JP2001022116A - Dry toner and image forming method - Google Patents

Abstract

(57) [Problem] To provide a dry toner in which fogging hardly occurs even under high humidity and a density change is small. SOLUTION: In the dry toner containing at least a binder resin, a colorant and a wax, a polycarbonate resin containing a halogen atom in a molecular structure is present on the surface of the toner particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dry toner (hereinafter referred to as "toner") used in a recording method utilizing an electrophotographic method, an electrostatic recording method, a magnetic recording method, a toner jet method, and the like. The present invention relates to an image forming method used. More specifically, the present invention relates to a toner used in an image recording apparatus that can be used in a copying machine, a printer, a facsimile, a plotter, and the like, and an image forming method using the toner.

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
Many methods are known as described in Japanese Patent Publication No. JP-A-Heisei 4-43748 and Japanese Patent Publication No. 43-24748. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means. Forming, then developing the latent image with toner, and transferring the toner image to a transfer material such as paper using direct or indirect means as necessary, and then heating, pressurizing, or solvent vapor or the like. To obtain a copy or the like, and the untransferred toner remaining without being transferred onto the photoreceptor is cleaned by various methods, and the above steps are repeated.

An example of a general method of forming a full-color image will be described below. A photosensitive member (electrostatic latent image carrier) of a photosensitive drum is uniformly charged by a primary charger and converted to a magenta image signal of a document. Image exposure using a laser beam modulated by a laser beam, an electrostatic latent image is formed on the photosensitive drum, and the electrostatic latent image is developed by a magenta developing device having magenta toner to form a magenta toner image. . Next, the magenta toner image developed on the photosensitive drum by the transfer charger is transferred to the conveyed transfer material using direct or indirect means.

On the other hand, the photosensitive drum after the development of the electrostatic latent image is neutralized by a static eliminator, cleaned by a cleaning unit, and charged again by a primary charger. A cyan toner image is formed, and a cyan toner image is formed on the transfer material on which the magenta toner image has been transferred. Then, the same process is performed in the same manner as the yellow color and the black color to transfer the four color toner images to the transfer material. . The transfer material having the four color toner images is fixed by the action of heat and pressure by a fixing roller to form a full color image.

In recent years, such an apparatus is not only a copy machine for office work for copying an original document, but also a laser beam printer (LBP) as an output of a computer or a personal copy (PC) for individuals. Started to be used in the field.

In addition to the fields represented by LBP and PC, the development of plain paper facsimile machines using a basic engine is also rapidly developing.

For this reason, smaller, lighter, faster, higher image quality, and higher reliability have been strictly pursued, and machines have been constructed with simpler elements in various respects. . As a result, the performance required of the toner becomes higher, and if the performance of the toner cannot be improved, a better machine cannot be realized. In recent years, demands for color copying have rapidly increased in accordance with various needs for copying, and further higher image quality, higher resolution, and the like are desired in order to more faithfully copy an original color image. In addition, there is an increasing demand for copying original color originals on both sides.

From these viewpoints, the toner used in the color image forming method needs to have good meltability and color mixing when heated, and has a low softening point and a low melt viscosity. It is preferable to use a toner having a high sharp melt property.

That is, by using such a sharp melt toner, the color reproduction range of a copy can be widened and a color copy faithful to the original image can be obtained.

However, such a color toner having a high sharp melt property generally has a high affinity with a fixing roller, and tends to be easily offset to the fixing roller during fixing.

Particularly, in the case of a fixing device in a color image forming apparatus, since magenta, cyan, yellow, and black toner layers are formed on a transfer material, offset tends to occur particularly due to an increase in toner layer thickness. It is in.

Conventionally, for the purpose of preventing toner from adhering to the surface of the fixing roller, for example, the roller surface is coated with a material having excellent releasability from the toner, such as silicone rubber or fluorine resin, and the surface is further prevented from being offset. In order to prevent the roller surface from being fatigued, the roller surface is coated with a thin film of a liquid having high releasability such as silicone oil or fluorine oil. However, this method is extremely effective in preventing toner offset, but has a problem that a fixing device is complicated because a device is required to supply an anti-offset liquid. Needless to say, this oil application causes delamination between the layers constituting the fixing roller, and consequently has a disadvantage that the life of the fixing roller is shortened.

In view of this, instead of using a silicone oil supply device, a release agent such as low-molecular-weight polyethylene or low-molecular-weight polypropylene is added to the toner in view of supplying the anti-offset liquid during heating from the toner. A way to do that has been proposed.

Techniques for incorporating a wax as a release agent in a toner are disclosed in, for example, Japanese Patent Publication No. 52-3304, Japanese Patent Publication No. 52-3305, and Japanese Patent Application Laid-Open No. 57-52574. .

