invention, the above monofunctional polymerizable monomers are used alone or in combination of two or more, or the above monofunctional polymerizable monomers and polyfunctional polymerizable monomers are used in combination. To do. The polyfunctional polymerizable monomer can also be used as a crosslinking agent. Furthermore, it is also possible to use these in combination with a macromonomer.

  The polymerization initiator used in the polymerization of the polymerizable monomer described above is an oil-soluble initiator and / or a water-soluble initiator other than those used in the present invention as long as the effects of the present invention are not impaired. An agent can be used as appropriate. For example, as the oil-soluble initiator, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile) Azo compounds such as 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, t-butylperoxyneodecanoate, t-hexylperoxypivalate, lauroyl peroxide, t-butylperoxide Examples thereof include peroxides such as oxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, di-t-butyl peroxyisophthalate, and di-t-butyl peroxide.

Water-soluble initiators include ammonium persulfate, potassium persulfate, 2,2'-azobis (N, N'-dimethyleneisobutyroamidine) hydrochloride, 2,2'-azobis (2-aminodinopropane) hydrochloric acid Salt, azobis (isobutylamidine) hydrochloride, sodium 2,2'-azobisisobutyronitrile sulfonate, 2,2'-azobis {2-methyl-N- [1,1
-Bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'-
Azobis {2-methyl-N- [2- (1-hydroxybutyl)]-propionamide}, hydrochloride ferrous sulfate or hydrogen peroxide.

  In the present invention, in order to control the polymerization degree of the polymerizable monomer, a chain transfer agent, a polymerization inhibitor and the like can be further added and used.

  Moreover, in this invention, it can also be set as resin which has bridge | crosslinking using a crosslinking agent, The compound which has a 2 or more polymerizable double bond can be used as a crosslinking agent. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; divinylaniline; And divinyl compounds such as divinyl ether, divinyl sulfide and divinyl sulfone; and compounds having three or more vinyl groups. These are used alone or as a mixture.

  As a method for controlling the shape factor of the toner particles of the present invention, for example, there is a method for producing a toner by controlling the polymerization conditions when producing toner particles by a polymerization method such as emulsion polymerization, suspension polymerization, dispersion polymerization or the like. Can be mentioned.

  Specifically, the shape factor of the toner particles can be adjusted by controlling the type and amount of the dispersion stabilizer in the production of the toner particles, the stirring conditions, the pH and polymerization conditions of the aqueous layer, and the molecular weight of the additive. it can. Furthermore, after drying the produced toner particles, it is possible to obtain toner particles having a desired particle size, particle size distribution, and circularity by using means such as classification and sieving.

  In addition, in the method of obtaining toner particles using the suspension polymerization method, it is particularly preferable to add the polar resin simultaneously from the viewpoint of allowing the polymerization reaction of the polymerization monomer to occur without hindrance. Examples of polar resins used in the present invention include copolymers of styrene and (meth) acrylic acid, copolymers of styrene and unsaturated carboxylic acid esters, nitrile monomers such as acrylonitrile, and vinyl chloride. Polymers such as halogenated monomers, unsaturated carboxylic acids such as acrylic acid or methacrylic acid, other unsaturated dibasic acids and unsaturated dibasic acid anhydrides, nitro monomers, or these monomers A copolymer with a styrene monomer or the like, a maleic acid copolymer, a polyester resin, or an epoxy resin is preferably used. The polar resin is particularly preferably one containing no unsaturated group capable of reacting with the monomer in the molecule. As addition amount of these polar polymers and / or copolymers, 0.1-30 mass% of a polymerizable monomer is preferable, and it is especially preferable in it being 0.5-20 mass%.

  In the toner of the present invention, various inorganic and organic additives can be used for the purpose of imparting various properties. The additive to be used preferably has a particle size of 1/10 or less of the weight average diameter of the toner particles from the viewpoint of durability when added to the toner. The particle size of the additive means the average particle size obtained by observing the surface of the toner particles with a scanning electron microscope. As additives for the purpose of imparting these characteristics, for example, the following are used, but are not particularly limited.

  1) Fluidity-imparting agents: metal oxides (silica, hydrophobic silica, silicon oxide, aluminum oxide, titanium oxide, etc.), carbon black, carbon fluoride, etc. Each of them is more preferably hydrophobized.

2) As abrasives: metal oxides (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide, etc.), nitrides (silicon nitride, etc.), carbides (silicon carbide, etc.), metal salts (calcium sulfate, Barium sulfate, calcium carbonate, etc.) are preferred.

  3) As the lubricant: Fluorine-based resin powder (vinylidene fluoride, polytetrafluoroethylene, etc.) is preferable.

  4) As the charge controllable particles: metal oxides (tin oxide, titanium oxide, zinc oxide, silicon oxide, aluminum oxide, etc.), carbon black and the like are preferable.

  In addition, the organic fine particles include, for example, a single component of a monomer component used for a binder resin for toner such as styrene, acrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate by an emulsion polymerization method or a spray drying method. A polymer or copolymer can be used as appropriate.

  These additives may be used in an amount of 0.01 to 5 parts by mass (preferably 0.02 to 3 parts by mass) with respect to 100 parts by mass of the toner. These additives may be used alone or in combination. Of these additives, the inorganic fine particles are desirably hydrophobized. The range of the degree of hydrophobicity is preferably 20% or more and 99% or less, more preferably 40% or more and 99% or less, and particularly in the case of silica, 80% or more is desirable.

<Measurement method of hydrophobicity of inorganic fine powder>
The methanol titration test is an experimental test for confirming the degree of hydrophobicity of an inorganic fine powder having a hydrophobized surface. The “methanol titration test” for evaluating the degree of hydrophobicity of the treated inorganic fine powder is performed as follows. 0.2 g of the test inorganic fine powder is added to 50 ml of water in the container. Methanol is titrated from the burette until the entire amount of inorganic fine powder is wet. At this time, the solution in the container is constantly stirred with a magnetic stirrer. The end point is observed by suspending the total amount of inorganic fine powder in the liquid, and the degree of hydrophobicity is expressed as the percentage of methanol in the liquid mixture of methanol and water when the end point is reached.

  As the method for hydrophobizing the inorganic fine particles, a conventionally known method is used. For example, specifically, the titanium oxide fine particles are heated in advance to 100 to 150 ° C. under vacuum and stored in a desiccator to remove water. For example, a method (solvent wet processing method) in which dehydrated titanium oxide fine particles and a silane coupling agent are reacted in toluene to hydrophobize OH groups on the surface of titanium oxide. In addition, a solvent dry spray method, an aqueous emulsion treatment method, an aqueous hydrolysis method and the like can be mentioned.

  Silane coupling agents, titanium coupling agents, silicone oils and the like can be used as hydrophobic treatment agents for hydrophobizing inorganic fine particles as follows.

Examples of silane coupling agents include hexamethyldisilazane, methyltrimethoxysilane, octyltrimethoxysilane, isobutyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-aminopropyl. Trimethoxysilane, γ- (2-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, methyltrichlorosilane , Dimethyldichlorosilane, trimethylchlorosilane, γ-glycidoxypropyltrimethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, Diethylaminopropyltrimethoxysilane, dipropylaminopropyltrimethoxysilane, dibutylaminopropyltrimethoxysilane, monobutylaminopropyltrimethoxysilane, dioctylaminopropyltrimethoxysilane, dibutylaminopropyldimethoxysilane, dibutylaminopropylmonomethoxysilane, dimethyl Examples thereof include aminophenyltriethoxysilane, trimethoxysilyl-γ-propylphenylamine, trimethoxysilyl-γ-propylbenzylamine, γ-anilinopropyltrimethoxysilane, polyethyleneimine-containing silane, and the like. Octyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane are preferable, and γ-mercaptopropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane are more preferable.

  Examples of the titanium coupling agent include bis [dioctyl pyrophosphate] oxyacetate titanate, bis [dioctyl pyrophosphate] ethylene titanate, tetrabutyl titanate, and tetraoctyl titanate. Particularly preferred is bis [dioctylpyrophosphate] ethylene titanate.

  Further, it is desirable to add silica fine powder treated with silicone oil to the toner particles.

  The inorganic fine powder used in the present invention is preferably hydrophobic, and various coupling agents such as a silane coupling agent and a titanium coupling agent can be used, but the degree of hydrophobicity should be increased with silicone oil. Therefore, moisture adsorption of the inorganic fine powder under high humidity is suppressed, and further, contamination of the regulating member and the charging member is suppressed, so that a high-quality image can be obtained, which is more preferable.

  Examples of the silicone oil include dimethyl silicone oil, alkyl-modified silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, carboxylic acid-modified silicone oil, alcohol-modified silicone oil, α-methylstyrene-modified silicone oil, methylphenyl silicone oil, and chlorophenyl silicone. Oils, fluorine-modified silicone oils, and the like, and those having aromatic functional groups such as chlorophenyl silicone oil and methylphenyl silicone oil, amino-modified silicone oils, and epoxy-modified silicone oils are preferred. It is not limited.

The silicone oil preferably has a viscosity of 50 to 1,000 mm ² / s at a temperature of 25 ° C. If it is less than 50 mm ² / s, it is partially volatilized by the application of heat, and the charging characteristics tend to deteriorate. In the case of exceeding 1,000 mm ² / s, handling becomes difficult in terms of processing work. A known technique can be used as a method for treating the silicone oil. For example, silicate fine powder and silicone oil are mixed using a mixer. Silicone oil is sprayed into the silicate fine powder using a sprayer. Or the method of mixing a silicic acid fine powder after dissolving silicone oil in a solvent is mentioned. The processing method is not limited to this.

  Next, the toner of the present invention can be applied to, for example, the following image forming method, process cartridge and developing device. Details will be described below.

  First, FIG. 2 shows a specific example of an image forming method and a developing apparatus in a non-magnetic one-component contact developing method applied to the present invention. In FIG. 2, a developing device 13 is located in a developer container 23 containing a non-magnetic toner 17 as a one-component developer, and an opening extending in the longitudinal direction in the developer container 23. A drum) 10 and a toner carrier 14 disposed opposite to each other, and an electrostatic latent image on the latent image carrier 10 is developed and visualized. The photoreceptor contact charging member 11 is in contact with the latent image carrier 10. The bias of the photoreceptor contact charging member 11 is applied by a power supply 12.

The toner carrier 14 has a substantially half right peripheral surface shown in the drawing through the opening and enters the developing container 23.
The substantially left half circumferential surface is exposed outside the developer container 23 and is arranged horizontally. The surface exposed to the outside of the developing container 23 is in contact with the latent image carrier 10 located on the left side of the developing device 13 as shown in FIG.

The toner carrier 14 is rotationally driven in the direction of the arrow B, and the surface thereof has appropriate unevenness for increasing the probability of rubbing with the toner 17 and carrying the toner 17 well. When the toner carrier 14 is used by contacting the latent image carrier 10 with the toner carrier 14 as shown in FIG. 2, as an example, the NBR base layer is coated with ether urethane as a surface layer, having a diameter of 14 to 25 mm and a surface. An elastic roller having a roughness Rz of 0.1 to 10 μm and a resistance of 10 ⁴ to 10 ⁸ Ω can be used. The peripheral speed of the latent image carrier 10 is 50 to 170 mm / s, and the peripheral speed of the toner carrier 14 is rotated at a peripheral speed of 1 to 2 times the peripheral speed of the latent image carrier 10.

  At the upper position of the toner carrier 14, a metal plate such as SUS, a rubber material such as urethane and silicone, or a metal thin plate of SUS or phosphor bronze having spring elasticity is used as a base, and the contact surface to the toner carrier 14. A regulating member 16 made of a rubber material bonded to the side is supported by the blade support metal plate 24 and is provided so that the vicinity of the free end side is in contact with the outer peripheral surface of the toner carrier 14 by surface contact. The contact direction is a so-called counter direction in which the tip side with respect to the contact portion is located upstream of the rotation direction of the toner carrier 14. As an example of the toner regulating member, a plate-like urethane rubber having a thickness of 1.0 to 1.5 mm is bonded to the contact portion or the entire surface of the blade support sheet metal 24, and the contact pressure against the toner carrier 14 is set. Are set as appropriate. The linear pressure was converted from a value obtained by inserting three metal thin plates having a known friction coefficient into the abutting portion and pulling out the central one with only a spring. In addition, an L-shaped metal plate may be used for the restricting member 16, and a method in which a portion corresponding to an L-shaped corner is brought into contact with the toner carrier 14 may be used.

  The elastic roller 15 is in contact with the contact portion of the toner regulating member 16 with the surface of the toner carrier 14 on the upstream side in the rotation direction of the toner carrier 14 and is rotatably supported. Examples of this structure include a foamed skeleton-like sponge structure and a fur brush structure in which fibers such as rayon and nylon are planted on a cored bar in terms of supplying the toner 17 to the toner carrier 14 and stripping off the undeveloped toner. As an example of the elastic roller, an elastic roller 15 having a diameter of 12 to 18 mm in which a polyurethane foam is provided on the core metal 15a is used. As the contact width of the elastic roller 15 with respect to the toner carrier 14, 0.5 to 8 mm is effective, and it is preferable that the toner carrier 14 has a relative speed at the contact portion.

  In this developing portion, the toner layer formed on the toner carrier 14 is formed by a DC bias applied between the toner carrier 14 and the latent image carrier 10 by the power source 27 as shown in FIG. The electrostatic latent image on the latent image carrier 10 is developed as a toner image.

  Although the above description has been given of the development method and the case where the present invention is applied to a process cartridge comprising a developing device detachable from the image forming apparatus main body, the developing apparatus is configured to be fixed in the image forming apparatus main body and replenish only toner. You may apply to. In addition, the photosensitive drum, cleaning blade, waste toner container, and charging device can be provided with at least the above-described developing device, or can be applied to a process cartridge that can be attached to and detached from the image forming apparatus main body. May be.

  Further, when there is a step of cleaning the toner remaining on the photoconductor without being transferred by placing a blade-like cleaning member in pressure contact with the photoconductor, etc., in order to facilitate cleaning in the previous stage of the cleaning step. It is desirable to add a static eliminating step for neutralizing the surface of the photoreceptor.

  Furthermore, it is possible to apply a bias to the elastic roller 15 and the toner regulating member 16 that are toner supply members by using the power source 9, and in FIG. 2, the applied bias is a bias in which a DC bias is superimposed on an AC bias. FIG. 3 is a schematic diagram of the image apparatus when only a DC bias is applied.

  Further, an image forming method by non-magnetic one-component non-contact development using a non-magnetic one-component developer and a developing apparatus will be described with reference to a schematic configuration diagram shown in FIG.

  The developing device 170 carries a developing container 171 containing a non-magnetic one-component developer 176 as non-magnetic toner, and a one-component non-magnetic developer 176 contained in the developing container 171 and transports it to the developing area. Developer carrier 172 for supply, supply roller 173 for supplying a one-component non-magnetic developer onto the developer carrier, developer layer thickness regulation for regulating the developer layer thickness on the developer carrier An elastic blade 174 as a member and a stirring member 175 for stirring the one-component nonmagnetic developer 176 in the developing container 171 are provided.

Reference numeral 169 denotes a latent image carrier for carrying an electrostatic latent image, and the latent image is formed by electrophotographic process means or electrostatic recording means (not shown). Reference numeral 172 denotes a developing sleeve as a developer carrying member, which is a nonmagnetic sleeve made of aluminum or stainless steel. Alternatively, an elastic roller such as the toner carrier 14 shown in FIG. 2 may be used as the developer carrier. In general, the developing sleeve includes an aluminum or stainless steel rough tube as it is, a surface whose surface is sprayed with glass beads to be uniformly roughened, a mirror-finished one, or a resin-coated one. However, in the present invention, it is unsuitable for setting μd to 1.35 or more, and an elastic roller is used as a developer carrier.

  The one-component nonmagnetic developer 176 is stored in the developing container 171 and is supplied onto the developer carrier 172 by the supply roller 173. The supply roller 173 is made of a foam material such as polyurethane foam, and rotates with a relative speed other than 0 in the forward or reverse direction with respect to the developer carrier, and the developer on the developer carrier 172 is developed along with the supply of the developer. The subsequent developer (undeveloped developer) is also stripped off. The one-component nonmagnetic developer supplied onto the developer carrier 172 is uniformly and thinly applied by an elastic blade 174 as a developer layer thickness regulating member.

  In this non-magnetic one-component non-contact development method, in a system in which a one-component non-magnetic developer is thinly coated on a developer carrier with a blade, in order to obtain a sufficient image density, the developer carrier It is preferable to make the thickness of the one-component nonmagnetic developer layer smaller than the facing gap α between the developer carrying member and the latent image carrying member, and to apply an alternating electric field to this gap. That is, by applying a developing bias in which a DC electric field is superimposed on an alternating electric field or an alternating electric field between the developing sleeve 172 and the latent image carrier 169 by a bias power source shown in FIG. It is possible to facilitate the movement of the one-component nonmagnetic developer and obtain a higher quality image.

  In the present invention, the gap α between the latent image carrier and the developer carrier is set to, for example, 50 to 500 μm, and the layer thickness of the developer layer carried on the developer carrier is, for example, 40 to 400 μm. It is preferably set.

The developing sleeve is rotated at a peripheral speed of 100 to 200% with respect to the latent image carrier. The alternating bias voltage may be 0.1 kV or more, preferably 0.2 to 3.0 kV, more preferably 0.3 to 2.0 kV, peak-to-peak. The alternating bias frequency is 1.0 to 5.0 kHz, preferably 1.0 to 3.0 kHz, and more preferably 1.5 to 3.0 kHz. A waveform such as a rectangular wave, a sine wave, a sawtooth wave, or a triangular wave can be applied to the alternating bias waveform. In addition, asymmetrical AC bias with different forward and reverse voltages and time can be used. It is also preferable to superimpose a DC bias.