Further, JP-A-3-50559, JP-A-2-79860, JP-A-1-109359, JP-A-62-14166, and JP-A-61-27
3554, JP-A-61-94062, JP-A-61-138259, JP-A-60-25236
No. 1, Japanese Unexamined Patent Publication No. 60-252360, Japanese Unexamined Patent Publication No.
Japanese Patent Application Laid-Open No. 0-217366 discloses a technique for containing waxes.

Waxes are used to improve the offset resistance of the toner at low and high temperatures and to improve the fixability at low temperatures. In some cases, the toner is exposed to heat due to a rise in temperature inside the apparatus, or when the toner is left for a long time, the wax migrates to the surface of the toner to deteriorate the developability.

With respect to these problems, expectations for the development of new toners have been great.

To solve the above problem, a suspension polymerization method toner has been proposed (Japanese Patent Publication No. 36-10231). In this suspension polymerization method, a polymerizable monomer and a colorant (and, if necessary, a polymerization initiator, a crosslinking agent, a charge control agent, and other additives) are uniformly dissolved or dispersed to prepare a monomer composition. After that, this monomer composition is dispersed in a continuous phase (for example, an aqueous phase) containing a dispersion stabilizer using a suitable stirrer, and simultaneously undergoes a polymerization reaction, thereby obtaining toner particles having a desired particle size. Is what you get.

In this suspension polymerization method, since a droplet of the monomer composition is formed in a dispersion medium having a large polarity such as water, the component having a polar group contained in the monomer composition is an aqueous phase. A so-called core / shell structure in which a non-polar component does not easily exist in the surface layer portion, which is likely to be present in the surface layer portion at the interface with, can be formed. That is, the toner produced by the polymerization method can achieve the contradictory performances of low-temperature fixing property, anti-blocking property and durability, and anti-high-temperature offset property by incorporating a wax component as a release agent, and a fixing roller. It is possible to prevent high-temperature offset without applying a release agent such as oil to the surface.

By the way, it is generally known that when a large number of toners are printed out, deterioration such as the external additive being buried in the toner surface occurs, which adversely affects the image.
As one means to improve the durability of the toner,
There is a method of increasing the mechanical strength of the binder resin. However, in practice, problems arise in the pulverizability of the binder resin and the fixability of the toner, and it is generally difficult to use such a tough resin as the binder resin.

As a resin having excellent mechanical strength, electrical properties, aging resistance (weather resistance), etc., polycarbonate is generally widely known and used for various purposes. Regarding the toner for developing an electrostatic image, several methods using polycarbonate as a binder resin are disclosed. For example,
JP-A-46-28588 discloses an image forming method using a specific polycarbonate copolymer and a granular carrier. According to the publication, a toner excellent in blocking resistance can be obtained by using a specific polycarbonate copolymer as a binder resin. However, in this publication, a polycarbonate copolymer having a glass transition temperature of 70 to 95 ° C. is used as a binder resin, and a wax component is not contained in the toner, so that the low-temperature fixability is very poor and there is room for improvement. . In addition, there is no description that a halogen-modified polycarbonate resin can be suitably used, and the effect of impurities contained in the polycarbonate copolymer on electrophotographic properties and the like is not described at all. Further, in this publication, a method for producing a toner by a spray drying method and a pulverization method is disclosed in Examples, but the toner image coming from the shape of the obtained toner is transferred from the electrostatic image carrier to the transfer material. There is no description of a difference in transferability or a difference in charge uniformity.

Japanese Patent Application Laid-Open No. 63-208863 discloses a method in which a polycarbonate terpolymer having a specific structure having a glass transition temperature of about 50 ° C. is used as a binder resin for a flash fixing toner. ing. According to the publication, a toner having good fixation properties despite the fact that the polycarbonate terpolymer serving as a binder resin does not thermally decompose at the time of flash fixing, so that there is no odor or elution material and no wax component is contained. Can be obtained. However, on the other hand, since only a polycarbonate terpolymer having a low glass transition temperature is used as a binder resin, the blocking resistance and durability have not reached a satisfactory level, and it has been used for flash fixing. Therefore, it is difficult to apply the present invention to a fixing device in which a toner is in contact with a heating element such as a hot roll fixing device.

Further, US Pat. No. 4,457,998 discloses a toner having a structure in which a linear binder resin is incorporated into a highly crosslinked binder resin. It is said that a polycarbonate copolymer can be used as a highly crosslinked binder resin or a linear binder resin, or both. However, there is no description in the specification of the publication of the use of a polycarbonate copolymer, and the effect of using the polycarbonate copolymer as a binder resin is unknown.

Further, JP-A-6-43688 describes a method in which a polycarbonate copolymer having a specific structure exhibiting thermotropic liquid crystallinity is used as a binder resin. The polycarbonate copolymer exhibiting thermotropic liquid crystallinity usually has a high crystallinity, shows a gentle heat softening behavior up to the melting point, and when the temperature rises, it rapidly liquefies (melts) to lower the viscosity and the temperature. To exhibit the property of decreasing, the toner using the polycarbonate copolymer as a binder resin can be fixed with low energy without containing a wax component in the toner while maintaining the crushing property and the blocking resistance. . However, since the toner according to the publication is composed of only one kind of binder resin, the viscosity at the time of melting the toner is too low, and the so-called high-temperature offset occurs in which the melted toner adheres to a fixing device such as a hot roll. Problem has not been solved. Further, there is no specific description regarding the halogen-modified polycarbonate resin can be suitably used, the effect of impurities contained in the polycarbonate copolymer on the electrophotographic properties, and the shape of the toner. Also, there is no description in any of these publications that various performances and functions of the toner are improved by using a polycarbonate resin containing a halogen atom in a molecular structure.

Electrophotographic photoreceptors having a surface layer containing a polycarbonate containing a halogen atom in the molecular structure have been known for a long time, and photoreceptors using a polycarbonate substituted with a fluorine atom or a polycarbonate substituted with a chlorine atom have been known. It has been disclosed. However, there is no description that a polycarbonate containing the halogen atom in the molecular structure can be used in the toner, and only application to a photoreceptor has been studied in the prior art.

As described above, in recent years, there has been a great demand from users for copying original documents on both sides or duplexing original documents on one side, and for that purpose, both sides of images having higher image quality and higher reliability are required. Have been.

One of the most important issues is the paper curl that occurs after fixing one side, among the various disadvantages in the conventional color double-sided technique. When the paper curl is large, the transportability of the fixed image is remarkably deteriorated, and an image having high image quality and high reliability cannot be obtained. On the other hand, the performance required for the toner is, for example, how to obtain a high-quality image satisfying image density, color reproducibility, and the like in a state where the amount of the toner transferred to the transfer material is small. . This requires an improvement in the coloring power of the toner itself. Further, since an image which passes through the fixing device twice is generated on both sides, further improvement in high-temperature offset resistance is also required.

Conventionally, in a full-color copying machine, four photoconductors and a belt-shaped transfer belt are used, and an electrostatic latent image formed on each photoconductor is developed using cyan, magenta, yellow, and black toners. After transferring the transfer material between the photoreceptor and the belt transfer member and transferring it between straight passes, a full-color image can be formed, or the transfer material can be applied to the surface of the transfer member facing the photoreceptor by electrostatic force or mechanical action such as a gripper. Is generally used in which a full-color image is obtained by performing the development-transfer step four times.

In recent years, ordinary paper and overhead projector films (OH
In addition to P), there is an increasing need to develop various materials for small-size paper such as cardboard, cards, and postcards. 4 above
In the method using one photoconductor, the transfer material is transported straight, so the application range to various transfer materials is wide.
It is necessary to accurately superimpose multiple toner images on a predetermined transfer material position, and it is difficult to obtain high-quality images with good reproducibility even with a slight registration difference, which complicates the transfer material transport mechanism. However, there is a problem that the reliability is reduced and the number of parts is increased. Also, when using thick paper with a large weight by the method of adsorbing and winding the transfer material on the surface of the transfer body, the back end of the transfer material causes poor adhesion due to the strength of the transfer material, resulting in an image based on the transfer. It is not preferable because it causes defects. Image defects may also occur on small-size paper.

A full-color image apparatus using a drum-shaped intermediate transfer member is already known from US Pat. No. 5,187,526, Japanese Patent Laid-Open No. 4-16426, and the like.
In U.S. Pat. No. 5,187,526, an intermediate transfer roller composed of a polyurethane-based surface layer has a volume resistivity of less than 10 ⁹ Ω · cm, and is constituted by a similar surface layer. The volume resistivity of the transfer roller is
It is described that high image quality can be obtained by setting it to 10 ¹⁰ Ω · cm or more. However, in such a system, a high output electric field is required in order to provide a sufficient amount of transfer charge to the toner at the time of transfer of the toner to the transfer material, so that the system is made of polyurethane in which a conductivity-imparting material is dispersed. The undesired surface layer locally causes breakdown, and undesired image disturbance occurs in a halftone image with a small amount of toner applied. Further, in such a high voltage application, in an environment under a high humidity where the relative humidity exceeds 60% RH, the transfer current leaks due to the reduction in the resistance of the transfer material, and the transfer failure is likely to occur. Is 40% RH
Even in the following low-humidity environment, transfer failure may be caused by uneven resistance unevenness of the transfer material.