  Furthermore, it is possible to apply a bias to the supply roller 173 and the elastic blade 174, which are toner supply members, using the power source 9, and FIG. 4 shows the case where the applied bias is a bias in which a DC bias is superimposed on an AC bias. FIG. 5 is a schematic diagram of the image apparatus when only a DC bias is applied.

  In the non-magnetic one-component developer, in both non-magnetic one-component contact development and non-magnetic one-component non-contact development, the contact pressure between the toner layer regulating member and the developer carrier is in the direction of the developer carrier bus. The linear pressure P (nip) [N / m] is preferably in contact with a linear pressure that satisfies the condition of 10 ≦ P (nip) ≦ 45. When the contact pressure is less than 10 N / m, uniform application of the one-component nonmagnetic developer becomes difficult, and the charge amount distribution of the one-component nonmagnetic developer becomes broad, causing fogging and scattering. If the contact pressure exceeds 45 N / m, a large pressure is applied to the one-component non-magnetic developer and the one-component non-magnetic developer deteriorates. It is not preferable that toner fusing to the regulating member and the toner carrier occurs. Further, it is not preferable because a large torque is required to drive the developer carrying member. That is, by adjusting the contact pressure to 10 to 45 N / m, it becomes possible to effectively loosen the aggregation of the one-component nonmagnetic developer using the toner of the present invention, and further, the one-component nonmagnetic It becomes possible to instantly raise the charge amount of the developer.

  As the elastic blade as the toner layer regulating member, rubber elastic bodies such as silicone rubber, urethane rubber and NBR; elastomers such as polyethylene terephthalate and polyamide; metal elastic bodies such as stainless steel, steel and phosphor bronze can be used. Even a complex can be used. Preferably, a material obtained by injection-molding rubber materials such as urethane and silicone and various elastomers such as polyamide elastomer on a metal thin plate of SUS or phosphor bronze having spring elasticity is preferable.

  In addition, in order to produce a sufficient image density, excellent dot reproducibility, and development without fogging or aggregation of one-component non-magnetic developer and toner fusion to the toner layer regulating member and toner carrier, The contact width (development nip) between the toner carrier and the toner layer regulating member is preferably 0.20 mm to 1.50 mm, more preferably 0.20 mm to 1.10 mm, and more preferably 0.25 to 0 More preferably, it is 80 mm. If the development nip is narrower than 0.20 mm, it is difficult to satisfactorily satisfy a sufficient image density and dot reproducibility. If the development nip is wider than 1.50 mm, the stress on the developer increases, so fog or one-component system is difficult. This is not desirable in terms of aggregation of the nonmagnetic developer and fusion of the toner to the toner layer regulating member and the toner carrier. As a method for adjusting the development nip, the nip width is appropriately adjusted by adjusting the distance between the toner layer regulating member and the toner carrier.

  In any of the development methods described above, transfer residual toner remaining on the photosensitive drum after transfer is transferred between the transfer unit in the transfer process and the charging unit in the charging process, and between the charging unit and the developing unit in the development process. Further, the simultaneous development cleaning recovered by the developing device in the developing process can be performed without providing a cleaning member that contacts the surface of the photosensitive drum.

  In the simultaneous development cleaning system, the developing unit, the transfer unit, and the charging unit are positioned in this order with respect to the moving direction of the latent image carrier, and between the transfer unit and the charging unit and between the charging unit and the developing unit. In the meantime, there is no cleaning member for removing the transfer residual toner existing on the surface of the latent image carrier in contact with the surface of the latent image carrier.

An image forming method using the simultaneous development cleaning method will be described by taking as an example reversal development in which development is performed with the charged polarity of the toner and the charged polarity of the electrostatic latent image of the latent image carrier being the same polarity in the developing step. In the case of using a negatively chargeable photosensitive member and a negatively chargeable toner, an image visualized by a positive polarity transfer member is transferred to the transfer material in the transfer process, but the type of transfer material (thickness, Depending on the relationship between the resistance and the dielectric constant) and the image area, the charge polarity of the residual toner varies from positive to negative. However, due to the negative charging member when charging the negatively chargeable photosensitive member, even the transfer residual toner as well as the surface of the photosensitive member is uniformly transferred to the negative side even if it is shifted to the negative polarity in the transfer process. Charge polarity can be made uniform. Therefore, even if toner particles that are uniformly charged to the negative polarity at the time of development are present on the surface of the photoreceptor, if the reverse development is used as the developing method, the residual transfer toner charged to the negative is not developed by the toner. It remains in the bright portion potential portion to be developed and does not remain in the dark portion potential where the toner should not be developed, and is attracted toward the magnetic brush or developer carrier of the developer and does not remain due to the development electric field. In addition, although it is not simultaneous development cleaning, another method is to use a negative charging member when charging a negatively chargeable photosensitive member, so that even the surface of the photosensitive member as well as the residual toner is transferred to a positive polarity in the transfer process. There is a method that is the same as the simultaneous development cleaning method up to the step of uniformly aligning the charging polarity to the negative side even if it is swung. After the transfer residual toner is uniformly charged to the negative side, the charging member different from the negative charging member is charged to the photosensitive member when charging the negatively charging photosensitive member. By charging the member negatively, the transfer residual toner having the same charging polarity toward the positive side is collected once. Thereafter, the charging member that collects the transfer residual toner at the time of non-printing is positively charged to discharge the collected transfer residual toner to the transfer residual toner collection container, or to the charging member that collects the transfer residual toner. There is a method of peeling off the untransferred toner by contacting a rubber blade or the like. These cleaning methods are desirable for long-term use because the cleaning blade is not brought into direct contact with the photosensitive member and therefore the photosensitive member is not damaged.

  In any of the image forming methods and image forming apparatuses described above, when the toner of the present invention is used, the image forming method and the image forming apparatus are such that the toner is transferred to the transfer medium via the intermediate transfer body. The toner of the present invention is desirable because of its excellent transfer efficiency and cleanability. This is because the dispersion state of raw materials such as crystalline polyester, colorant, and wax in the toner is uniform, the chargeability is high, the charge distribution is sharp, and the heat resistance and durability are excellent. This is desirable because the transfer efficiency is high and the toner is prevented from being fused to the intermediate transfer member when used for a period of time and when used in a high temperature and high humidity environment or a low temperature and low humidity environment.

  FIG. 6 shows an image formation using a transfer belt as a secondary transfer means when a color toner image of four colors transferred onto the intermediate transfer drum using the intermediate transfer drum is secondarily transferred collectively to a recording material. It is explanatory drawing of an apparatus.

In the apparatus system shown in FIG. 6, a developer having cyan toner, a developer having magenta toner, a developer having yellow toner, and a black are respectively added to the developing devices 244-1, 244-2, 244-3, and 244-4. A developer having toner is introduced to develop the electrostatic image formed on the photoreceptor 241, and each color toner image is formed on the photoreceptor 241. The photoreceptor 241 is a photosensitive drum or a photosensitive belt having a photoconductive insulating material layer such as a-Se, Cds, ZnO ₂ , OPC, or a-Si. The photoreceptor 241 is rotated in the direction of the arrow by a driving device (not shown).

  As the photoreceptor 241, an amorphous silicon photosensitive layer or a photoreceptor having an organic photosensitive layer is preferably used.

The organic photosensitive layer may be a single layer type in which the photosensitive layer contains a charge generation material and a material having charge transport performance in the same layer, or a function-separated type photosensitive layer comprising the charge transport layer and the charge generation layer as components. It may be. A laminated photosensitive layer having a structure in which a charge generation layer and then a charge transport layer are laminated in this order on a conductive substrate is one preferred example.

  The binder resin for the organic photosensitive layer is particularly a polycarbonate resin, a polyester resin, or an acrylic resin, and has good transferability and cleaning properties, and poor cleaning, toner fusion to the photoreceptor, and filming of external additives are unlikely to occur.

  In the charging process, there are a non-contact method using a corona charger 241 and a contact type method using a roller or the like. For efficient uniform charging, simplification, and low ozone generation, a contact type as shown in FIG. 5 is preferably used.

  The charging roller 242 has a basic configuration of a central cored bar 242b and a conductive elastic layer 242a that forms the outer periphery thereof. The charging roller 242 is pressed against the surface of the photoconductor 241 with a pressing force, and is driven to rotate as the photoconductor 241 rotates.

  As a preferable process condition when using a charging roller, when a roller contact pressure is 5 to 500 g / cm and an AC voltage is superimposed on a DC voltage, AC voltage = 0.5 to 5 kVpp, AC Frequency = 50 Hz to 5 kHz, DC voltage = ± 0.2 to ± 1.5 kV, and when DC voltage is used, DC voltage = ± 0.2 to ± 5 kV.

  Other charging means include a method using a charging blade and a method using a conductive brush. These contact charging means are effective in that a high voltage is unnecessary and generation of ozone is reduced.

  The material of the charging roller and charging blade as the contact charging means is preferably conductive rubber, and a release coating may be provided on the surface thereof. As the releasable coating, nylon resin, PVDF (polyvinylidene fluoride), PVDC (polyvinylidene chloride), and the like are applicable.

  The toner image on the photoreceptor is transferred to an intermediate transfer drum 245 to which a voltage (for example, ± 0.1 to ± 5 kV) is applied. The surface of the photoreceptor after the transfer is cleaned by a cleaning unit 249 having a cleaning blade 248.

  The intermediate transfer drum 245 includes a pipe-shaped conductive metal core 245b and a medium-resistance elastic layer 245a formed on the outer peripheral surface thereof. The cored bar 245b may be a plastic pipe with conductive plating.

Medium resistance elastic layer 245a is made of elastic material such as silicone rubber, Teflon rubber, chloroprene rubber, urethane rubber, EPDM (ethylene propylene diene terpolymer), carbon black, zinc oxide, tin oxide, silicon carbide. A solid or foamed meat layer in which the electrical conductivity value (volume resistivity) is adjusted to a medium resistance of 10 ⁵ to 10 ¹¹ Ω · cm by blending and dispersing the conductivity imparting material as described above.

  The intermediate transfer drum 245 is disposed in parallel with the photoconductor 241 and is in contact with the lower surface of the photoconductor 241, and rotates in the counterclockwise direction indicated by an arrow at the same peripheral speed as the photoconductor 241.

  The first color toner image formed and supported on the surface of the photosensitive member 241 passes through the transfer nip where the photosensitive member 241 and the intermediate transfer drum 245 are in contact with each other, and is applied to the transfer nip region by the transfer bias applied to the intermediate transfer drum 245. The intermediate transfer is sequentially performed on the outer surface of the intermediate transfer drum 245 by the formed electric field.

  If necessary, the surface of the intermediate transfer drum 245 is cleaned by a removable cleaning unit 280 after the toner image is transferred onto the transfer material. When there is a toner image on the intermediate transfer drum, the cleaning means 280 is separated from the surface of the intermediate transfer member so as not to disturb the toner image.

  A transfer unit is disposed in parallel with the intermediate transfer drum 245 and brought into contact with the lower surface of the intermediate transfer drum 245. The transfer unit is, for example, a transfer roller or a transfer belt, and has the same peripheral speed as the intermediate transfer drum. Rotate in the clockwise direction of the arrow. The transfer unit may be disposed so as to directly contact the intermediate transfer drum, or a belt or the like may be disposed between the intermediate transfer drum and the transfer unit.

  In the case of the transfer roller, the basic structure is a cored bar and a conductive elastic layer having an outer periphery formed in the center.

  Common materials can be used as the intermediate transfer drum and the transfer roller. By setting the volume resistivity of the elastic layer of the transfer roller smaller than the volume resistivity of the elastic layer of the intermediate transfer drum, the applied voltage to the transfer roller can be reduced and a good toner image is formed on the transfer material In addition, it is possible to prevent the transfer material from being wound around the intermediate transfer member. In particular, the volume specific resistance value of the elastic layer of the intermediate transfer member is particularly preferably 10 times or more than the volume specific resistance value of the elastic layer of the transfer roller.

  The hardness of the intermediate transfer drum and the transfer roller is measured according to JIS K-6301. The intermediate transfer drum used in the present invention is preferably composed of an elastic layer belonging to a range of 10 to 40 degrees, while the hardness of the elastic layer of the transfer roller is harder than the hardness of the elastic layer of the intermediate transfer drum. Those having a value of ˜80 degrees are preferable for preventing the transfer material from being wound around the intermediate transfer drum. When the hardness of the intermediate transfer drum and that of the transfer roller are reversed, a recess is formed on the transfer roller side, and the transfer material is easily wound around the intermediate transfer drum.

  In FIG. 6, a transfer belt 247 is disposed below the intermediate transfer drum 245. The transfer belt 247 is stretched between two rollers arranged in parallel to the axis of the intermediate transfer drum 245, that is, a bias roller 247a and a tension roller 247c, and is driven by a driving unit (not shown). Since the transfer belt 247 is configured such that the bias roller 247a side can move in the arrow direction around the tension roller 247c side, the transfer belt 247 can contact and separate from the intermediate transfer drum 245 in the arrow direction from below. A desired secondary transfer bias is applied to the bias roller 247a by a secondary transfer bias source 247d, while the tension roller 247c is grounded.

Next, regarding the transfer belt 247, in this embodiment, carbon is dispersed in a thermosetting urethane elastomer, and the thickness is controlled to about 300 μm and the volume resistivity is 10 ⁸ to 10 ¹² Ω · cm (when 1 kV is applied). Above, a rubber belt controlled to 20 μm fluororubber and a volume resistivity of 10 ¹⁵ Ω · cm (when 1 kV was applied) was used. The outer diameter is a tube shape with a circumference of 80 × width of 300 mm.

  The transfer belt 247 is applied with a tension that extends about 5% by the bias roller 247a and the tension roller 247c.

The transfer means 247 is rotated with a difference in speed or peripheral speed from the intermediate transfer drum 245. The transfer material 246 is conveyed between the intermediate transfer drum 245 and the transfer unit 247, and at the same time, a bias having a polarity opposite to the frictional charge of the toner is applied to the transfer unit 247 as the secondary transfer bias source 247.
By applying from d, the toner image on the intermediate transfer drum 245 is transferred to the surface side of the transfer material 246.

The material for the transfer rotator can be the same as that of the charging roller. Preferred transfer process conditions include a roller contact pressure of 5 to 500 g / cm ² and a DC voltage of ± 0.2. ~ ± 10 kV.

For example, the conductive elastic layer 247a ₁ of the bias roller 247a has a volume resistance of 10 ⁶ to 10 ¹⁰ Ω · cm such as polyurethane, ethylene-propylene-diene terpolymer (EPDM) in which a conductive material such as carbon is dispersed. It is made of elastic material. Core 247a ₂
A bias is applied by a constant voltage power source. The bias condition is ± 0.2 to
± 10 kV is preferred.

  Next, the transfer material 246 is conveyed to a fixing device 281 having a heating roller incorporating a heating element such as a halogen heater and an elastic pressure roller pressed against it with a pressing force. By passing between the pressure rollers, the toner image is fixed to the transfer material by heating and pressing. A method of fixing with a heater through a film may be used.

  In the present invention, for example, the following members are used as members constituting the image forming apparatus.

  The photosensitive layer of the electrophotographic photoreceptor used in the present invention has a single layer or a laminated structure. In the case of a single layer structure, the photosensitive layer contains both a charge generating material that generates carriers and a charge transport material that transports carriers. In the case of a laminated structure, a charge generation layer containing a charge generation material that generates carriers and a charge transport layer containing a charge transport material that transports carriers are stacked to form a photosensitive layer. The surface layer may be formed by either a charge generation layer or a charge transport layer.

  The single-layer photosensitive layer preferably has a thickness of 5 to 100 μm, particularly preferably 10 to 60 μm. Moreover, it is preferable to contain 20-80 mass% of charge generation materials and charge transport materials with respect to the total mass of a layer, and it is preferable that it is 30-70 mass% especially. The single-layer photosensitive layer contains a binder resin in addition to the charge generation material and the charge transport material, and may contain an ultraviolet absorber, an antioxidant, other additives and the like as necessary.

  In the laminated photosensitive layer, the thickness of the charge generation layer is preferably 0.001 to 6 μm, and particularly preferably 0.01 to 2 μm. The content of the charge generating material is preferably 10 to 100% by mass, particularly 40 to 100% by mass, based on the total mass of the layer. The charge generation layer may be composed of only a charge generation material. In other cases, the charge generation layer may contain the binder resin or the like. The thickness of the charge transport layer is preferably 5 to 100 μm, and particularly preferably 5 to 19 μm. The content of the charge transport material is preferably 20 to 80% by mass, and particularly preferably 30 to 70% by mass. The charge transport layer contains a binder resin in addition to the charge transport material, and may contain other optional components similar to those described above.

  In the electrophotographic photoreceptor used in the present invention, a protective layer may be laminated on the photosensitive layer as described above. The thickness of the protective layer is preferably from 0.01 to 20 μm, particularly preferably from 0.1 to 10 μm. The protective layer usually has a structure in which a charge generating material or a charge transporting material, a metal and its oxide, nitride, salt, alloy, and a conductive material such as carbon are dispersed in a binder resin. Examples of the binder resin, charge generating material, and charge transporting material used for the protective layer include the same materials as those used for the photosensitive layer.

  The conductive support used for the electrophotographic photoreceptor used in the present invention is a metal or alloy such as iron, copper, nickel, aluminum, titanium, tin, antimony, indium, lead, zinc, gold and silver, or their Oxides, carbon, conductive resins, etc. can be used. There are cylindrical, belt-like and sheet-like shapes. Moreover, although the said electroconductive material may be shape-processed, you may apply | coat as a coating material or may vapor-deposit. In addition, the electroconductive support body used for this example is a cylindrical thing about 30 mm in diameter.