JP-A-59-15739 and JP-A-59-5046 describe the relationship between the configuration using an intermediate transfer member and toner. However, this publication only discloses that a toner having a thickness of 10 μm or less can be efficiently transferred using an adhesive intermediate transfer member. Normally, in a system using an intermediate transfer member, it is necessary to transfer a developed color image of the toner from the photoreceptor to the intermediate transfer member once, and then transfer the developed image from the intermediate transfer member onto the transfer material again. It is necessary to increase the transfer efficiency of the comparative toner more than before. In particular, when a full-color copying machine that transfers a plurality of toner images after development is used, the amount of toner on the photoreceptor increases compared to the case of one-color black toner used in a black-and-white copying machine. It is difficult to improve the transfer efficiency only by using. Further, when a normal toner is used, the surface of the photoconductor or the surface of the photoconductor may be damaged due to a shearing force or a rubbing force between the photoconductor or the intermediate transfer member and the cleaning member and / or between the photoconductor and the intermediate transfer member. The transfer efficiency is deteriorated due to the fusion or filming of the toner on the surface of the intermediate transfer member, and the problem of color unevenness and color balance is liable to occur because the full-color toner image is not transferred uniformly. However, it has been difficult to stably output a high-quality full-color image.

Further, as a toner to be mounted on a normal full-color copying machine, it is necessary that each color toner is sufficiently mixed in a fixing process, and therefore, improvement in color reproducibility and transparency of an OHP image are important. In general, it is preferable to use a sharp-melt, low-molecular-weight resin for the black toner and the comparative color toner. In addition, a release agent having relatively high crystallinity represented by polyethylene wax or polypropylene wax is used for ordinary black toner in order to improve high-temperature offset resistance during fixing. However, in a full-color toner, the transparency of an OHP toner image is significantly impaired when output because of the crystallinity of the release agent. For this reason, by applying silicone oil or the like uniformly to the heat fixing roller without adding a release agent as a component of the color toner, the anti-high-temperature offset property is improved as a result. However, the transfer material having a toner-fixed image obtained in this manner is not preferable because extra silicone oil or the like adheres to the surface thereof, which causes discomfort when used by a user.
At present, there are many difficulties in forming a full-color image using an intermediate transfer member having many contact portions. JP-A-59-
JP-A-15739 and JP-A-59-5046 do not propose a device for the toner or the intermediate transfer member in this regard.

[0033]

SUMMARY OF THE INVENTION An object of the present invention is to provide a dry toner which hardly causes fog even under high humidity and has a small density change, and an image forming method using the toner.

[0034]

According to the present invention, there is provided a dry toner containing at least a binder resin, a colorant and a wax, wherein a polycarbonate resin containing a halogen atom in a molecular structure is formed on the surface of the toner particles. To a dry toner characterized by being present.

Further, the present invention relates to an image forming method using the toner.

As a result of intensive studies, the present inventors have found that a polycarbonate resin containing a halogen atom in its molecular structure can be present continuously or discontinuously on the surface of toner particles, so that even under high humidity conditions. The present inventors have found that fogging hardly occurs and a toner having a small density change can be obtained, and the present invention has been completed.

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION The toner according to the present invention contains at least a binder resin, a colorant and a wax component, and continuously or discontinuously contains a polycarbonate resin containing a halogen atom in its molecular structure. It is essential that it exists on the surface of the toner particles.

The polycarbonate resin containing a halogen atom, which is an essential component in the present invention, in its molecular structure is
It has a repeating unit represented by the following general formula (I) in its molecular structure.

[0039]

Embedded image[Wherein, R Is an organic group. ]

The polycarbonate resin containing a halogen atom represented by the above general formula (I) in its molecular structure has various structures. For example, a dihydric phenol at least partially substituted by a halogen atom may be used. A polycarbonate containing any known halogen atom in its molecular structure, which is produced by reacting a carbonate precursor with a solution method or a melting method, a dihydric phenol at least partially substituted by a halogen atom, Examples include all known copolymerized polycarbonates produced by reacting a polyhydric phenol and a carbonate precursor by a solution method or a melt method.

As an example of the dihydric phenol at least partially substituted by a halogen atom, the following general formulas (II) to (IV)

[0042]

Embedded image Wherein, R ¹ represents a halogen atom, a hydrogen atom, an aliphatic hydrocarbon group, an aromatic substituent, and when the R ¹ is plural,
They may be the same or different,
m is a number from 0 to 4. X is a single bond, an aliphatic hydrocarbon group at least partially substituted by a halogen atom, an aromatic hydrocarbon group at least partially substituted by a halogen atom, -S-, -SO-, -SO _2- ,
And a bond represented by a -O- or -CO- bond. However, at least one of R ^{1 and} X is a group containing a halogen atom. ] And the like.

Examples of the dihydric phenol containing no halogen atom include the following general formulas (V) to (VII):

[0044]

Embedded image [In the formula, R ² is a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic substituent. When a plurality of R ² are present, they may be the same or different, and m is , 0-4. And Y is a single bond, an aliphatic hydrocarbon group,
Aromatic hydrocarbon group, -S -, - SO -, - SO 2 -, -
And a bond represented by an O- or -CO- bond. ] And the like.

The dihydric phenols represented by the above general formulas (II) to (IV) can be optionally replaced with the general formulas (V) to (V)
By reacting with a carbonate precursor such as phosgene or a carbonate compound together with the dihydric phenol represented by II), a polycarbonate resin containing a halogen atom in a molecular structure used in the present invention can be easily produced. . That is, for example, in a solvent such as methylene chloride, in the presence of a known acid acceptor or a molecular weight regulator, a dihydric phenol at least partially substituted with a halogen atom, and containing no halogen atom (if necessary) Dihydric phenols and dihydric phenols at least partially substituted by halogen atoms, by reaction with carbonate precursors such as phosgene, (optionally) halogen-free dihydric phenols, and diphenyl carbonate It is produced by a transesterification reaction with a carbonate precursor such as

There are various dihydric phenols at least partially substituted by halogen atoms represented by the above general formulas (II) to (IV), and 2,2-bis (2,3,5,6 -Tetrabromo-4-hydroxyphenyl) propane, 2,2-bis (2,3,5,6-tetrachloro-4-hydroxyphenyl) propane, 2,2
-Bis (2,3,5,6-tetrafluoro-4-hydroxyphenyl) propane, 2,2-bis (2,3,5
6-tetraiodo-4-hydroxyphenyl) propane, 1,1-bis (2,3,5,6-tetrabromo-4)
-Hydroxyphenyl) cyclohexane, 1,1-bis (2,3,5,6-tetrachloro-4-hydroxyphenyl) cyclohexane, 1,1-bis (2,3,5,6
-Tetrachloro-4-hydroxyphenyl) cyclohexane, bis (3,5-dichloro-4-hydroxyphenyl) methane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-
Dibromo-4-hydroxyphenyl) propane, 2,2
-Bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 1,1-bis (3,5-dichloro-4)
-Hydroxyphenyl) cyclohexane, 1,1-bis (3-fluoro-4-hydroxyphenyl) cyclohexane, bis (3-chloro-4-hydroxyphenyl) sulfone, 2,2-bis (4-hydroxyphenyl)-
1,1,1,3,3,3-hexafluoropropane,
2,2-bis (4-hydroxyphenyl) -1,1,1
3,3-tetrafluoropropane, 2,2-bis (4-
Hydroxyphenyl) -1,3-difluoropropane,
2,2-bis (4-hydroxyphenyl) -1-fluoropropane, 2,2-bis (4-hydroxyphenyl)
-1,1,1,3,3,3-hexachloropropane,
2,2-bis (4-hydroxyphenyl) -1,1,1
3,3-tetrachloropropane, 2,2-bis (4-hydroxyphenyl) -1,3-dichloropropane, 2,
2-bis (4-hydroxyphenyl) -1-chloropropane, 1,1-bis (4-hydroxyphenyl) -2,
3,4,5,6-pentafluorocyclohexane, 1,
1-bis (4-hydroxyphenyl) -2,3,5,6
-Tetrafluorocyclohexane, 1,1-bis (4-
(Hydroxyphenyl) -2,4,6-trifluorocyclohexane, 1,1-bis (4-hydroxyphenyl)
-2,6-difluorocyclohexane, 1,1-bis (4-hydroxyphenyl) -2,2-difluorocyclohexane, 1,1-bis (4-hydroxyphenyl)
-2-fluorocyclohexane, 1,1-bis (4-hydroxyphenyl) -2,3,4,5,6-pentachlorocyclohexane, 1,1-bis (4-hydroxyphenyl) -2,3,5 6-tetrachlorocyclohexane, 1,1-bis (4-hydroxyphenyl) -2,
4,6-trichlorocyclohexane, 1,1-bis (4
-Hydroxyphenyl) -2,6-dichlorocyclohexane, 1,1-bis (4-hydroxyphenyl) -2,
2-dichlorocyclohexane, 1,1-bis (4-hydroxyphenyl) -2-chlorocyclohexane, 1,1
-Bis (4-hydroxy-2-trichloromethylphenyl) cyclohexane, 2,2-bis (4-hydroxy-
2-trichloromethylphenyl) propane, 1,1-bis (4-hydroxy-2-trifluoromethylphenyl) cyclohexane, 2,2-bis (4-hydroxy-
2-trifluoromethylphenyl) propane and, in addition to the above dihydric phenols, 1,4-dihydroxy-
Various things such as 2,5-dichlorobenzene,
These dihydric phenols may be used alone or in combination of two or more.