  Further, as described above, an undercoat layer may be provided between the conductive support and the photosensitive layer. The undercoat layer is mainly composed of a binder resin, but may contain the conductive material or an acceptor compound. The binder resin that forms the undercoat layer is polyester, polyurethane, polyarylate, polyethylene, polystyrene, polybutadiene, polycarbonate, polyamide, polypropylene, polyimide, polyamideimide, polysulfone, polyallyl ether, polyacetal, phenol resin, acrylic resin, silicone Examples thereof include resins, epoxy resins, urea resins, allyl resins, alkyd resins, and butyral resins.

  Further, as described above, a conductive layer may be provided between the conductive support and the photosensitive layer. When the photoreceptor has both the undercoat layer and the conductive layer, the conductive support, the conductive layer, the undercoat layer, and the photosensitive layer are usually laminated in this order. The conductive layer generally has a configuration in which the conductive material is dispersed in a binder resin similar to that used in the undercoat layer.

  As a method for producing the electrophotographic photosensitive member used in the present invention, a method of laminating an undercoat layer, a photosensitive layer, a protective layer and the like on a conductive support by vapor deposition or coating is usually used. For coating, a bar coater, knife coater, roll coater, attritor, spray, dip coating, electrostatic coating, powder coating and the like are used. In addition, in order to form the undercoat layer, the photosensitive layer, the protective layer, and the like by a coating method, a solution in which each component is dissolved and dispersed in an organic solvent, a dispersion, or the like is applied by the above method. After that, the solvent may be removed by drying or the like. Alternatively, when a reaction-curable binder resin is used, a solution, a dispersion, or the like in which the constituent components of each layer are dissolved and dispersed in the resin raw material component and an appropriate organic solvent that is added as necessary is used as described above. After the coating, for example, the resin raw material may be reacted and cured by heat or light, and the solvent may be removed by drying or the like as necessary.

As the photosensitive member contact charging member, in the case of a roller or a blade, a metal such as iron, copper or stainless steel, a carbon dispersion resin, a metal or a metal oxide dispersion resin, or the like is used as a conductive substrate. A plate shape or the like can be used. For example, the elastic roller is composed of a conductive substrate provided with an elastic layer, a conductive layer, and a resistance layer. The roller elastic layer includes chloroprene rubber, isoprene rubber, EPDM rubber, polyurethane rubber, epoxy rubber. It can be made of rubber or sponge such as butyl rubber, thermoplastic elastomer such as styrene-butadiene thermoplastic elastomer, polyurethane thermoplastic elastomer, polyester thermoplastic elastomer, ethylene-vinyl acetate thermoplastic elastomer, etc., conductive layer the, the volume resistivity of 10 ⁷ Ω · cm or less and desirably 10 ⁶ Ω · cm. For example, metal vapor deposition film, conductive particle dispersion resin, conductive resin, etc. are used. Specific examples include vapor deposition films of aluminum, indium, nickel, copper, iron, etc., and examples of conductive particle dispersion resin include carbon. In addition, conductive particles such as aluminum, nickel, and titanium oxide are dispersed in a resin such as urethane, polyester, vinyl acetate-vinyl chloride copolymer, and polymethyl methacrylate. Examples of the conductive resin include quaternary ammonium salt-containing polymethyl methacrylate, polyvinyl aniline, polyvinyl pyrrole, polydiacetylene, and polyethyleneimine. The resistance layer is, for example, a layer having a volume resistivity of 10 ⁶ to 10 ¹² Ω · cm, and a semiconductive resin, a conductive particle-dispersed insulating resin, or the like can be used. As the semiconductive resin, resins such as ethyl cellulose, nitrocellulose, methoxymethylated nylon, ethoxymethylated nylon, copolymerized nylon, polyvinyl hydrin, and casein are used. Examples of conductive particle-dispersed resins include small amounts of conductive particles such as carbon, aluminum, indium oxide, and titanium oxide in insulating resins such as urethane, polyester, vinyl acetate-vinyl chloride copolymer, and polymethyl methacrylate. Examples include dispersed ones.

As the charging member, a brush whose resistance is adjusted by dispersing a conductive material in commonly used fibers is used. As the fiber, generally known fiber can be used, and examples thereof include nylon, acrylic, rayon, polycarbonate, polyester and the like. As the conductive material, generally known conductive materials can also be used, and metals such as copper, nickel, iron, aluminum, gold and silver, or iron oxide, zinc oxide, tin oxide, antimony oxide and titanium oxide. Metal oxides such as carbon black, and conductive powder such as carbon black. These conductive powders may be subjected to surface treatment for the purpose of hydrophobization and resistance adjustment as necessary. In use, it is selected in consideration of dispersibility with fibers and productivity. As the shape of the brush, the fiber thickness is 1 to 20 denier (fiber diameter of about 10 to 500 μm), the brush fiber length is 1 to 15 mm, and the brush density is 10,000 to 300,000 per square inch (1 (About 1.5 × 10 ^{7 to} 4.5 × 10 ⁸ per square meter) is preferably used.

  In the image forming method of the present invention, it is desirable that the photosensitive member contact charging member is a roller because of excellent charging uniformity.

  Hereinafter, the evaluation method used in the examples in this specification will be described in detail.

For the measurement of fog, an evaluation machine, which will be described later, is used as an image forming apparatus. .5 ° C, humidity 80% RH) and low temperature and low humidity environment (L / L: temperature 10 ° C, humidity 10% RH). After printing 10,000 sheets of durability from the beginning, it was left in each environment for 6 days, and then the fog amount of the first image sample was measured using REFECT METER MODELTC-6DS manufactured by Tokyo Denshoku. , Calculated from the following formula. The smaller the value, the less fog. A fogging amount of 2% or less was regarded as no practical problem. As a transfer material used for the durability test, A4 size CLC paper (manufactured by Canon, 80 g / m ² ) was used.
Fog amount (%) = (Whiteness before printing out) − (Whiteness of non-image forming portion (white background portion) of recording material after printing)

Dropping is described below in a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and in a high temperature and high humidity environment (H / H: temperature 32.5 ° C., humidity 80% RH). Using an evaluation machine, a durability test was conducted with a method of pausing for 1 minute each time two sheets were printed at a printing rate of 1%. After printing 10,000 sheets from the beginning, the sheet was left in each environment for 6 days, and then one sheet. Eye image samples were evaluated visually. As the transfer material, A4 size CLC paper (manufactured by Canon, 80 g / m ² ) was used.
A: Not generated at all B: One present on the image C: Two to three present on the image, but no practical problem D: Generated, practically problematic

Image density reduction is described below in a normal temperature and normal humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and in a high temperature and high humidity environment (H / H: temperature 32.5 ° C., humidity 80% RH). A durability test was conducted with a test method of 1 minute each time two sheets were printed at a printing rate of 1%, and Tokyo Denshoku for the 5,000th and 8,000th image samples from the beginning. The concentration was measured using a REFLECT METER MODELTC-6DS manufactured by the company, and the concentration difference was evaluated. As the transfer material, A4 size CLC paper (manufactured by Canon, 80 g / m ² ) was used.
A: No decrease in density B: Density decrease is 0.02 or less C: Density decrease is 0.03 or more and 0.05 or less D: Density decrease is 0.06 or more and 0.07 or less E: Density decrease is 0.08 or more and 0 .10 or less F: Concentration decrease is 0.11 or more

Solid image uniformity was evaluated in a room temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and a low temperature and low humidity environment (L / L: temperature 15 ° C., humidity 10% RH) as described below. After printing the 10th and 4,000th images and after leaving them in each environment for 7 days after printing 4,000 sheets, Each sheet was printed with a single solid chart, and image evaluation was performed. As the transfer material, A4 size CLC paper (manufactured by Canon, 80 g / m ² ) was used. The image samples were evaluated as follows: A: The toner was uniformly transferred and colored on the entire surface. B: A portion with a low density partially existed after 50 mm from the image leading edge. C: The toner after 50 mm from the image leading edge. Is not transferred to the paper, there is a place where the paper background is exposed

Image unevenness is in a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH), in a high temperature and high humidity environment (H / H: temperature 32.5 ° C., humidity 80% RH), and in a low temperature and low humidity environment. Under the following (L / L: temperature 15 ° C., humidity 10% RH), using an evaluation machine described later, after printing 6,000 sheets of continuous printing at a printing rate of 1%, left in each environment for 2 days, The subsequent first halftone image was evaluated. As the transfer material, A4 size CLC paper (manufactured by Canon, 80 g / m ² ) was used. As the evaluation image, an image having a 50% density halftone image printed on the entire surface was used.
Image samples evaluated as follows: A: No unevenness on image B: Minor unevenness on image, but no problem in practical use C: Unevenness on image, practical problem

The initial image density is an evaluation machine described below in a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and in a low temperature and low humidity environment (L / L: temperature 15 ° C., humidity 10% RH). , The durability test was performed with continuous printing at a printing rate of 1%, and before printing the durability test and immediately after printing the 10th and 100th images of the durability test, a single solid chart was printed on each image. The image density of was measured. About the density | concentration of the image sample, the density | concentration was measured using Tokyo Denshoku Co., Ltd. REFLECT METER MODELTC-6DS. When the image density is 1.20 or more, there is no practical problem. As the transfer material, A4 size CLC paper (manufactured by Canon, 80 g / m ² ) was used.
A: Concentration 1.30 or more B: Concentration 1.25 or more and 1.29 or less C: Concentration 1.20 or more and 1.24 or less D: Concentration 1.15 or more and 1.19 or less E: Concentration 1.14 or less

The fixability was measured in a room temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and in a low temperature and low humidity environment (L / L: temperature 15 ° C., humidity 10% RH). Using the machine and the toner-filled cartridge in an environment-friendly state (after being left in that environment for 24 hours), the printer is printed with a 200 μm-wide horizontal line pattern (width 200 μm, interval 200 μm) immediately after the power is turned on, The 50th printed image was used for the evaluation of fixability. The fixing property was evaluated by rubbing the image with Sylbon paper at a load of 100 g for 5 reciprocations, and the peeling of the image was evaluated by the average reduction rate (%) of reflection density.

For the evaluation, bond paper having a surface smoothness of 10 [sec] or less was used. The evaluation criteria are shown below. A: Density reduction rate of less than 3% B ... Density reduction rate of 3% or more and less than 5% C ... Density reduction rate of 5% or more and less than 10% D ... Concentration reduction rate of 10% or more and less than 15% E ... Concentration reduction rate of 15% or more 20 %Less than

  Offset resistance is described below in a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and in a high temperature and high humidity environment (H / H: temperature 32.5 ° C., humidity 80% RH). Using this evaluation machine, 100 sheets of solid images were printed out immediately after turning on the power and waiting for the machine and toner-filled cartridges to become familiar with the environment (after being left in the environment for 24 hours). Was evaluated.

For the evaluation, an OHP film (CG3700, manufactured by Sumitomo 3M Limited) was used. The evaluation criteria are shown below.
A: No offset is generated at all B: Offset is very slight, but there is no problem in practical use (and 1 sheet is generated)
C: Offset occurred very slightly, but there was no practical problem (and 2 sheets were generated)
D: Offset occurred very slightly, but there was no practical problem (and 3 to 4 sheets generated)
E ... Offset occurs, causing practical problems

Toner adhesion and adhesion to the toner layer regulating member is performed in a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH), and in a high temperature and high humidity environment (H / H: temperature 32.5 ° C.). , Humidity 80% RH) using an evaluation machine to be described later, a durability test was performed by a method of pausing for 1 minute every time two sheets were printed at a printing rate of 1%. The toner layer regulating member was visually evaluated. As the transfer material, A4 size CLC paper (manufactured by Canon, 80 g / m ² ) was used.
A: Not generated at all B: Slightly generated on the toner layer regulating member, but not generated on the image C: Slightly generated on the image, but no problem in practical use (one small streak at the end) )
D: Minor occurrence on the image but no practical problem (2-3 minor streaks on the edge)
E: Occurred on the image and has practical problems

Filming on the latent image carrier is performed in a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and in a low temperature and low humidity environment (L / L: temperature 15 ° C., humidity 10% RH). Then, using an evaluation machine described later, a durability test was performed by continuous printing at a printing rate of 1%, and the 2,000th durability image sample from the beginning was visually evaluated. As the transfer material, A4 size CLC paper (manufactured by Canon, 80 g / m ² ) was used.
A: Not generated at all B: Slightly generated but practically no problem C: Slightly generated but practically no problem D: Generated and practically problematic

The cleaning properties are normal temperature and humidity (N / N: temperature 23.5 ° C., humidity 60% RH), low temperature and low humidity (L / L: temperature 15 ° C., humidity 10% RH), high temperature and high humidity ( H / H: Temperature 32.5 ° C., Humidity 80% RH) Using an evaluation machine described later, 4,000 sheets were continuously printed at a printing rate of 2%, and the cleaning property and image quality were visually evaluated. As the transfer material, A4 size CLC paper (manufactured by Canon, 80 g / m ² ) was used. (A with good cleaning
In the case of a defective one, that is, a black horizontal streak is slightly generated in the image due to a drop in the elasticity of the blade and the toner slipping through. Indicated by C. )

The transfer efficiency is described below in a normal temperature and normal humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and in a high temperature and high humidity environment (H / H: temperature 32.5 ° C., humidity 80% RH). Using an evaluator, a durability test was performed with a system that pauses for 1 minute every time two sheets were printed at a printing rate of 1%. After printing 10,000 sheets from the beginning, the latent image was left for 2 days in each environment. The transfer efficiency from the carrier to the intermediate transfer member (primary transfer) and from the intermediate transfer member to the transfer material (secondary transfer) was measured. As the transfer material, A4 size CLC paper (manufactured by Canon, 80 g / m ² ) was used. The transfer efficiency is calculated as follows.

A solid image of 10 cm ² is formed on the photoconductor, and the amount of toner on the photoconductor (W1) and the amount of toner on the paper after transfer (W2) are used, and the ratio between them: W2 / W1 × 100 (% ).

After the endurance test, a solid image with a 5% image area ratio was formed, and the toner amount (per unit area) in the toner image before transfer and the toner amount (per unit area) after transfer were measured. The transfer efficiency was calculated from the value as follows. Note that image formation was performed for each of the primary transfer evaluation and the secondary transfer evaluation.
Primary transfer efficiency (%)
= {(Toner amount on intermediate transfer member) / (toner amount before transfer on photoconductor)} × 100 A: 92% or more B: 88% to less than 92% C: 84% to less than 88% D: 84% Less than

Ａ：鮮明な画像
Ｂ：細線再現性が若干劣るものの良好な画像
Ｃ：細線再現性が劣るものの実用的には問題の無いレベル
Ｄ：細線再現性が悪く、不均一な画像 In the present invention, the fine line reproducibility was measured by the following method. That is, an image obtained by copying an original document with a fine line with a width of 100 μm accurately under an appropriate copying condition is used as a measurement sample. Measure. At this time, since the measurement position of the line width is uneven in the width direction of the fine line image of the toner, the average line width of the unevenness is used as the measurement point. From this, the fine line reproducibility value (%) is calculated by the following equation.

A: clear image B: good image although fine line reproducibility is slightly inferior C: practically no problem although fine line reproducibility is inferior level D: non-uniform image with poor fine line reproducibility

The filming of the toner carrier was evaluated by visual observation and image of the surface of the toner carrier. In the initial halftone image after printing 20,000 sheets and 40,000 sheets, it was visually evaluated whether or not unevenness in density occurred between the 1% printed image portion and the non-printed image portion. Thereafter, the toner on the surface of the toner carrier was blown with air, and the surface of the toner carrier was observed.
A: There is no occurrence of uneven density on the image and the surface of the toner carrier is good. B: No unevenness of density is generated on the image, but some filming is confirmed on the surface of the toner carrier.
C: Extremely slight shading unevenness occurs on the image but no problem D: Mild shading unevenness occurs on the image but no problem E: Unusual shading unevenness occurs on the image, causing a problem

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but this does not limit the present invention in any way. “Parts” in the following examples and the like are “parts by mass”.

[Crystalline polyester resin production example 1]
In an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device. Dimethyl sebacate: 200 parts by mass Sebacic acid: 50 parts by mass 1,4-cyclohexanedimethanol: 145 Part by mass: Potassium oxalate titanate: 0.45 part by mass The above polyester monomer was charged and reacted at 200 ° C. for 8 hours under a nitrogen atmosphere and at normal pressure. By reacting for 5 hours, a crystalline polyester resin 1 was obtained. The physical properties of the obtained crystalline polyester resin are shown in Table 1.

[Crystalline polyester resin production example 2]
In an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirrer. Sebacic acid: 210 parts by mass Dimethyl succinate: 15 parts by mass 1,10-decanedicarboxylic acid: 25 Parts by mass, triethylene glycol: 120 parts by mass, diethylene glycol: 35 parts by mass, potassium oxalate titanate: 0.60 parts by mass, charged with the above polyester monomer, and reacted at 200 ° C. under a nitrogen atmosphere under normal pressure for 5 hours. Thereafter, the reaction was further carried out at 220 ° C. under reduced pressure of 10 to 20 mmHg for 1.5 hours to obtain a crystalline polyester resin 2. Table 1 shows the physical properties of the obtained polyester resin.

[Amorphous polyester resin production example 1]
In an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, terephthalate: 20 parts by mass, isophthalate: 20 parts by mass, bisphenol A-propylene oxide 2 mol adduct: 59 Part by mass: Bisphenol A-propylene oxide 3 mol adduct: 37 parts by mass Potassium oxalate titanate: 0.025 part by mass The above polyester monomer was charged, and the reaction was performed at 220 ° C. for 22 hours under a nitrogen atmosphere and normal pressure. Furthermore, it was made to react under reduced pressure of 10-20 mmHg for 2 hours. Thereafter, the temperature was lowered to 190 ° C., 1.5 parts by mass of trimellitic anhydride was added, and the mixture was reacted at 190 ° C. for 1.5 hours to obtain amorphous polyester resin 1. Table 2 shows the physical properties of the obtained polyester resin.