Further, there are various dihydric phenols containing no halogen atom represented by any of the general formulas (V) to (VII) in the molecular structure, and 2,2-bis (4-hydroxyphenyl) propane [Common name: Bisphenol A]
And, for example, bis (4-hydroxyphenyl) methane; bis (4-hydroxyphenyl) phenylmethane; bis (4-hydroxyphenyl) naphthylmethane;
Bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane; bis (3,5-dimethyl-4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 1-naphthyl-1, 1-bis (4
-Hydroxyphenyl) ethane; 1-phenyl-1,1
-Bis (4-hydroxyphenyl) ethane; 1,2-bis (4-hydroxyphenyl) ethane; 2-methyl-
1,1-bis (4-hydroxyphenyl) propane;
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane; 1-ethyl-1,1-bis (4-hydroxyphenyl) propane; 2,2-bis (3-methyl-4-hydroxyphenyl) ) Propane; 1,1-bis (4-hydroxyphenyl) butane; 2,2-bis (4
1,4-bis (4-hydroxyphenyl) butane; 2,2-bis (4-hydroxyphenyl) pentane; 4-methyl-2,2-bis (4-hydroxyphenyl) pentane; , 1-bis (4-hydroxyphenyl) cyclohexane; 2,2-
Bis (4-hydroxyphenyl) hexane; 4,4-bis (4-hydroxyphenyl) heptane; 2,2-bis (4-hydroxyphenyl) nonane; 1,10-bis (4-hydroxyphenyl) decane; 1-bis (4
Dihydroxyarylalkanes such as -hydroxyphenyl) cyclodecane; bis (4-hydroxyphenyl) sulfone; dihydroxyarylsulfones such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) ether Dihydroxyaryl ethers such as bis (3,5-dimethyl-4-hydroxyphenyl) ether, 4,4 ′
-Dihydroxybenzophenone; 3,3 ', 5,5'-
Dihydroxyarylketones such as tetramethyl-4,4'-dihydroxybenzophenone, bis (4-hydroxyphenyl) sulfide; bis (3-methyl-4-
Hydroxyphenyl sulfide; dihydroxyaryl sulfides such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, dihydroxyaryl sulfoxides such as bis (4-hydroxyphenyl) sulfoxide, 4,4′-dihydroxydiphenyl and the like Dihydroxydiphenyls, hydroquinone; solcinol; dihydroxybenzenes such as methylhydroquinone; 1,5-dihydroxynaphthalene; dihydroxynaphthalenes such as 2,6-dihydroxynaphthalene. These dihydric phenols may be used alone or in combination of two or more.

The polycarbonate resin containing a halogen atom in the molecular structure used in the present invention does not necessarily need to contain a halogen atom in its repeating unit as described above. A polymer having a halogen atom only at the terminal of the polymer chain may be used by using a contained polymerization terminator. The polymerization terminator that can be used at this time is not particularly limited. For example, 2-methyl-2- (4-hydroxy-2,3,5,6-tetrafluorophenyl) propane, 2-trifluoromethyl-2- (4-hydroxyphenyl) -1,1,1,3,
3,3-hexafluoropropane, 4-trifluoromethylphenol, 2-trichloromethylphenol, bromophenol, chlorophenol, fluorophenol, dibromophenol, dichlorophenol, difluorophenol, tribromophenol, trichlorophenol, trifluorophenol, Monohydric phenols such as tetrabromophenol, tetrachlorophenol, tetrafluorophenol, pentabromophenol, pentachlorophenol, and pentafluorophenol are exemplified.

The polycarbonate resin containing a halogen atom in the molecular structure used in the present invention may be a homopolymer using one of the above-mentioned dihydric phenols, or a mixture of two or more thereof. Or a blend. further,
It may be a thermoplastic random branched polycarbonate resin obtained by reacting a polyfunctional aromatic compound with the above-mentioned dihydric phenol and / or carbonate precursor.

In order to adjust the glass transition temperature and the viscoelasticity of the polycarbonate resin containing a halogen atom in the molecular structure, a part of the dihydric phenol is replaced with ethylene glycol, diethylene glycol, triethylene glycol, 1,2- Propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (2-hydroxyethyl) benzene, 1,4-cyclohexane Dimethanol, polyethylene glycol, propylene glycol, hydrogenated products of 2,2-bis (4-hydroxyphenyl) propane and derivatives thereof, ethylene oxide adducts of 2,2-bis (4-hydroxyphenyl) propane, 2,2 -Bis (4-hydroxy Eniru) propylene oxide adducts of propane, glycerol, trimethylolpropane, polyhydric form of modified polycarbonate resin was replaced with alcohol such as pentaerythritol may also be suitably used. In this case, it is possible to produce by the above-mentioned method by simply substituting a part of the dihydric phenol, but as an example of another production method, dihydric phenol and aliphatic or aromatic bischloroformate And the like are reacted in a methylene chloride solvent using pyridine as a catalyst. Of course, synthesis by other production methods is also possible. Further, in the present invention, those in which these polyhydric alcohols contain a halogen atom in the molecular structure may be used, in which case, the above-mentioned dihydric phenols may contain a halogen atom, It may not be included.