[Amorphous polyester resin production example 2]
In an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirrer ・ Terephthalic acid: 24 parts by mass ・ Isophthalic acid: 24 parts by mass 87.5 parts by mass-Bisphenol A-propylene oxide 3 mol adduct: 20.5 parts by mass-Bisphenol A-ethylene oxide 2 mol adduct: 2.5 parts by mass-Neopentyl glycol: 1 part by mass-Oxalic acid titanic acid Potassium: 0.035 parts by mass The above polyester monomer was charged, and the reaction was carried out at 210 ° C. for 23 hours under a nitrogen atmosphere and at normal pressure. The reaction was allowed to proceed for a further 1.5 hours under a reduced pressure of 10 to 20 mmHg. Thereafter, the temperature was lowered to 180 ° C., 0.10 parts by mass of trimellitic anhydride was added, and the mixture was reacted at 180 ° C. for 1.5 hours to obtain amorphous polyester resin 2. Table 2 shows the physical properties of the obtained polyester resin.

[Amorphous polyester resin production example 3]
In an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirrer ・ Terephthalic acid: 21 parts by mass • Isophthalic acid: 21 parts by mass 120 parts by mass · Potassium oxalate titanate: 0.030 parts by mass The above polyester monomer was charged, and the reaction was carried out at 220 ° C for 15 hours under a nitrogen atmosphere and under normal pressure. Thereafter, the temperature was lowered to 180 ° C., 0.01 part by mass of trimellitic anhydride was added, and the mixture was reacted at 180 ° C. for 1.5 hours to obtain amorphous polyester resin 3. Table 2 shows the physical properties of the obtained polyester resin.

[Amorphous polyester resin production example 4]
In an autoclave equipped with a decompression device, water separation device, nitrogen gas introduction device, temperature measurement device, and stirring device ・ Terephthalic acid: 45.0 parts by mass ・ Fumaric acid: 3 parts by mass ・ Addition of 2 mol of bisphenol A-propylene oxide Product: 55 parts by mass-Bisphenol A-propylene oxide 3 mol adduct: 64 parts by mass-Dibutyltin oxide: 0.030 parts by mass The above polyester monomer was charged, and the reaction was carried out at 220 ° C for 18 hours under nitrogen atmosphere and normal pressure. The reaction was further carried out for 1 hour under a reduced pressure of 10 to 20 mmHg. Thereafter, the temperature was lowered to 170 ° C., 0.08 parts by mass of trimellitic anhydride was added, and the mixture was reacted at 170 ° C. for 1.5 hours to obtain a polyester resin 4. Table 2 shows the physical properties of the obtained polyester resin.

[Resin having sulfonic acid or sulfonate group and sulfonic acid ester (hereinafter also referred to as negatively chargeable charge control resin) Production Example 1]
In a 2 L flask equipped with a stirrer, condenser, thermometer, nitrogen introduction tube, 100 parts of toluene, 350 parts of methanol, 470 parts of styrene, 40 parts of 2-acrylamido-2-methylpropanesulfonic acid, 70 parts of 2-ethylhexyl acrylate, Charge 20 parts of benzyl methacrylate and 10 parts of lauryl peroxide, stir, polymerize for 10 hours at 65 ° C. under nitrogen introduction, remove the contents from the flask, wash with isopropyl alcohol, and dry under reduced pressure at 40 ° C. for 96 hours. The mixture was roughly crushed with a hammer mill, and the crushed product was further dried under reduced pressure at 40 ° C. for 48 hours. Resin 1 having a sulfonic acid, a sulfonic acid base, or a sulfonic acid ester was produced. The physical properties of the obtained resin were Mw = 24,000, Tg = 67 ° C., and residual monomer = 350 ppm. Moreover, the acid value of the obtained resin 1 having a sulfonic acid or a sulfonic acid base and a sulfonic acid ester was 20 mgKOH / g.

[Resin Production Example 2 Having Sulfonic Acid or Sulfonic Acid Base and Sulfonic Acid Ester]
In a 2 L flask equipped with a stirrer, condenser, thermometer, nitrogen introduction tube, 300 parts of toluene, 150 parts of methanol, 470 parts of styrene, 40 parts of 2-acrylamido-2-methylpropanesulfonic acid, 70 parts of 2-ethylhexyl acrylate, 20 parts of benzyl methacrylate and 7 parts of lauryl peroxide were charged, stirred and subjected to solution polymerization at 65 ° C. for 10 hours under introduction of nitrogen. The contents were taken out from the flask, dried under reduced pressure at 40 ° C. The coarsely crushed material was further dried under reduced pressure at 40 ° C. for 48 hours. Resin 2 having sulfonic acid, sulfonic acid base, or sulfonic acid ester was produced. The physical properties of the obtained resin were Mw = 40,000, resin Tg = 68 ° C., and residual monomer = 380 ppm. Moreover, the acid value of the obtained resin 2 having a sulfonic acid, a sulfonic acid base, or a sulfonic acid ester was 18 mgKOH / g.

[Production Example 1 of hydrophobic silica]
Silica (AEROSIL 200CF, manufactured by Nippon Aerosil Co., Ltd.) was treated with 10 parts of hexamethyldisilazane to obtain hydrophobic silica 1. The primary particle size was 12 nm and the degree of hydrophobicity was 70.

[Production Example 2 of hydrophobic silica]
Silica (AEROSIL 200CF, manufactured by Nippon Aerosil Co., Ltd.) was treated with 10 parts of hexamethyldisilazane and 15 parts of methylphenyl silicone oil to obtain hydrophobic silica 2. The primary particle size was 12 nm and the degree of hydrophobicity was 97.

[Production example 1 of hydrophobic titanium oxide]
Titanium oxide (P25, manufactured by Nippon Aerosil Co., Ltd.) was treated with 20 parts of γ-mercaptopropyltrimethoxysilane in toluene, filtered and dried to obtain hydrophobic titanium oxide 1. The primary particle size was 25 nm and the degree of hydrophobicity was 60.

  Next, production examples of fatty acid metal salts used in the present invention will be described.

<Production of fatty acid metal salt 1>
A receiving container with a stirrer was prepared, and the stirrer was rotated at 350 rpm. 500 mass parts of 0.5 mass% sodium stearate aqueous solution was thrown into this receiving container, and liquid temperature was adjusted to 85 degreeC. Next, 525 mass parts of 0.2 mass% zinc sulfate aqueous solution was dripped at this receptacle over 15 minutes. After the completion of charging the whole amount, the reaction was terminated by aging for 10 minutes at the temperature during the reaction. Next, the fatty acid metal salt slurry thus obtained was washed by filtration. The obtained washed fatty acid metal salt cake was roughly crushed and then dried at 105 ° C. using a continuous instantaneous air dryer. Thereafter, the air volume was 6.0 m ³ / min. In a nano grinding mill [NJ-300] (manufactured by Sanrex). After pulverizing at a processing speed of 80 kg / h, reslurry and remove fine particles and coarse particles using a wet centrifugal classifier, then dry at 80 ° C. using a continuous instantaneous air dryer and fatty acid metal Salt 1 was obtained. The fatty acid metal salt 1 obtained had a volume-based median diameter (D50) of 0.47 μm. The physical properties of the fatty acid metal salt 1 are shown in Table 3, and the particle size distribution is shown in FIG.

<Production of fatty acid metal salt 2>
In fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was changed to 2.0% by mass sodium stearate, and 0.2% by mass zinc sulfate aqueous solution was changed to 1.0% by mass calcium chloride aqueous solution. The reaction was terminated by aging for 5 minutes. Other steps were carried out in the same manner as fatty acid metal salt 1 to obtain fatty acid metal salt 2. The fatty acid metal salt 2 obtained had a volume-based median diameter (D50) of 0.60 μm. The physical properties of the fatty acid metal salt 2 are shown in Table 3, and the particle size distribution is shown in FIG.

<Production of fatty acid metal salt 3>
In fatty acid metal salt 1, the 0.2% by mass zinc sulfate aqueous solution was changed to a 0.3% by mass lithium chloride aqueous solution. Other than that was carried out similarly to the fatty-acid metal salt 1, and obtained the fatty-acid metal salt 3. FIG. The fatty acid metal salt 3 obtained had a volume-based median diameter (D50) of 0.33 μm. Table 3 shows the physical properties of the fatty acid metal salt 3.

<Production of fatty acid metal salt 4>
In the fatty acid metal salt 1, the 0.2 mass% zinc sulfate aqueous solution was changed to a 0.2 mass% magnesium sulfate aqueous solution. Otherwise, the fatty acid metal salt 4 was obtained in the same manner as the fatty acid metal salt 1. The resulting fatty acid metal salt 4 had a volume-based median diameter (D50) of 0.47 μm. Table 3 shows the physical properties of the fatty acid metal salt 4.

<Production of fatty acid metal salt 5>
In the fatty acid metal salt 1, a fatty acid metal salt 5 was obtained in the same manner as the fatty acid metal salt 1, except that the 0.5 mass% sodium stearate aqueous solution was changed to 0.5 mass% sodium laurate. The fatty acid metal salt 5 obtained had a volume-based median diameter (D50) of 0.62 μm. Table 3 shows the physical properties of the fatty acid metal salt 5.

<Production of fatty acid metal salt 6>
In fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was added to 0.25% by mass sodium laurate aqueous solution, 0.2% by mass zinc sulfate aqueous solution to 0.15% by mass zinc sulfate aqueous solution, and pulverized The condition is that the air volume is 10.0 m ³ / min. The pulverization process was changed to 3 times. The fatty acid metal salt 6 obtained had a volume-based median diameter (D50) of 0.16 μm. Table 3 shows the physical properties of the fatty acid metal salt 6.

<Production of fatty acid metal salt 7>
In fatty acid metal salt 1, except that 0.5% by mass sodium stearate aqueous solution is changed to 0.22% by mass sodium laurate aqueous solution and 0.2% by mass zinc sulfate aqueous solution is changed to 0.12% by mass zinc sulfate aqueous solution. In the same manner as fatty acid metal salt 1, fatty acid metal salt 7 was obtained. The volume-based median diameter (D50) of the obtained fatty acid metal salt 7 is 0.28 μm, and the physical properties of the fatty acid metal salt 7 are shown in Table 3.

<Production of fatty acid metal salt 8>
In fatty acid metal salt 1, except that 0.5 mass% sodium stearate aqueous solution is changed to 0.26 mass% sodium laurate aqueous solution and 0.2 mass% zinc sulfate aqueous solution is changed to 0.16 mass% zinc sulfate aqueous solution. Fatty acid metal salt 8 was obtained in the same manner as fatty acid metal salt 1. The fatty acid metal salt 8 obtained had a volume-based median diameter (D50) of 0.32 μm. Table 3 shows the physical properties of the fatty acid metal salt 8.

<Production of fatty acid metal salt 9>
In fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was changed to 1.0% by mass sodium laurate, and 0.2% by mass zinc sulfate aqueous solution was changed to 0.4% by mass zinc sulfate aqueous solution. Further, the reaction was terminated by aging for 15 minutes. In addition, the pulverization conditions were such that the air volume was 4.0 m ³ / min. I made it. Other steps were carried out in the same manner as fatty acid metal salt 1 to obtain fatty acid metal salt 9. The resulting fatty acid metal salt 9 had a volume-based median diameter (D50) of 0.73 μm. Table 3 shows the physical properties of the fatty acid metal salt 9.

<Production of fatty acid metal salt 10>
In fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was changed to 1.0% by mass sodium laurate, and 0.2% by mass zinc sulfate aqueous solution was changed to 0.4% by mass zinc sulfate aqueous solution. Moreover, the classification process after performing a grinding | pulverization process was not performed but the fatty-acid metal salt 10 was obtained. The resulting fatty acid metal salt 10 had a volume-based median diameter (D50) of 0.63 μm. Table 3 shows the physical properties of the fatty acid metal salt 10.

<Production of fatty acid metal salt 11>
In fatty acid metal salt 1, except that 0.5% by mass sodium stearate aqueous solution is changed to 0.35% by mass sodium stearate aqueous solution and 0.2% by mass zinc sulfate aqueous solution is changed to 0.25% by mass zinc sulfate aqueous solution. Fatty acid metal salt 11 was obtained in the same manner as fatty acid metal salt 1. The resulting fatty acid metal salt 11 had a volume-based median diameter (D50) of 0.47 μm. Table 3 shows the physical properties of the fatty acid metal salt 11.

<Production of fatty acid metal salt 12>
In fatty acid metal salt 1, changing 0.5% by mass sodium stearate aqueous solution to 0.26% by mass sodium laurate aqueous solution and 0.2% by mass zinc sulfate aqueous solution to 0.16% by mass zinc sulfate aqueous solution, sulfuric acid Fatty acid metal salt 12 was obtained in the same manner as fatty acid metal salt 1 except that the aqueous zinc solution was added dropwise over 30 minutes. The resulting fatty acid metal salt 12 had a volume-based median diameter (D50) of 0.32 μm. Table 3 shows the physical properties of the fatty acid metal salt 12.

<Production of fatty acid metal salt 13>
In fatty acid metal salt 1, 0.5 mass% sodium stearate aqueous solution was changed to 0.25 mass% sodium laurate aqueous solution, 0.2 mass% zinc sulfate aqueous solution was changed to 0.15 mass% zinc sulfate aqueous solution, and zinc sulfate was changed. The aqueous solution was added dropwise over 30 minutes, and the pulverization conditions were changed to an air volume of 10.0 m ³ / min. Then, the fatty acid metal salt 13 was obtained in the same manner as the fatty acid metal salt 1 except that the pulverization process was changed to be performed three times. The resulting fatty acid metal salt 13 had a volume-based median diameter (D50) of 0.14 μm. Table 3 shows the physical properties of the fatty acid metal salt 13.

<Production of fatty acid metal salt 14>
In fatty acid metal salt 1, 0.5% by mass of sodium stearate aqueous solution is 1.0% by mass.
It changed to sodium laurate, changed 0.2 mass% zinc sulfate aqueous solution into 0.4 mass% zinc sulfate aqueous solution, and dripped the zinc sulfate aqueous solution over 30 minutes. Further, the reaction was terminated by aging for 15 minutes. In addition, the pulverization conditions were such that the air volume was 4.0 m ³ / min. I made it. Other steps were carried out in the same manner as in fatty acid metal salt 1 to obtain fatty acid metal salt 14. The obtained fatty acid metal salt 14 had a volume-based median diameter (D50) of 0.78 μm. Table 3 shows the physical properties of the fatty acid metal salt 14.

<Production of fatty acid metal salt 15>
In fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was changed to 1.1% by mass sodium laurate, and 0.2% by mass zinc sulfate aqueous solution was changed to 0.45% by mass zinc sulfate aqueous solution. Further, the reaction was terminated by aging for 15 minutes. In addition, the pulverization conditions were such that the air volume was 3.5 m ³ / min. I made it. Other steps were carried out in the same manner as the fatty acid metal salt 1 to obtain a fatty acid metal salt 15. The fatty acid metal salt 15 obtained had a volume-based median diameter (D50) of 0.95 μm. Table 3 shows the physical properties of the fatty acid metal salt 15.

<Production of fatty acid metal salt 16>
In fatty acid metal salt 1, the 0.5 mass% sodium stearate aqueous solution was changed to 1.2 mass% sodium laurate, and the 0.2 mass% zinc sulfate aqueous solution was changed to 0.5 mass% zinc sulfate aqueous solution. Further, the reaction was terminated by aging for 15 minutes. In addition, the pulverization conditions were such that the air volume was 3.3 m ³ / min. I made it. Other steps were carried out in the same manner as in fatty acid metal salt 1 to obtain fatty acid metal salt 16. The resulting fatty acid metal salt 16 had a volume-based median diameter (D50) of 1.20 μm. Table 3 shows the physical properties of the fatty acid metal salt 16.

<Fatty acid metal salt 17>
Commercially available zinc stearate (MZ2 manufactured by NOF Corporation) is used as fatty acid metal salt 17. The volume-based median diameter (D50) was 1.29 μm. Table 3 shows the physical properties of the fatty acid metal salt 17. The particle size distribution is shown in FIG.

<Fatty acid metal salt 18>
Commercially available zinc stearate (manufactured by SZ2000 Sakai Chemical Industry) is designated as fatty acid metal salt 18. The volume-based median diameter (D50) was 5.30 μm. Table 3 shows the physical properties of the fatty acid metal salt 18. The particle size distribution is shown in FIG.

  Next, production examples of the toner carrier used in the image forming method of the present invention will be described.

[Synthesis example of urethane resin raw material]
<Synthesis of polyurethane raw material U-1>
Polytetramethylene glycol [PTG1000SN (trade name), manufactured by Hodogaya Chemical Co., Ltd.] 100.0 parts by mass, and isocyanate compound [Cosmonate MDI (trade name), manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.] 24.4 parts by mass of methyl ethyl ketone (MEK) ) In stepwise mixing in a solvent, the mixture was reacted at a temperature of 80 ° C. for 5 hours under a nitrogen atmosphere to obtain a polyurethane polyol having a weight average molecular weight Mw = 9,000 and a hydroxyl value of 22. Next, with respect to 100.0 parts by mass of this polyurethane polyol, 41.5 parts by mass of isocyanate [Coronate 2521 (trade name), Nippon Polyurethane Industry Co., Ltd.] was sufficiently mixed and stirred with a stirring motor to obtain polyurethane raw material U-1. It was.

<Synthesis of polyurethane raw material U-2>
10.0 parts by mass of an isocyanate compound [Takenate D140N (trade name), manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.] in 100.0 parts by mass of polypropylene glycol [Actol Diol-1000 (trade name), manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.] MEK solvent The mixture was mixed stepwise and reacted at 80 ° C. for 5 hours under a nitrogen atmosphere to obtain a polyurethane polyol having a weight average molecular weight Mw = 11,000 and a hydroxyl value of 24. Next, with respect to 100.0 parts by mass of this polyurethane polyol, 34.2 parts by mass of isocyanate [Coronate 2521 (trade name), manufactured by Nippon Polyurethane Industry Co., Ltd.] was sufficiently mixed and stirred with a stirring motor to obtain polyurethane raw material U-2. It was.

<Synthesis of polyurethane raw material U-3>
A polyurethane raw material U-3 was obtained in the same manner as U-1, except that the isocyanate compound [Cosmonate MDI] was changed to 22.1 parts by mass and the isocyanate [Coronate 2521] was changed to 34.8 parts by mass.

<Synthesis of polyurethane raw material U-4>
A polyurethane raw material U-4 was obtained in the same manner as U-1, except that the isocyanate compound [Cosmonate MDI] was changed to 18.8 parts by mass and the isocyanate [Coronate 2521] was changed to 33.3 parts by mass.

<Synthesis of polyurethane raw material U-5>
A polyurethane raw material U-5 was obtained in the same manner as U-1, except that the isocyanate compound [Cosmonate MDI] was changed to 30.9 parts by mass and the isocyanate [Coronate 2521] was changed to 44.3 parts by mass.

[Synthesis example of acrylic resin]
<Synthesis of acrylic resin A-1>
300.0 parts by mass of toluene was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux tube, a dropping device, and a nitrogen gas introduction tube, and the temperature was raised to 120 ° C. under a nitrogen gas stream. Next, 18.8 parts by mass of methyl methacrylate (MMA), 23.2 parts by mass of styrene, 44.0 parts by mass of 2-ethylhexyl methacrylate (EHMA), 14.5 parts by mass of hydroxyethyl methacrylate (HEMA), initiator [Kaya Ester O (trade name), manufactured by Kayaku Akzo Co., Ltd.] 0.3 parts by mass of the mixture was added dropwise over 1.5 hours, and the mixture was heated to reflux for 2 hours while maintaining the temperature at 120 ° C. Next, after the temperature was lowered to 50 ° C., 200.0 parts by mass of toluene was distilled off under reduced pressure. The mixture was allowed to cool and the temperature was lowered to room temperature to obtain acrylic resin A-1.

<Synthesis of acrylic resin A-2>
300.0 parts by mass of toluene was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux tube, a dropping device, and a nitrogen gas introduction tube, and the temperature was raised to 120 ° C. under a nitrogen gas stream. Next, methyl methacrylate (MMA) 8.7 parts by mass, 2-ethylhexyl methacrylate (EHMA) 17.2 parts by mass, cyclohexyl methacrylate (CHMA) 10.9 parts by mass, stearyl methacrylate (SMA) 63.2 parts by mass, start A mixture of 0.4 parts by mass of an agent [Kaya Ester O (trade name), manufactured by Kayaku Akzo Co., Ltd.] was dropped over 1.5 hours, and the mixture was further heated and refluxed for 2 hours while maintaining the temperature at 120 ° C. Next, after the temperature was lowered to 50 ° C., 200.0 parts by mass of toluene was distilled off under reduced pressure. The mixture was allowed to cool and the temperature was lowered to room temperature to obtain acrylic resin A-2.

<Synthesis of acrylic resin A-3>
300.0 parts by mass of toluene was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux tube, a dropping device, and a nitrogen gas introduction tube, and the temperature was raised to 120 ° C. under a nitrogen gas stream. Next, 20.7 parts by mass of methyl methacrylate (MMA), 38.7 parts by mass of styrene, 24.5 parts by mass of 2-ethylhexyl methacrylate (EHMA), 16.1 parts by mass of hydroxyethyl methacrylate (HEMA), initiator [Kaya Ester O (trade name), manufactured by Kayaku Akzo Co., Ltd.] A 0.35 part by mass mixture was added dropwise over 1.2 hours, and the mixture was further heated to reflux for 1 hour while maintaining the temperature at 120 ° C. Next, after the temperature was lowered to 50 ° C., 200.0 parts by mass of toluene was distilled off under reduced pressure. The mixture was allowed to cool and the temperature was lowered to room temperature to obtain acrylic resin A-3.

<Synthesis of acrylic resin A-4>
300.0 parts by mass of toluene was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux tube, a dropping device, and a nitrogen gas introduction tube, and the temperature was raised to 120 ° C. under a nitrogen gas stream. Next, methyl methacrylate (MMA) 8.7 parts by mass, 2-ethylhexyl methacrylate (EHMA) 17.2 parts by mass, cyclohexyl methacrylate (CHMA) 10.9 parts by mass, stearyl methacrylate (SMA) 63.2 parts by mass, start A mixture of 0.1 part by mass of an agent [Kaya Ester O (trade name), manufactured by Kayaku Akzo Co., Ltd.] was added dropwise over 1.5 hours, and the mixture was further heated to reflux for 2 hours while maintaining the temperature at 120 ° C. Next, after the temperature was lowered to 50 ° C., 200.0 parts by mass of toluene was distilled off under reduced pressure. After allowing to cool, the temperature was lowered to room temperature to obtain acrylic resin A-4.

<Synthesis of acrylic resin A-5>
300.0 parts by mass of toluene was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux tube, a dropping device, and a nitrogen gas introduction tube, and the temperature was raised to 120 ° C. under a nitrogen gas stream. Next, 27.9 parts by mass of methyl methacrylate (MMA), 24.9 parts by mass of styrene, 31.6 parts by mass of 2-ethylhexyl methacrylate (EHMA), 15.6 parts by mass of hydroxyethyl methacrylate (HEMA), initiator [Kaya Ester O (trade name), manufactured by Kayaku Akzo Co., Ltd.] 0.08 parts by mass of the mixture was added dropwise over 3 hours, and the mixture was further heated and refluxed for 5 hours while maintaining the temperature at 120 ° C. Next, after the temperature was lowered to 50 ° C., 200.0 parts by mass of toluene was distilled off under reduced pressure. The mixture was allowed to cool and the temperature was lowered to room temperature to obtain acrylic resin A-5.

<Synthesis of acrylic resin A-6>
300.0 parts by mass of toluene was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux tube, a dropping device, and a nitrogen gas introduction tube, and the temperature was raised to 120 ° C. under a nitrogen gas stream. Next, 14.5 parts by mass of methyl methacrylate (MMA), 28.8 parts by mass of 2-ethylhexyl methacrylate (EHMA), 56.7 parts by mass of hydroxyethyl methacrylate (HEMA), initiator [Kayaester O (trade name), (Manufactured by Kayaku Akzo Co., Ltd.) 0.4 parts by mass of the mixture was added dropwise over 3 hours, and the mixture was further heated and refluxed for 5 hours while maintaining the temperature at 120 ° C. Next, after the temperature was lowered to 50 ° C., 200.0 parts by mass of toluene was distilled off under reduced pressure. The mixture was allowed to cool and the temperature was lowered to room temperature to obtain acrylic resin A-6.

<Synthesis of Acrylic Resin A-7>
300.0 parts by mass of toluene was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux tube, a dropping device, and a nitrogen gas introduction tube, and the temperature was raised to 120 ° C. under a nitrogen gas stream. Next, 20.0 parts by mass of methyl methacrylate (MMA), 13.9 parts by mass of styrene, 66.1 parts by mass of 2-ethylhexyl methacrylate (EHMA), initiator [Kaya Ester O (trade name), manufactured by Kayaku Akzo Corporation 0.1 parts by mass of the mixture was added dropwise over 4 hours, and the mixture was further heated to reflux for 7 hours while maintaining the temperature at 120 ° C. Next, after the temperature was lowered to 50 ° C., 200.0 parts by mass of toluene was distilled off under reduced pressure. The mixture was allowed to cool and the temperature was lowered to room temperature to obtain acrylic resin A-7.

<Synthesis of acrylic resin A-8>
300.0 parts by mass of toluene was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux tube, a dropping device, and a nitrogen gas introduction tube, and the temperature was raised to 120 ° C. under a nitrogen gas stream. Next, a mixture of 33.9 parts by mass of methyl methacrylate (MMA), 66.1 parts by mass of hydroxyethyl methacrylate (HEMA), and 0.2 parts by mass of an initiator [Kayaester O (trade name), manufactured by Kayaku Akzo Co., Ltd.] Was added dropwise over 2 hours, and the mixture was further heated to reflux for 3 hours while maintaining the temperature at 120 ° C. Next, after the temperature was lowered to 50 ° C., 200.0 parts by mass of toluene was distilled off under reduced pressure. The mixture was allowed to cool and the temperature was lowered to room temperature to obtain acrylic resin A-8.

[Production example of toner carrier]
<Production Example 1 of Toner Carrier>
As a conductive shaft core body 1 in FIG. 12, a SUS 8 mm diameter metal core is nickel-plated, and a primer [DY35-051 (trade name), manufactured by Toray Dow Corning Silicone Co., Ltd.] is applied and baked. Using. Next, the conductive shaft core 1 is placed in a mold, and carbon black [Toker Black # 7360SB (for Toray Dow Corning Silicone Co., Ltd.) 100 parts by mass of a liquid silicone rubber material [SE6724A / B (trade name), manufactured by Toray Dow Corning Silicone Co., Ltd.] (Trade name), manufactured by Tokai Carbon Co., Ltd.], 35 parts by mass, 0.2 parts by mass of silica powder as a heat resistance imparting agent, and 0.1 parts by mass of a platinum catalyst were mixed in the mold. Was injected into the cavity formed. Subsequently, the mold was heated to cure and cure the silicone rubber at a temperature of 150 ° C. for 15 minutes. After demolding, the silicone rubber was further heated at 180 ° C. for 1 hour to complete the curing reaction. It was provided on the outer periphery of the core body 1.

Next, with respect to 200 parts by mass of the polyurethane raw material U-1, 24.0 parts by mass of carbon black [Special black 4 (trade name), manufactured by Degussa Japan Co., Ltd.] and 4.4 parts by mass of the acrylic resin A-1 are sufficiently obtained by a stirring motor. Were mixed and stirred. Next, the mixture was dissolved and mixed in MEK so as to have a total solid content ratio of 30% by mass, and dispersed for 2 hours in a horizontal continuous bead mill [NVM-03 (trade name), manufactured by IMEX Co., Ltd.] to obtain a dispersion. Further, this dispersion is diluted with MEK to a viscosity of 7 to 10 cps, dip-coated on the elastic layer, dried, and heat-treated at a temperature of 150 ° C. for 1 hour to form a film thickness of about 10 μm on the outer periphery of the elastic layer 2. The surface layer 3 was provided to obtain a toner carrier 1.

<Toner carrier production example 2>
A toner carrier 2 was obtained in the same manner as in Toner Carrier Production Example 1 except that the acrylic resin was changed to A-2.

<Production Example 3 of Toner Carrier>
A toner carrier 3 was obtained in the same manner as in Production Example 1 of the toner carrier except that the urethane resin was changed to U-2, the acrylic resin was changed to A-3, and the acrylic resin content was changed as shown in Table 5. .

<Toner carrier production example 4>
A toner carrier 4 was obtained in the same manner as in Production Example 1 of the toner carrier except that the urethane resin was changed to U-3, the acrylic resin was changed to A-4, and the acrylic resin content was changed as shown in Table 5. .

<Manufacturing Example 5 of Toner Carrier>
A toner carrier 5 was obtained in the same manner as in Production Example 1 of the toner carrier except that the urethane resin was changed to U-4, the acrylic resin was changed to A-5, and the acrylic resin content was changed as shown in Table 5. .

<Manufacturing Example 6 of Toner Carrier>
A toner carrier 6 was obtained in the same manner as in Toner Carrier Production Example 1 except that the urethane resin was changed to U-5 and the acrylic resin was changed to A-6.

<Production Example 7 of Toner Carrier>
A toner carrier 7 was obtained in the same manner as in Toner Carrier Production Example 1 except that the acrylic resin was changed to A-3.

<Manufacturing Example 8 of Toner Carrier>
A toner carrier 8 was obtained in the same manner as in Toner Carrier Production Example 1 except that the acrylic resin was changed to A-7.

<Production Example 9 of Toner Carrier>
A toner carrier 9 was obtained in the same manner as in Toner Carrier Production Example 1 except that the acrylic resin was changed to A-8 and the acrylic resin content was changed as shown in Table 5.

<Manufacturing Example 10 of Toner Carrier>
A toner carrier 10 was obtained in the same manner as in Toner Carrier Production Example 1 except that the acrylic resin was changed to A-8 and the acrylic resin content was changed as shown in Table 5.

<Manufacturing Example 11 of Toner Carrier>
A toner carrier 11 was obtained in the same manner as in Production Example 1 of the toner carrier except that the urethane resin was changed to U-5, the acrylic resin was changed to A-6, and the content of the acrylic resin was changed as shown in Table 5. . Data on the obtained toner carriers 1 to 11 are shown in Table 5 together with the composition.

  Next, an example of manufacturing a toner supply roller that can be used in the present invention is shown below. 90 parts by weight of polyol (trade name: FA908, manufactured by Sanyo Chemical Industries), 10 parts by weight of polyol (trade name: POP34-28, manufactured by Sanyo Chemical Industries), TOYOCAT-ET (trade name, manufactured by Tosoh Corporation, third grade) Amine catalyst) 0.1 parts by mass, TOYOCAT-L33 (trade name, tertiary amine catalyst manufactured by Tosoh Corporation) 0.5 parts by mass, water (foaming agent) 2.5 parts by mass, silicone and polyether copolymer 1 part by weight of SH190 (trade name, manufactured by Toray Dow Corning Silicone Co., Ltd.) was mixed in advance. Thereafter, 24 parts by mass of coronate 1021 (trade name, manufactured by Nippon Polyurethane Industry Co., Ltd., NCO% = 45) as a polyisocyanate was added to this mixture, mixed and stirred, and then subjected to foam molding using the above-mentioned mold. A toner supply roller 1 was produced in which a foamed elastic layer made of a 4.5 mm thick polyurethane sponge was integrally formed around a 5 mm cored bar.

Next, an example of manufacturing the toner used in the examples will be described.
(Toner Production Example 1)
To 1,000 parts by mass of ion-exchanged water in the reaction vessel, 15.3 parts by mass of sodium phosphate and 4.9 parts by mass of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . While stirring at 12,000 rpm using a TK homomixer (manufactured by Koki Kogyo Kogyo Co., Ltd.), a calcium chloride aqueous solution in which 8.5 parts by mass of calcium chloride is dissolved in 10 parts by mass of ion-exchanged water is added all at once. An aqueous medium containing a dispersion stabilizer was prepared.

Styrene 48 parts by mass Colorant (CI Pigment Red 122 / CI Pigment Red 57 = 1/1) 7 parts by mass Charge control agent (Orient: Bontron E-88) 0.20 parts by mass Charge control agent (Orient: Bontron E-89) 0.20 parts by mass Subsequently, the above material was charged into an attritor dispersing machine (Mitsui Miike Chemical Co., Ltd.), and further using zirconia particles having a diameter of 1.7 mm, 220 rpm For 5 hours to obtain a polymerizable monomer composition.

In the above polymerizable monomer composition, styrene 16 parts by mass, n-butyl acrylate 20 parts by mass, amorphous polyester resin 3 2.5 parts by mass, crystalline polyester 2 10 parts by mass, synthetic wax (Schumann Sazo- Product name = “SAZOL SPRAY30”, melting point = 98 ° C.) 12 parts by mass, negatively chargeable charge control resin 2 1.0 part by mass
-20 mass parts of low molecular weight styrene-acrylic resin 1 was added.

  The above material was kept at 69 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). In this, 2.5 parts by mass of a polymerization initiator t-hexyl peroxypivalate (manufactured by NOF Corporation, trade name “Perhexyl PV”, molecular weight: 202, 10 hour half-life temperature: 53.2 ° C.) are dissolved, A polymerizable monomer composition was prepared.

The polymerizable monomer composition is charged into the aqueous medium in the reaction vessel, stirred at 10,000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N ₂ purge, and prepared at pH 5.5. Grained. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours.

  After completion of the polymerization reaction, the reaction vessel is cooled, and the dispersion stabilizer is dissolved while stirring for 2 hours in a state where pH is 2 by adding 10% hydrochloric acid. The emulsion is filtered under pressure and further washed with 2,000 parts by mass or more of ion exchange water. The obtained cake is again returned to 1,000 parts by mass of ion-exchanged water and washed again with stirring for 2 hours in a state where 10% hydrochloric acid is added and the pH is adjusted to 1 or less. In the same manner as above, the emulsion was filtered under pressure, washed with 2,000 parts by mass or more of ion-exchanged water, sufficiently ventilated, dried under reduced pressure, and then air-classified to obtain magenta colored particles.

  First, 0.3 part by mass of hydrophobic titanium oxide 1 is added to 100 parts by mass of the obtained magenta colored particles, mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.), and then 1.5 parts by mass of hydrophobic silica 2 is added. 0.10 parts by mass of fatty acid metal salt 1 was added and mixed with a Henschel mixer (manufactured by Mitsui Miike) to obtain toner 1 having an external additive. The composition and physical properties of the obtained toner 1 are shown in Tables 6 and 7.

(Toner Production Example 2)
A toner 2 having an external additive was obtained in the same manner as in Toner Production Example 1 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 2. The composition and physical properties of the obtained toner 2 are shown in Tables 6 and 7.