Further, in the present invention, as a polycarbonate resin containing a halogen atom in its molecular structure,
Blocks of the above-mentioned polycarbonate containing a halogen atom in its molecular structure and polystyrene, styrene- (meth) acrylic copolymer, polyester, polyurethane, epoxy resin, polyolefin, polyamide, polysulfone, polycyanoaryl ether, polyarylene sulfide, etc. It is also possible to use a copolymer or a graft-modified copolymer obtained by grafting an alkyl (meth) acrylate, (meth) acrylic acid, maleic acid, a styrene monomer or the like.

Although the molecular weight of the polycarbonate resin containing a halogen atom in the molecular structure used in the present invention is not particularly limited, the peak molecular weight measured by gel permeation chromatography (GPC) described later is in the range of 1,000 to 500,000. A certain thing is preferable, More preferably, it is 2000-100,000. If the peak molecular weight is lower than 1,000, the charging characteristics may be adversely affected, and if the peak molecular weight is higher than 500,000, the melt viscosity becomes too high, which may cause a problem in fixability. In producing the polycarbonate resin used in the present invention, a suitable molecular weight regulator, a branching agent for improving viscoelasticity, a catalyst for accelerating the reaction, and the like can be used as required.

In the present invention, it is essential that a polycarbonate resin containing a halogen atom in the molecular structure is present on the surface of the toner particle, and at least a part of the binder resin in the toner particle contains a halogen atom. Is required to be a polycarbonate resin containing in a molecular structure. The binder resin may be a toner composed of only a polycarbonate-based resin containing a halogen atom in its molecular structure. However, in consideration of the adjustment of the viscoelasticity of the toner and the low-temperature fixability as described above, the resin may be used. Is continuous or
It is preferable that the resin is a polycarbonate resin that is discontinuously present on the surface of the toner particles, and that 0.1 to 50% by weight of the binder resin contains a halogen atom in the molecular structure. At this time, 50 to 99.9% by weight of another resin is used as a binder resin together with a polycarbonate resin containing a halogen atom in its molecular structure. The toner is designed to have a viscoelasticity of the toner by using as a binder resin a high molecular weight resin or a crosslinked resin having a GPC molecular weight of more than 500,000 and a low molecular weight resin having a molecular weight of about 1,000 to 50,000. It is generally practiced to prevent high-temperature offset. However, if the content of the polycarbonate-based resin in the binder resin exceeds 50% by weight, it becomes difficult to manufacture a toner having such a design. Is generated. Therefore, when a polycarbonate resin containing no halogen atom in its molecular structure is used together with a polycarbonate resin containing a halogen atom in its molecular structure as a binder resin, the total amount of these resins is 50% by weight of the total binder resin. Is preferably not exceeded. Further, when the content of the polycarbonate resin containing a halogen atom in the molecular structure in the binder resin is less than 0.1% by weight,
The excellent fluidity and low-temperature fixability, which are the effects of the present invention, cannot be achieved.

In the present invention, it is desirable to use another resin as a binder resin together with the polycarbonate resin containing a halogen atom in the molecular structure. Various resins such as styrene- (meth) acrylic copolymer, polyester-based resin, epoxy-based resin, and styrene-butadiene copolymer, which are generally used, may be used in this case. In a method of directly obtaining toner particles by a polymerization method, a monomer for forming them is used. Specifically, styrene monomers such as styrene, o (m-, p-)-methylstyrene, m (p-)-ethylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, ( Propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate,
(Meth) such as dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate ) Acrylic ester monomers, butene monomers such as butadiene, isoprene, cyclohexene, (meth) acrylonitrile and acrylamide are preferably used. These may be used alone or generally in the published Polymer Handbook, 2nd edition III-pl39-192.
The monomers are appropriately mixed and used so that the theoretical glass transition temperature (Tg) described in (John Wiley & Sons) indicates 40 to 75 ° C. If the theoretical glass transition temperature is lower than 40 ° C., problems tend to occur in terms of storage stability and durability stability of the toner, while if it exceeds 75 ° C., the fixing point of the toner increases. In particular, in the case of a color toner for forming a full-color image, the color mixing at the time of fixing each color toner is reduced and the color reproducibility is poor,
Further, the transparency of the OHP image is undesirably reduced.