(Toner Production Example 3)
5.0 parts by mass of amorphous polyester resin 3, 10 parts by mass of synthetic wax (manufactured by Schumann-Sazol, trade name = “Sazol SPRAY30”, melting point = 98 ° C.), polymerization initiator t- Hexyl peroxypivalate (manufactured by NOF Corporation, trade name “Perhexyl PV”, molecular weight: 202, 10 hour half-life temperature: 53.2 ° C.) Thus, Toner 3 having an external additive was obtained. The composition and physical properties of the obtained toner 3 are shown in Tables 6 and 7.

(Toner Production Example 4)
5.0 parts by mass of amorphous polyester resin 3, 10 parts by mass of synthetic wax (manufactured by Schumann-Sazol, trade name = “Sazol SPRAY30”, melting point = 98 ° C.), polymerization initiator t- Hexyl peroxypivalate (Nippon Yushi Co., Ltd., trade name “Perhexyl PV”, molecular weight: 202, 10 hour half-life temperature: 53.2 ° C.) Thus, Toner 4 having an external additive was obtained. The composition and physical properties of the obtained toner 4 are shown in Tables 6 and 7.

(Toner Production Example 5)
2.0 parts by mass of amorphous polyester resin 3 and 13 parts by mass of synthetic wax (manufactured by Schumann-Sazol, trade name = “Sazol SPRAY30”, melting point = 98 ° C.), polymerization initiator t- Hexyl peroxypivalate (Nippon Yushi Co., Ltd., trade name “Perhexyl PV”, molecular weight: 202, 10 hour half-life temperature: 53.2 ° C.) Thus, Toner 5 having an external additive was obtained. The composition and physical properties of the obtained toner 5 are shown in Tables 6 and 7.

(Toner Production Example 6)
2.0 parts by mass of amorphous polyester resin 3 and 14 parts by mass of synthetic wax (manufactured by Schumann-Sazol, trade name = “Sazol SPRAY30”, melting point = 98 ° C.), polymerization initiator t- Hexyl peroxypivalate (manufactured by NOF Corporation, trade name “Perhexyl PV”, molecular weight: 202, 10 hour half-life temperature: 53.2 ° C.) Thus, Toner 6 having an external additive was obtained. The composition and physical properties of the obtained toner 6 are shown in Tables 6 and 7.

(Toner Production Example 7)
Amorphous polyester resin 3 in 6.0 parts by mass, synthetic wax (manufactured by Schumann-Sazol, trade name = “Sazol SPRAY30”, melting point = 98 ° C.) 9 parts by mass, polymerization initiator t- Hexyl peroxypivalate (manufactured by NOF Corporation, trade name “Perhexyl PV”, molecular weight: 202, 10 hour half-life temperature: 53.2 ° C.) Thus, Toner 7 having an external additive was obtained. The composition and physical properties of the obtained toner 7 are shown in Tables 6 and 7.

(Toner Production Example 8)
2.0 parts by mass of amorphous polyester resin 3 and 14 parts by mass of synthetic wax (manufactured by Schumann-Sazol, trade name = “Sazol SPRAY30”, melting point = 98 ° C.), polymerization initiator t- Hexyl peroxypivalate (manufactured by NOF Corporation, trade name “Perhexyl PV”, molecular weight: 202, 10 hour half-life temperature: 53.2 ° C.) Thus, Toner 8 having an external additive was obtained. The composition and physical properties of the obtained toner 8 are shown in Tables 6 and 7.

(Toner Production Example 9)
2.0 parts by mass of amorphous polyester resin 3 and 14 parts by mass of synthetic wax (manufactured by Schumann-Sazol, trade name = “Sazol SPRAY30”, melting point = 98 ° C.), polymerization initiator t- Hexyl peroxypivalate (Nippon Yushi Co., Ltd., trade name “Perhexyl PV”, molecular weight: 202, 10 hour half-life temperature: 53.2 ° C.) Thus, Toner 9 having an external additive was obtained. The composition and physical properties of the obtained toner 9 are shown in Tables 6 and 7.

(Toner Production Example 10)
9.0 parts by mass of amorphous polyester resin 3, 9 parts by mass of synthetic wax (manufactured by Schumann-Sazol, trade name = “Sazol SPRAY30”, melting point = 98 ° C.), polymerization initiator t- Hexyl peroxypivalate (Nippon Yushi Co., Ltd., trade name “Perhexyl PV”, molecular weight: 202, 10 hour half-life temperature: 53.2 ° C.) Thus, Toner 10 having an external additive was obtained. The composition and physical properties of the obtained toner 10 are shown in Tables 6 and 7.

(Toner Production Example 11)
A toner 11 having an external additive was obtained in the same manner as in Toner Production Example 9 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 3. The composition and physical properties of the obtained toner 11 are shown in Tables 6 and 7.

(Toner Production Example 12)
A toner 12 having an external additive was obtained in the same manner as in Toner Production Example 9 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 4. The composition and physical properties of the obtained toner 12 are shown in Tables 6 and 7.

(Toner Production Example 13)
A toner 13 having an external additive was obtained in the same manner as in Toner Production Example 9 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 5. The composition and physical properties of the obtained toner 13 are shown in Tables 6 and 7.

(Toner Production Example 14)
The preparation of the dispersion medium was changed as follows: 20.5 parts by mass of sodium phosphate and 6.2 parts by mass of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 11.5 parts by mass of calcium chloride was dissolved in 10 parts by mass of ion-exchanged water was added. A toner 14 was obtained in the same manner as in Toner Production Example 13 except that an aqueous medium containing a dispersion stabilizer was prepared and the fatty acid metal salt 5 was changed to the fatty acid metal salt 6. The composition and physical properties of the obtained toner 14 are shown in Tables 6 and 7.

(Toner Production Example 15)
The preparation of the dispersion medium was changed as follows: 11.3 parts by mass of sodium phosphate and 3.7 parts by mass of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 6.4 parts by mass of calcium chloride is dissolved in 10 parts by mass of ion-exchanged water is added. A toner 15 was obtained in the same manner as in Toner Production Example 13 except that an aqueous medium containing a dispersion stabilizer was prepared and the fatty acid metal salt 5 was changed to the fatty acid metal salt 6. The composition and physical properties of the obtained toner 15 are shown in Tables 6 and 7.

(Toner Production Example 16)
The preparation of the dispersion medium was changed as follows: 20.5 parts by mass of sodium phosphate and 6.2 parts by mass of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 11.5 parts by mass of calcium chloride was dissolved in 10 parts by mass of ion-exchanged water was added. A toner 16 was obtained in the same manner as in Toner Production Example 13 except that an aqueous medium containing a dispersion stabilizer was prepared and the fatty acid metal salt 5 was changed to the fatty acid metal salt 7. The composition and physical properties of the obtained toner 16 are shown in Tables 6 and 7.

(Toner Production Example 17)
The preparation of the dispersion medium was changed as follows: 9.0 parts by mass of sodium phosphate and 3.0 parts by mass of 10% hydrochloric acid were added, and the mixture was kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 5.4 parts by mass of calcium chloride is dissolved in 10 parts by mass of ion-exchanged water is added. Toner particles 17 were obtained in the same manner as in Toner Production Example 13 except that an aqueous medium containing a dispersion stabilizer was prepared and that the fatty acid metal salt 5 was changed to the fatty acid metal salt 7. The composition and physical properties of the obtained toner 17 are shown in Tables 6 and 7.

(Toner Production Example 18)
A toner 18 having an external additive was obtained in the same manner as in Toner Production Example 9 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 6. The composition and physical properties of the obtained toner 18 are shown in Tables 6 and 7.

(Toner Production Example 19)
A toner 19 having an external additive was obtained in the same manner as in Toner Production Example 9 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 7. The composition and physical properties of the obtained toner 19 are shown in Tables 6 and 7.

(Toner Production Example 20)
The preparation of the dispersion medium was changed as follows: 20.5 parts by mass of sodium phosphate and 6.2 parts by mass of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 11.5 parts by mass of calcium chloride was dissolved in 10 parts by mass of ion-exchanged water was added. Toner 20 was obtained in the same manner as in Toner Production Example 13 except that an aqueous medium containing a dispersion stabilizer was prepared and that fatty acid metal salt 5 was changed to fatty acid metal salt 8. The composition and physical properties of the obtained toner 20 are shown in Tables 6 and 7.

(Toner Production Example 21)
The preparation of the dispersion medium was changed as follows: 9.0 parts by mass of sodium phosphate and 3.0 parts by mass of 10% hydrochloric acid were added, and the mixture was kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 5.4 parts by mass of calcium chloride is dissolved in 10 parts by mass of ion-exchanged water is added. Toner 21 was obtained in the same manner as in Toner Production Example 13 except that an aqueous medium containing a dispersion stabilizer was prepared and that fatty acid metal salt 5 was changed to fatty acid metal salt 8. The composition and physical properties of the obtained toner 21 are shown in Tables 6 and 7.

(Toner Production Example 22)
The preparation of the dispersion medium was changed as follows: 20.5 parts by mass of sodium phosphate and 6.2 parts by mass of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 11.5 parts by mass of calcium chloride was dissolved in 10 parts by mass of ion-exchanged water was added. A toner 22 was obtained in the same manner as in Toner Production Example 13 except that an aqueous medium containing a dispersion stabilizer was prepared and the fatty acid metal salt 5 was changed to the fatty acid metal salt 9. The composition and physical properties of the obtained toner 22 are shown in Tables 6 and 7.

(Toner Production Example 23)
The preparation of the dispersion medium was changed as follows: 9.0 parts by mass of sodium phosphate and 3.0 parts by mass of 10% hydrochloric acid were added, and the mixture was kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 5.4 parts by mass of calcium chloride is dissolved in 10 parts by mass of ion-exchanged water is added. A toner 23 was obtained in the same manner as in Toner Production Example 13 except that an aqueous medium containing a dispersion stabilizer was prepared and the fatty acid metal salt 5 was changed to the fatty acid metal salt 9. The composition and physical properties of the obtained toner 23 are shown in Tables 6 and 7.

(Toner Production Example 24)
A toner 24 having an external additive was obtained in the same manner as in Toner Production Example 9 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 8. The composition and physical properties of the obtained toner 24 are shown in Tables 6 and 7.

(Toner Production Example 25)
A toner 25 having an external additive was obtained in the same manner as in Toner Production Example 9 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 10. The composition and physical properties of the obtained toner 25 are shown in Tables 6 and 7.

(Toner Production Example 26)
The preparation of the dispersion medium was changed as follows: 9.0 parts by mass of sodium phosphate and 3.0 parts by mass of 10% hydrochloric acid were added, and the mixture was kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 5.4 parts by mass of calcium chloride is dissolved in 10 parts by mass of ion-exchanged water is added. Toner 26 was obtained in the same manner as in Toner Production Example 13 except that an aqueous medium containing a dispersion stabilizer was prepared and that fatty acid metal salt 5 was changed to fatty acid metal salt 11. The composition and physical properties of the obtained toner 26 are shown in Tables 6 and 7.

(Toner Production Example 27)
The preparation of the dispersion medium was changed as follows: 20.5 parts by mass of sodium phosphate and 6.2 parts by mass of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 11.5 parts by mass of calcium chloride was dissolved in 10 parts by mass of ion-exchanged water was added. A toner 27 was obtained in the same manner as in Toner Production Example 13, except that an aqueous medium containing a dispersion stabilizer was prepared and the fatty acid metal salt 5 was changed to the fatty acid metal salt 11. The composition and physical properties of the obtained toner 27 are shown in Tables 6 and 7.

(Toner Production Example 28)
A toner 28 having an external additive was obtained in the same manner as in Toner Production Example 9 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 12. The composition and physical properties of the obtained toner 28 are shown in Tables 6 and 7.

(Toner Production Example 29)
A toner 29 having an external additive was obtained in the same manner as in Toner Production Example 9 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 6. The composition and physical properties of the obtained toner 29 are shown in Tables 6 and 7.

(Toner Production Example 30)
A toner 30 having an external additive was obtained in the same manner as in Toner Production Example 9 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 14. The composition and physical properties of the obtained toner 30 are shown in Tables 6 and 7.

(Toner Production Example 31)
The preparation of the dispersion medium was changed as follows: 20.5 parts by mass of sodium phosphate and 6.2 parts by mass of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 11.5 parts by mass of calcium chloride was dissolved in 10 parts by mass of ion-exchanged water was added. Toner Production Example 13 except that an aqueous medium containing a dispersion stabilizer was prepared, and the hydrophobic titanium oxide 1 was changed from 0.3 parts by weight to 0.6 parts by weight, and the fatty acid metal salt 5 was changed to the fatty acid metal salt 14. Similarly, toner 31 was obtained. The composition and physical properties of the obtained toner 31 are shown in Tables 6 and 7.

(Toner Production Example 32)
The preparation of the dispersion medium was changed as follows: 9.0 parts by mass of sodium phosphate and 3.0 parts by mass of 10% hydrochloric acid were added, and the mixture was kept at 65 ° C. for 60 minutes while purging with N ₂ . Ion-exchanged water 1 while stirring at 12,000 rpm using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.)
Aqueous calcium chloride solution in which 5.4 parts by mass of calcium chloride was dissolved in 0 parts by mass was prepared to prepare an aqueous medium containing a dispersion stabilizer, and hydrophobic titanium oxide 1 from 0.3 parts by mass to 0.6 parts by mass. A toner 32 was obtained in the same manner as in Toner Production Example 13 except that the fatty acid metal salt 5 was changed to the fatty acid metal salt 15 in parts by mass. The composition and physical properties of the obtained toner 32 are shown in Tables 6 and 7.

(Toner Production Example 33)
The preparation of the dispersion medium was changed as follows: 9.0 parts by mass of sodium phosphate and 3.0 parts by mass of 10% hydrochloric acid were added, and the mixture was kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 5.4 parts by mass of calcium chloride is dissolved in 10 parts by mass of ion-exchanged water is added. Toner Production Example 13 except that an aqueous medium containing a dispersion stabilizer was prepared, and the hydrophobic titanium oxide 1 was changed from 0.3 parts by weight to 0.6 parts by weight, and the fatty acid metal salt 5 was changed to the fatty acid metal salt 14. Similarly, toner particles 33 were obtained. The composition and physical properties of the obtained toner 33 are shown in Tables 6 and 7.

(Toner Production Example 34)
The preparation of the dispersion medium was changed as follows: 11.3 parts by mass of sodium phosphate and 3.7 parts by mass of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 6.4 parts by mass of calcium chloride is dissolved in 10 parts by mass of ion-exchanged water is added. Toner Production Example 13 except that an aqueous medium containing a dispersion stabilizer was prepared, and that the hydrophobic titanium oxide 1 was changed from 0.3 parts by weight to 0.6 parts by weight, and the fatty acid metal salt 5 was changed to the fatty acid metal salt 6. Similarly, toner 34 was obtained. The composition and physical properties of the obtained toner 34 are shown in Tables 6 and 7.

(Toner Production Example 35)
The preparation of the dispersion medium was changed as follows: 19.3 parts by mass of sodium phosphate and 6.1 parts by mass of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . While stirring at 12,000 rpm using a TK homomixer (manufactured by Koki Kogyo Kogyo Co., Ltd.), a calcium chloride aqueous solution in which 10.6 parts by mass of calcium chloride is dissolved in 10 parts by mass of ion-exchanged water is added all at once. Toner Production Example 13 except that an aqueous medium containing a dispersion stabilizer was prepared, and that the hydrophobic titanium oxide 1 was changed from 0.3 parts by weight to 0.6 parts by weight and the fatty acid metal salt 5 was changed to the fatty acid metal salt 15 Similarly, toner 35 was obtained. The composition and physical properties of the obtained toner 35 are shown in Tables 6 and 7.

(Toner Production Example 36)
The preparation of the dispersion medium was changed as follows: 7.3 parts by mass of sodium phosphate and 2.3 parts by mass of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 4.0 parts by mass of calcium chloride is dissolved in 10 parts by mass of ion-exchanged water is added. Toner Production Example 13 except that an aqueous medium containing a dispersion stabilizer was prepared, and that the hydrophobic titanium oxide 1 was changed from 0.3 parts by weight to 0.6 parts by weight, and the fatty acid metal salt 5 was changed to the fatty acid metal salt 6. Similarly, toner particles 36 were obtained. The composition and physical properties of the obtained toner 36 are shown in Tables 6 and 7.

(Toner Production Example 37)
The preparation of the dispersion medium was changed as follows: 20.5 parts by mass of sodium phosphate and 6.2 parts by mass of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 11.5 parts by mass of calcium chloride was dissolved in 10 parts by mass of ion-exchanged water was added. Toner Production Example 13 except that an aqueous medium containing a dispersion stabilizer was prepared, and that the hydrophobic titanium oxide 1 was changed from 0.3 parts by weight to 0.6 parts by weight and the fatty acid metal salt 5 was changed to the fatty acid metal salt 15 Similarly, toner particles 37 were obtained. The composition and physical properties of the obtained toner 37 are shown in Tables 6 and 7.

(Toner Production Example 38)
The preparation of the dispersion medium was changed as follows: 23.3 parts by mass of sodium phosphate and 7.5 parts by mass of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 13.0 parts by mass of calcium chloride is dissolved in 10 parts by mass of ion-exchanged water is added. Toner Production Example 13 except that an aqueous medium containing a dispersion stabilizer was prepared, and that the hydrophobic titanium oxide 1 was changed from 0.3 parts by weight to 0.6 parts by weight and the fatty acid metal salt 5 was changed to the fatty acid metal salt 13 Similarly, toner 38 was obtained. The composition and physical properties of the obtained toner 38 are shown in Tables 6 and 7.

(Toner Production Example 39)
The preparation of the dispersion medium was changed as follows: 23.3 parts by mass of sodium phosphate and 7.5 parts by mass of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 13.0 parts by mass of calcium chloride is dissolved in 10 parts by mass of ion-exchanged water is added. Toner Production Example 13 except that an aqueous medium containing a dispersion stabilizer was prepared, and that the hydrophobic titanium oxide 1 was changed from 0.3 parts by mass to 0.6 parts by mass and the fatty acid metal salt 5 was changed to the fatty acid metal salt 16 Similarly, toner 39 was obtained. The composition and physical properties of the obtained toner 39 are shown in Tables 6 and 7.

(Toner Production Example 40)
The preparation of the dispersion medium was changed as follows: 7.3 parts by mass of sodium phosphate and 2.3 parts by mass of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 4.0 parts by mass of calcium chloride is dissolved in 10 parts by mass of ion-exchanged water is added. Toner Production Example 13 except that an aqueous medium containing a dispersion stabilizer was prepared, and that the hydrophobic titanium oxide 1 was changed from 0.3 parts by weight to 0.6 parts by weight and the fatty acid metal salt 5 was changed to the fatty acid metal salt 13 Similarly, toner 40 was obtained. The composition and physical properties of the obtained toner 40 are shown in Tables 6 and 7.

(Toner Production Example 41)
The preparation of the dispersion medium was changed as follows: 7.3 parts by mass of sodium phosphate and 2.3 parts by mass of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 4.0 parts by mass of calcium chloride is dissolved in 10 parts by mass of ion-exchanged water is added. Toner Production Example 13 except that an aqueous medium containing a dispersion stabilizer was prepared, and that the hydrophobic titanium oxide 1 was changed from 0.3 parts by mass to 0.6 parts by mass and the fatty acid metal salt 5 was changed to the fatty acid metal salt 16 Similarly, toner 41 was obtained. The composition and physical properties of the obtained toner 41 are shown in Tables 6 and 7.

(Toner Production Example 42)
To 1,000 parts by mass of ion-exchanged water in the reaction vessel, 14 parts by mass of sodium phosphate and 4.5 parts by mass of 10% hydrochloric acid were added and kept at 65 ° C. for 60 minutes while purging with N ₂ . While stirring at 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), an aqueous solution of calcium chloride in which 7.8 parts by mass of calcium chloride is dissolved in 10 parts by mass of ion-exchanged water is added. An aqueous medium containing a dispersion stabilizer was prepared.

Styrene 48 parts by mass Colorant (CI Pigment Red 122 / CI Pigment Red 57 = 1/1) 7 parts by mass Charge control agent (Orient: Bontron E-88) 0.20 parts by mass Above The material was put into an attritor dispersing machine (Mitsui Miike Chemical Co., Ltd.), and further dispersed at 220 rpm for 5 hours using zirconia particles having a diameter of 1.7 mm to obtain a polymerizable monomer composition.

To the above polymerizable monomer composition, styrene 16 parts by mass, n-butyl acrylate 20 parts by mass, dipentaerythritol hexamyristate (melting point = 66 ° C., molecular weight 1514)
9.0 parts by mass / charge control agent (Orient: Bontron E-88) 0.20 parts by mass / negatively chargeable charge control resin 1 0.50 parts by mass / polymethacrylate macromonomer (manufactured by Toagosei Co., Ltd., (Product name “AA6”, Tg = 94 ° C.) 0.15 parts by mass and 10 parts by mass of crystalline polyester 1 were added.

  The above material was kept at 66 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). In this, 4.0 parts by mass of a polymerization initiator t-hexyl peroxypivalate (manufactured by NOF Corporation, trade name “Perhexyl PV”, molecular weight: 202, 10 hour half-life temperature: 53.2 ° C.) is dissolved, A polymerizable monomer composition was prepared.

The polymerizable monomer composition is charged into the aqueous medium in the reaction vessel, stirred at 10,000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N ₂ purge, and prepared at pH 5.8. Grained. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours.

  After completion of the polymerization reaction, the mixture is cooled, and then the dispersion stabilizer is dissolved with stirring for 2 hours in a state where pH is added by adding 10% hydrochloric acid. The emulsion is filtered under pressure and further washed with 2,000 parts by mass or more of ion exchange water. The obtained cake is again returned to 1,000 parts by mass of ion-exchanged water and washed again with stirring for 2 hours in a state where 10% hydrochloric acid is added and the pH is adjusted to 1 or less. In the same manner as above, the emulsion was filtered under pressure, washed with 2,000 parts by mass or more of ion-exchanged water, sufficiently ventilated, dried under reduced pressure, and then air-classified to obtain toner particles.

  First, 0.3 part by mass of hydrophobic titanium oxide 1 is added to 100 parts by mass of the obtained magenta colored toner particles, mixed with a Henschel mixer (manufactured by Mitsui Miike), and then 1.5 parts by mass of hydrophobic silica 1 is added. Then, 0.10 parts by mass of fatty acid metal salt 13 was added and mixed with a Henschel mixer (manufactured by Mitsui Miike) to obtain toner 42 having an external additive. The composition and physical properties of the obtained toner 42 are shown in Tables 6 and 7.

(Toner Production Example 43)
<Preparation of resin particle dispersion 1>
-Styrene 75 parts by mass-n-Butyl acrylate 25 parts by mass-Acrylic acid 3 parts by mass The above mixture was dissolved, and the nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd .: Nonipol 400) 1.5 parts by mass Parts and anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 2.2 parts by mass dissolved in 120 parts by mass of ion-exchanged water, dispersed in a flask, emulsified, and slowly for 10 minutes 10 parts by mass of ion-exchanged water in which 1.5 parts by mass of ammonium persulfate was dissolved and mixed with nitrogen, followed by nitrogen substitution, and then 1-cyclohexyl-1-methylethylperoxyneodecanoate (Japan) A product name "Percyclo ND-40E", manufactured by Yufu Co., Ltd., 2.5 parts by mass of 5 parts by weight is slowly stirred for 5 minutes. It was further added while stirring. Thereafter, while stirring the inside of the flask, the contents are heated in an oil bath until the temperature reaches 70 ° C., and emulsion polymerization is continued for 4 hours to disperse resin particles having an average particle diameter of 0.29 μm. Dispersion 1 was prepared.

<Preparation of resin particle dispersion 2>
-Styrene 40 parts by mass-n-Butyl acrylate 58 parts by mass-Divinylbenzene 0.03 parts by mass-Acrylic acid 3 parts by mass A mixture of the above and dissolved is a nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd.) : Nonipol 400) 1.5 parts by weight and anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 2.2 parts by weight were dissolved in 120 parts by weight of ion-exchanged water and dispersed in a flask. After emulsifying and slowly mixing for 10 minutes, 10 parts by mass of ion-exchanged water in which 2.4 parts by mass of ammonium persulfate was dissolved was added, and after replacing with nitrogen, the contents were stirred while stirring the inside of the flask. The product was heated in an oil bath until the product reached 70 ° C., and emulsion polymerization was continued for 4 hours to prepare resin particle dispersion 2 in which resin particles having an average particle size of 0.31 μm were dispersed. .

<Preparation of resin particle dispersion 3>
-Styrene 73 parts by mass-n-Butyl acrylate 25 parts by mass-Divinylbenzene 0.25 part by mass-Acrylic acid 3 parts by mass The above mixture was dissolved and a nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd.) : Nonipol 400) 1.5 parts by weight and anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 2.2 parts by weight were dissolved in 120 parts by weight of ion-exchanged water and dispersed in a flask. The mixture was emulsified and slowly mixed for 10 minutes. Then, 10 parts by mass of ion-exchanged water in which 1.9 parts by mass of ammonium persulfate was dissolved was added, and the atmosphere was replaced with nitrogen. The product was heated in an oil bath until the product reached 70 ° C., and emulsion polymerization was continued for 4 hours to prepare resin particle dispersion 3 in which resin particles having an average particle size of 0.31 μm were dispersed. .

<Preparation of Colorant Particle Dispersion 1>
・ C. I. Pigment Red 122 20 parts by mass / Anionic surfactant 3 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-Ion exchange water 78 mass parts The above was mixed and it disperse | distributed using the sand grinder mill. When the particle size distribution in the colorant particle dispersion 1 was measured using a particle size measuring device (LA-700, manufactured by Horiba, Ltd.), the average particle size of the contained colorant particles was 0.2 μm and 1 μm. No coarse particles exceeding were observed.

<Preparation of release agent particle dispersion>
・ Release agent No. 5 (melting point = 70 ° C.) 50 parts by mass / anionic surfactant 7 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
・ Ion-exchanged water 200 parts by mass The above was heated to 95 ° C. and dispersed using a homogenizer (manufactured by IKA: Ultra Turrax T50), and then dispersed with a pressure discharge homogenizer, and the average particle size was 0.5 μm. A release agent particle dispersion was prepared by dispersing the release agent.

<Adjustment of charge control particle dispersion>
-5 parts by mass of a metal compound of di-alkyl-salicylic acid (charge control agent, Bontron E-88, manufactured by Orient Chemical Industries)
-3 parts by weight of anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-Ion exchange water 78 mass parts The above was mixed and it disperse | distributed using the sand grinder mill. When the particle size distribution in the charge control particle dispersion 1 was measured using a particle size measuring device (LA-700, manufactured by Horiba, Ltd.), the average particle size of the charge control particles contained was 0.2 μm and 1 μm. No coarse particles exceeding were observed.

<Preparation of liquid mixture>
-Resin particle dispersion 1 280 parts by mass-Resin particle dispersion 2 100 parts by mass-Colorant dispersion 1 40 parts by mass-Release agent dispersion 70 parts by mass The above was equipped with a stirrer, condenser, and thermometer The mixture was put into a 1 liter separable flask and stirred. The mixture was adjusted to pH = 5.2 using 1N potassium hydroxide.

<Agglomerated particle formation>
As a flocculant, 150 parts by mass of an 8% aqueous sodium chloride solution was added dropwise to the mixed solution, and the flask was heated to 55 ° C. while stirring the inside of the flask. At this temperature, 3 parts by mass of resin particle dispersion 3 and 10 parts by mass of charge control agent particle dispersion were added. After maintaining at 55 ° C. for 2 hours, observation with an optical microscope confirmed that aggregated particles having an average particle diameter of about 3.3 μm were formed.

<Fusion process>
Then, after adding 3 parts by mass of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC), the mixture was heated to 95 ° C. while continuing stirring using a magnetic seal in a stainless steel flask. Hold for 12.5 hours. And after cooling, the reaction product is filtered, washed thoroughly with ion-exchanged water, then fluidized-bed dried at 45 ° C, and the shape is adjusted by dispersing it in a gas phase of 200-300 ° C with a spray dryer. As a result, toner particles were obtained.

  First, 0.3 part by mass of hydrophobic titanium oxide 1 is added to 100 parts by mass of the obtained magenta colored toner particles, mixed with a Henschel mixer (manufactured by Mitsui Miike), and then 2.5 parts by mass of hydrophobic silica 1. 0.10 parts by mass of fatty acid metal salt 15 was added and mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) to obtain toner 43 having an external additive. The physical properties and the like of the obtained toner 43 are shown in Table 7.

(Toner Production Example 44)
To 1,000 parts by mass of ion-exchanged water in the reaction vessel, 14 parts by mass of sodium phosphate and 4.5 parts by mass of 10% hydrochloric acid were added and kept at 65 ° C. for 60 minutes while purging with N ₂ . While stirring at 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), an aqueous solution of calcium chloride in which 7.8 parts by mass of calcium chloride is dissolved in 10 parts by mass of ion-exchanged water is added. An aqueous medium containing a dispersion stabilizer was prepared.

Styrene 48 parts by mass Colorant (CI Pigment Red 122 / CI Pigment Red 57 = 1/1) 7 parts by mass Charge control agent (Orient: Bontron E-88) 0.20 parts by mass Above The material was put into an attritor dispersing machine (Mitsui Miike Chemical Co., Ltd.), and further dispersed at 220 rpm for 5 hours using zirconia particles having a diameter of 1.7 mm to obtain a polymerizable monomer composition.

To the above polymerizable monomer composition, styrene 16 parts by mass, n-butyl acrylate 20 parts by mass, dipentaerythritol hexamyristate (melting point = 66 ° C., molecular weight 1514)
9.0 parts by mass / charge control agent (Orient: Bontron E-88) 0.20 parts by mass / negatively chargeable charge control resin 1 0.50 parts by mass / polymethacrylate macromonomer (manufactured by Toagosei Co., Ltd., Trade name “AA6”, Tg = 94 ° C.) 0.20 parts by mass Amorphous polyester 4 2.50 parts by mass Crystalline polyester 1 15 parts by mass were added.

  The above material was kept at 66 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). In this, 1.5 parts by mass of a polymerization initiator t-hexyl peroxypivalate (manufactured by NOF Corporation, trade name “Perhexyl PV”, molecular weight: 202, 10 hour half-life temperature: 53.2 ° C.) is dissolved, A polymerizable monomer composition was prepared.

The polymerizable monomer composition is charged into the aqueous medium in the reaction vessel, stirred at 10,000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N ₂ purge, and prepared at pH 5.8. Grained. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours.

  After completion of the polymerization reaction, the mixture is cooled, and then the dispersion stabilizer is dissolved with stirring for 2 hours in a state where pH is added by adding 10% hydrochloric acid. The emulsion is filtered under pressure and further washed with 2,000 parts by mass or more of ion exchange water. The obtained cake is again returned to 1,000 parts by mass of ion-exchanged water and washed again with stirring for 2 hours in a state where 10% hydrochloric acid is added and the pH is adjusted to 1 or less. In the same manner as above, the emulsion was filtered under pressure, washed with 2,000 parts by mass or more of ion-exchanged water, sufficiently ventilated, dried under reduced pressure, and then air-classified to obtain toner particles.

  First, 0.3 part by mass of hydrophobic titanium oxide 1 is added to 100 parts by mass of the obtained magenta colored toner particles, mixed with a Henschel mixer (manufactured by Mitsui Miike), and then 2.5 parts by mass of hydrophobic silica 1. Then, 0.10 parts by mass of fatty acid metal salt 13 was added and mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) to obtain toner 44 having an external additive. The composition and physical properties of the obtained toner 44 are shown in Tables 6 and 7.

(Toner Production Example 45)
Styrene-n-butyl acrylate-hydroxyethyl acrylate-octyl acrylate copolymer (Tg 61.5 ° C., molecular weight: Mw 53,000) 80 parts by mass Styrene-n-butyl acrylate-tetrafluoropropyl methacrylate copolymer (Tg 64 .5 ° C., molecular weight: Mw 55,000) 20 parts by mass / colorant (CI Pigment Red 122 / CI Pigment Red 57 = 1/1
)
5 parts by mass of aluminum salicylate compound (Bontron E-88: manufactured by Orient Chemical Co., Ltd.)
1 part by mass / polypropylene wax (mp 115 ° C.) 2 parts by mass After the above materials are mixed with a Henschel mixer, the kneaded product is melt-kneaded at 125 ° C. with a three roll mill, and the kneaded product is discharged from the kneaded product discharge unit. Then, the kneaded product was melt-kneaded twice at 120 ° C. with a three-roll mill twice. Further, the kneaded product was melt kneaded at 135 ° C. with a twin-screw kneading extruder. The obtained kneaded product is rapidly cooled to a predetermined temperature, allowed to stand at room temperature and gradually cooled, then coarsely pulverized with a cutter mill, pulverized with a fine pulverizer using a jet stream, and further hybridizer (Nara Machinery Co., Ltd.). And then pulverizing with a fine pulverizer using a jet air stream and air classification to obtain magenta colored toner particles.

  First, 0.3 part by mass of hydrophobic titanium oxide 1 is added to 100 parts by mass of the obtained magenta colored toner particles, mixed with a Henschel mixer (manufactured by Mitsui Miike), and then 7.5 parts by mass of hydrophobic silica 1. 0.20 parts by mass of fatty acid metal salt 13 and 0.2 parts by mass of resin particles (Tg 74.5 ° C., molecular weight: Mw 25000) of methyl methacrylate-pentafluorooctyl acrylate copolymer having a primary particle size of 100 nm are added, and Henschel is added. The toner 45 having an external additive was obtained by mixing with a mixer (manufactured by Mitsui Miike). The physical properties and the like of the obtained toner 45 are shown in Table 7.

(Toner Production Example 46)
<Synthesis of toner binder>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 660 parts of bisphenol A ethylene oxide 2-mole adduct, 100 parts of bisphenol A propylene oxide 2-mole adduct, 290 parts of terephthalic acid and 2.5 parts of dibutyltin oxide The reaction was conducted at 220 ° C. for 12 hours at normal pressure, and further for 6.5 hours at a reduced pressure of 10 to 15 mmHg, then cooled to 190 ° C., and 32 parts of phthalic anhydride was added thereto, followed by reaction for 2 hours. did. Next, the mixture was cooled to 80 ° C. and reacted with 180 parts of isophorone diisocyanate in ethyl acetate for 2 hours to obtain an isocyanate-containing prepolymer (1). Next, 267 parts of prepolymer (1) and 14 parts of isophoronediamine were reacted at 50 ° C. for 2 hours to obtain urea-modified polyester (1) having a weight average molecular weight of 65,000. As above, 624 parts of bisphenol A ethylene oxide 2-mole adduct, 100 parts of bisphenol A propylene oxide 2-mole adduct, 138 parts of terephthalic acid, and 138 parts of isophthalic acid were subjected to polycondensation at 230 ° C. for 5 hours under normal pressure. Reaction was performed at a reduced pressure of ˜15 mmHg for 5.5 hours to obtain unmodified polyester (a) having a peak molecular weight of 6,300. 250 parts of urea-modified polyester (1) and 750 parts of unmodified polyester (a) were dissolved and mixed in 2,000 parts of tetrahydrofuran solvent to obtain a tetrahydrofuran solution of toner binder (1).

<Create toner>
In a beaker, 240 parts of a tetrahydrofuran solution of the toner binder (1), C.I. I. 4 parts of Pigment Red 122 pigment, 3 parts of a charge control agent (Bontron E-88, manufactured by Orient Chemical Industries), 1-cyclohexyl-1-methylethyl peroxyneodecanoate (manufactured by NOF Corporation, trade name “Percyclo ND”) ”, Molecular weight: 313, 10 hour half-life temperature: 41.4 ° C., active oxygen content: 3.58%) 1.0 part by mass, stirred at 12,000 rpm with a TK homomixer at 55 ° C., It was uniformly dissolved and dispersed. In a beaker, 706 parts of ion-exchanged water, 294 parts of hydroxyapatite 10% suspension (Superite 10 manufactured by Nippon Chemical Industry Co., Ltd.) and 0.17 part of sodium dodecylbenzenesulfonate were uniformly dissolved. Next, the temperature was raised to 55 ° C., and the toner material solution was added and stirred for 10 minutes while stirring at 12,000 rpm with a TK homomixer. The mixture was then transferred to a Kolben equipped with a stirrer and a thermometer, heated to 98 ° C. to remove the solvent, filtered, washed and dried, and then air classified to obtain toner particles.

  First, 0.3 part by mass of hydrophobic titanium oxide 1 is added to 100 parts by mass of the obtained magenta-colored toner particles, mixed with a Henschel mixer (manufactured by Mitsui Miike), and then 4.5 parts by mass of hydrophobic silica 1. Then, 0.40 part by mass of fatty acid metal salt 13 was added and mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) to obtain toner 46 having an external additive. The physical properties of the obtained toner 46 are shown in Table 7.

(Toner Production Example 47)
Toner particles were obtained in the same manner as in Toner Production Example 43.
First, 0.3 part by mass of hydrophobic titanium oxide 1 is added to 100 parts by mass of the obtained magenta-colored toner particles, mixed with a Henschel mixer (manufactured by Mitsui Miike), and then 5.5 parts by mass of hydrophobic silica 1. Then, 0.30 part by mass of fatty acid metal salt 15 was added and mixed with a Henschel mixer (manufactured by Mitsui Miike) to obtain toner 47 having an external additive. The physical properties and the like of the obtained toner 47 are shown in Table 7.

(Toner Production Example 48)
Styrene-n-butyl acrylate copolymer (Tg 57.1 ° C., molecular weight: Mw 27000)
100 parts by weight of colorant (CI Pigment Red 122 / CI Pigment Red 57 = 1/1)
5 parts by mass charge control agent (Orient: Bontron E-88) 1.5 parts by mass polypropylene wax (mp 115 ° C.) 2 parts by mass After the above materials were mixed with a Henschel mixer, a twin-screw kneading extruder at 125 ° C. Then, the kneaded product was gradually cooled to room temperature, coarsely pulverized by a cutter mill, pulverized using a fine pulverizer using a jet stream, and classified by wind to obtain toner particles.

  First, 0.3 part by mass of hydrophobic titanium oxide 1 is added to 100 parts by mass of the obtained magenta-colored toner particles, mixed with a Henschel mixer (manufactured by Mitsui Miike), and then 3.5 parts by mass of hydrophobic silica 1. Then, 0.70 parts by mass of fatty acid metal salt 17 was added and mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) to obtain toner 48 having an external additive. The physical properties and the like of the obtained toner 48 are shown in Table 7.

(Toner Production Example 49)
A toner 49 having an external additive was obtained in the same manner as in Toner Production Example 48 except that the fatty acid metal salt 17 was changed to the fatty acid metal salt 18. The physical properties and the like of the obtained toner 49 are shown in Table 7.

(Toner Production Example 50)
<Synthesis of toner binder>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 660 parts of bisphenol A ethylene oxide 2-mole adduct, 100 parts of bisphenol A propylene oxide 2-mole adduct, 290 parts of terephthalic acid and 2.5 parts of dibutyltin oxide The reaction was conducted at 220 ° C. for 12 hours at normal pressure, and further for 6.5 hours at a reduced pressure of 10 to 15 mmHg, then cooled to 190 ° C., and 40 parts of phthalic anhydride was added thereto, followed by reaction for 2 hours. did. Next, the mixture was cooled to 80 ° C. and reacted with 180 parts of isophorone diisocyanate in ethyl acetate for 2 hours to obtain an isocyanate-containing prepolymer (1). Next, 267 parts of prepolymer (1) and 14 parts of isophoronediamine were reacted at 50 ° C. for 2 hours to obtain a urea-modified polyester (1) having a weight average molecular weight of 72,000. As above, 624 parts of bisphenol A ethylene oxide 2-mole adduct, 100 parts of bisphenol A propylene oxide 2-mole adduct, 138 parts of terephthalic acid, and 138 parts of isophthalic acid were subjected to polycondensation at 230 ° C. for 5 hours under normal pressure. Reaction was performed at a reduced pressure of ˜15 mmHg for 5.5 hours to obtain unmodified polyester (a) having a peak molecular weight of 6,300. A solution of 220 parts of urea-modified polyester (1), 750 parts of unmodified polyester (a) and 30 parts of amorphous polyester 6 are dissolved and mixed in 2,000 parts of tetrahydrofuran solvent, and a tetrahydrofuran solution of toner binder (1). Got.

<Create toner>
In a beaker, 240 parts of a tetrahydrofuran solution of the toner binder (1), C.I. I. 4 parts of Pigment Red 122 pigment, 3 parts of a charge control agent (Bontron E-88, manufactured by Orient Chemical Industries), 1-cyclohexyl-1-methylethyl peroxyneodecanoate (manufactured by NOF Corporation, trade name “Percyclo ND”) ”, Molecular weight: 313, 10 hour half-life temperature: 41.4 ° C., active oxygen content: 3.58%) 1.0 part by mass, stirred at 12,000 rpm with a TK homomixer at 55 ° C., It was uniformly dissolved and dispersed. In a beaker, 706 parts of ion-exchanged water, 294 parts of hydroxyapatite 10% suspension (Superite 10 manufactured by Nippon Chemical Industry Co., Ltd.) and 0.17 part of sodium dodecylbenzenesulfonate were uniformly dissolved. Next, the temperature was raised to 55 ° C., and the toner material solution was added and stirred for 10 minutes while stirring at 12,000 rpm with a TK homomixer. The mixture was then transferred to a Kolben equipped with a stirrer and a thermometer, heated to 98 ° C. to remove the solvent, filtered, washed and dried, and then air classified to obtain toner particles.

  First, 0.3 part by mass of hydrophobic titanium oxide 1 is added to 100 parts by mass of the obtained magenta colored toner particles, mixed with a Henschel mixer (manufactured by Mitsui Miike), and then 6.5 parts by mass of hydrophobic silica 1. Then, 1.2 parts by mass of fatty acid metal salt 17 was added and mixed with a Henschel mixer (manufactured by Mitsui Miike) to obtain toner 50 having an external additive. The physical properties of the obtained toner 50 are shown in Table 7.

(Toner Production Example 51)
A toner 51 having an external additive was obtained in the same manner as in Toner Production Example 48 except that the fatty acid metal salt 17 was not used. The physical properties and the like of the obtained toner 51 are shown in Table 7.

(Toner Production Example 52)
To 1,000 parts by mass of ion-exchanged water in the reaction vessel, 14 parts by mass of sodium phosphate and 4.5 parts by mass of 10% hydrochloric acid were added and kept at 65 ° C. for 60 minutes while purging with N ₂ . While stirring at 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), an aqueous solution of calcium chloride in which 7.8 parts by mass of calcium chloride is dissolved in 10 parts by mass of ion-exchanged water is added. An aqueous medium containing a dispersion stabilizer was prepared.

Styrene 48 parts by mass Colorant (CI Pigment Red 122 / CI Pigment Red 57 = 1/1) 7 parts by mass Charge control agent (Orient: Bontron E-88) 0.20 parts by mass Above The material was put into an attritor dispersing machine (Mitsui Miike Chemical Co., Ltd.), and further dispersed at 220 rpm for 5 hours using zirconia particles having a diameter of 1.7 mm to obtain a polymerizable monomer composition.

To the above polymerizable monomer composition, styrene 16 parts by mass, n-butyl acrylate 20 parts by mass, dipentaerythritol hexamyristate (melting point = 66 ° C., molecular weight 1,514)
9.0 parts by mass, charge control agent (Orient: Bontron E-88) 0.20 parts by mass, negatively chargeable charge control resin 1 0.50 parts by mass, amorphous polyester 1 2.50 parts by mass, amorphous 2.50 parts by mass of polyester 2 and 2.50 parts by mass of amorphous polyester 4 were added.

  The above material was kept at 66 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). To this was dissolved 2.0 parts by mass of a polymerization initiator t-hexyl peroxypivalate (manufactured by NOF Corporation, trade name “Perhexyl PV”, molecular weight: 202, 10 hour half-life temperature: 53.2 ° C.), A polymerizable monomer composition was prepared.

The polymerizable monomer composition is charged into the aqueous medium in the reaction vessel, stirred at 10,000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N ₂ purge, and prepared at pH 5.8. Grained. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours.

  After completion of the polymerization reaction, the mixture is cooled, and then the dispersion stabilizer is dissolved with stirring for 2 hours in a state where pH is added by adding 10% hydrochloric acid. The emulsion is filtered under pressure and further washed with 2,000 parts by mass or more of ion exchange water. The obtained cake is again returned to 1,000 parts by mass of ion-exchanged water and washed again with stirring for 2 hours in a state where 10% hydrochloric acid is added and the pH is adjusted to 1 or less. In the same manner as above, the emulsion was filtered under pressure, washed with 2,000 parts by mass or more of ion-exchanged water, sufficiently ventilated, dried under reduced pressure, and then air-classified to obtain toner particles.

  First, 0.3 part by mass of hydrophobic titanium oxide 1 is added to 100 parts by mass of the obtained magenta colored toner particles, mixed with a Henschel mixer (manufactured by Mitsui Miike), and then 6.5 parts by mass of hydrophobic silica 1. In addition, the toner was mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) to obtain a toner 52 having an external additive. The composition and physical properties of the obtained toner 52 are shown in Tables 6 and 7.

(Toner Production Example 53)
A toner 53 having an external additive was obtained in the same manner as in Toner Production Example 48 except that the hydrophobic silica 1 was changed to 4.0 parts by mass and the fatty acid metal salt 17 was not used. The physical properties and the like of the obtained toner 53 are shown in Table 7.

(Toner Production Example 54)
A toner 54 having an external additive was obtained in the same manner as in Toner Production Example 52 except that the hydrophobic silica 1 was changed to 4.5 parts by mass. The composition and physical properties of the obtained toner 54 are shown in Tables 6 and 7.

(Toner Production Example 55)
A toner 55 having an external additive was obtained in the same manner as in Toner Production Example 52 except that the hydrophobic silica 1 was changed to 5.5 parts by mass. The composition and physical properties of the obtained toner 55 are shown in Tables 6 and 7.

(Evaluation machine)
The evaluation machine used for the evaluation of the examples of the present invention will be described. Commercially available HP Color L
The process speed of aser Jet 3500 (manufactured by HP) was modified to 150 mm / s, and an external power source was installed so that a bias could be applied to the toner regulating member as shown in FIG. A bias corresponding to −100 V of the bias applied to the toner carrier was applied to the toner regulating member. Also, the product toner is removed from the commercially available magenta cartridge, the interior is cleaned by air blow, the resin film laminated on the surface of the toner regulating member is peeled off, and the toner carrier and the toner supply roller 1 are appropriately replaced. The toner of the present invention was filled with 100 g, and for the other cyan, yellow, and black cartridges, the product toner was removed and inserted into each station for evaluation.

<Examples 1 to 64>
Various evaluations were performed using the toners and toner carriers described in Table 7 under the setting conditions described in Table 7 using the evaluation machine. The evaluation results are shown in Tables 8, 9 and 10.

<Comparative Examples 1-8>
Various evaluations were performed using the toners and toner carriers described in Table 7 under the setting conditions described in Table 7 using the evaluation machine. The evaluation results are shown in Tables 8, 9 and 10.

It is a figure about the change of a friction coefficient with time at the time of friction coefficient measurement. 1 is a schematic diagram of an image forming apparatus that performs non-magnetic one-component contact development. 1 is a schematic diagram of an image forming apparatus that performs non-magnetic one-component contact development. 1 is a schematic view of an image forming apparatus that performs non-magnetic one-component non-contact development. 1 is a schematic view of an image forming apparatus that performs non-magnetic one-component non-contact development. Schematic diagram of an image forming apparatus that uses a transfer belt as a secondary transfer means for secondary transfer of four color toner images that have been primarily transferred onto the intermediate transfer drum using an intermediate transfer drum. It is. It is a particle size distribution of the fatty acid metal salt 1 used in the examples of the present invention. It is a particle size distribution of the fatty acid metal salt 2 used for the Example of this invention. It is a particle size distribution of the fatty acid metal salt 17 (made by NOF Corporation) used for the comparative example of this invention. It is a particle size distribution of the fatty acid metal salt 18 (made by Sakai Chemical) used for the comparative example of this invention. Conceptual diagram of a friction coefficient measuring device according to the present invention Conceptual diagram of toner carrier

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Conductive shaft core 2 Elastic layer 3 Surface layer 9 Power supply 10 Latent image carrier (photosensitive drum)
11 Photoconductor contact charging member (elastic roller)
DESCRIPTION OF SYMBOLS 12 Power supply 13 Development apparatus 14 Toner carrier 15 Elastic roller 15a Core metal 16 Elastic blade (regulation member)
DESCRIPTION OF SYMBOLS 17 Toner 23 Developer container 24 Blade support metal plate 25 Stirring means 26 Toner leakage prevention member 27 Power supply 31 Weight 32 Digital force gauge 33 Personal computer 34 PET film 169 Latent image carrier 170 Developing device 171 Developer container 172 Developer carrier 173 Supply roller 174 Elastic blade as developer layer thickness regulating member 175 Stirring member 176 Non-magnetic one-component developer 241 Photoconductor 242 Charging roller 244 Developer 245 Intermediate transfer drum 246 Transfer material 247 Transfer belt 248 Cleaning blade 249 Cleaning unit 280 Cleaning unit 281 Fixing device

Claims (10)

A toner layer is formed by a regulating member for forming a thin layer of toner on the toner carrier, and the toner is developed by a toner carrier that is developed in a non-contact or contact manner with the photoconductor to form a toner image on the photoconductor. An image forming method to obtain,
The friction coefficient μd of the toner carrier is 1.35 to 2.00,
The toner is a one-component developing toner having at least a binder resin, a toner particle containing a colorant, and at least an inorganic fine powder;
An image forming method, wherein the toner has a friction coefficient μt of 0.06 to 0.35 in a state where a thin layer of toner is formed on the toner carrier.   The image forming method according to claim 1, wherein the toner has a friction coefficient μt of 0.06 to 0.20. The toner is a toner further containing a fatty acid metal salt in the toner particles;
When the number average particle diameter (D1) of the toner particles is Dt (μm) and the volume-based median diameter (D50) of the fatty acid metal salt is Df (μm),
0.022 ≦ Df / Dt ≦ 0.270
3.00 ≦ Dt ≦ 8.00
0.15 ≦ Df ≦ 1.00
The image forming method according to claim 1, wherein the relationship is satisfied. The fatty acid metal salt has a Df of 0.15 ≦ Df ≦ 0.75, a span value B defined by the following formula (1) of 1.75 or less,
4. The image forming method according to claim 3, wherein the toner has a liberation rate of the fatty acid metal salt in the toner of 1.0% or more and 30.0% or less.
Span value B = (D95s−D5s) / D50s (1)
D5s: 5% cumulative diameter based on volume of fatty acid metal salt D50s: Median diameter based on volume of fatty acid metal salt D95s: 95% cumulative diameter based on volume of fatty acid metal salt   5. The image forming method according to claim 3, wherein the fatty acid metal salt is zinc stearate or calcium stearate. The toner has a particle size of D (μm) to be measured in a minute compression test for the toner, and a load of 9.8 × 10 ⁻⁴ N / sec at a load speed of 9.8 × 10 ⁻⁵ N / sec. D1 + 0.20 ≧ D ≧ D1−0.20 where the maximum displacement when X is loaded is X ₁₀₀ (μm) and the displacement when the load is 2.0 × 10 ⁻⁴ N is X ₂₀ (μm). D1: Number average particle diameter of toner)
0.40 ≦ X ₁₀₀ /D≦0.80
0.020 ≦ X ₂₀ /D≦0.060
The image forming method according to claim 1, wherein:   The toner carrier is abutted at a linear pressure satisfying a condition that a linear pressure P (nip) [N / m] between the toner carrier and the regulating member satisfies 10 ≦ P (nip) ≦ 45. The image forming method according to claim 1.   8. The image forming method according to claim 1, wherein the toner carrier is in contact with the toner carrier and the regulating member with a nip width of 0.20 mm or more and 1.50 mm or less. . The toner carrier has an elastic layer and a surface layer around a core, the surface layer contains resins A and B, and the resin A is made of a polypropylene glycol or polytetramethylene glycol skeleton. An ether polyurethane resin,
The image formation according to claim 1, wherein the resin B is an acrylic resin having a Tg of 30 ° C. or more and 70 ° C. or less and a weight average molecular weight of 30,000 or more and 100,000 or less. Method. A developer container for containing toner; a toner carrier provided in an opening of the developer container; and a layer thickness of the toner carried on the toner carrier, forming a nip with the toner carrier. And a toner supply member that supplies toner to the toner carrier, and a developing device that includes:
The developing device according to claim 1, wherein the toner carrier and the toner are the toner carrier and the toner according to claim 1.

Images