The molecular weight of the binder resin is measured by gel permeation chromatography (GPC). As a specific GPC measurement method, a solution obtained by dissolving a binder resin or a toner in tetrahydrofuran (THF) over 24 hours at room temperature is filtered through a solvent-resistant membrane filter having a pore diameter of 0.2 μm to obtain a sample solution. And measure under the following conditions. The sample was prepared so that the concentration of the component soluble in THF was 0.4 to 0.6% by weight.
Adjust the amount of F. Apparatus: High-speed GPC HLC8120 GPC (manufactured by Tosoh Corporation) Column: Shodex KF-801, 802, 80
7, 804, 805, 806, 807 (Showa Denko KK) Eluent: Tetrahydrofuran Flow rate: 1.0 ml / min Oven temperature: 40.0 ° C. Sample injection amount: 0.10 ml

In calculating the molecular weight of the sample,
Standard polystyrene resin (Tosoh Corporation TSK Standard Polystyrene F-850, F-450, F-28
8, F-128, F-80, F-40, F-20, F-
10, F-4, F-2, F-1, A-5000, A-2
500, A-1000, A-500).

When the toner of the present invention is produced by a polymerization method, the main peak molecular weight of the binder resin of the obtained polymer particles is 5000 to 100,000, the weight average molecular weight (Mw) and the number average molecular weight (Mn). (Mw / Mn) is 2 to 300
Are preferred for the present invention.

The shape of the toner of the present invention is not particularly limited, but in order to improve transferability and developability in a well-balanced manner,
The following shapes are preferred. In other words, the number average diameter of the circle-equivalent number in the number-based particle size frequency distribution is 2 to 10 μm, and the average circularity in the circularity frequency distribution is 0.920.
０．９0.995, preferably 0.950-0.995, more preferably 0.970-0.995, and the circularity standard deviation is less than 0.060, preferably less than 0.050, more preferably 0.040. By precisely controlling the particle shape of the toner so as to be less than the above, transferability and developability can be improved in a well-balanced manner.

By reducing the average particle diameter equivalent to a circle in the particle size frequency distribution based on the number of toners to 2 to 10 μm, the reproducibility of the outline portion of an image, especially a character image or a line pattern in development is good. It becomes something. However, in general, when the particle size of the toner particle is reduced, the existence ratio of the toner having a small particle size necessarily increases, so that it becomes difficult to uniformly charge the toner, and not only image fogging occurs, but also the electrostatic latent image carrying Adhesion to the body surface is increased, resulting in an increase in transfer residual toner.

However, by controlling the circularity standard deviation of the circularity frequency distribution as described above, the toner of the present invention has good stability with respect to environmental changes in developability and transferability, and furthermore has good durability. Become. The reason is that when forming a thin layer of toner on the toner carrier in the developing step, the present inventors have to maintain a sufficient amount of toner coating even if the regulating force of the toner layer regulating member is made stronger than usual. Therefore, it is considered that the toner charge amount on the toner carrier can be made higher than usual without damaging the toner carrier.

Further, by controlling the average circularity of the circularity frequency distribution as described above, the transferability of a toner having a small particle diameter, which has been difficult in the past, is greatly improved, and the development of a low potential latent image is improved. The ability is also greatly improved. It is particularly effective when developing a digital minute spot latent image.

The average circularity is particularly preferably 0.970 or more, and if it is less than 0.970, the transferability may deteriorate and the developability may decrease. The average circularity is 0.995
If it exceeds, the surface of the toner deteriorates remarkably, causing problems in durability and the like.

The circle equivalent diameter, circularity, and frequency distribution of the toner in the present invention are used as a simple method for quantitatively expressing the shape of the toner particles. The measurement was performed using an apparatus FPIA-1000 (manufactured by Toa Medical Electronics Co., Ltd.), and calculated using the following equation.

[0064]

(Equation 1)

Here, the “particle projection area” is the area of the binarized toner particle image, and the “perimeter of the particle projection image”
Is defined as the length of the contour obtained by connecting the edge points of the toner particle image.

The circularity in the present invention is an index indicating the degree of unevenness of the toner particles. The circularity is 1.00 when the toner particles are perfectly spherical, and the circularity decreases as the surface shape becomes more complicated. Become.

In the present invention, the circle-equivalent number average particle diameter D1 means the average value of the number-based particle diameter frequency distribution of the toner.
And the particle size standard deviation SDd are calculated from the following equation, where di is the particle size (central value) at the dividing point i of the particle size distribution, and f _i is the frequency.

[0068]

(Equation 2)

[0069]

[0070]

(Equation 3)

As a specific measurement method, 10 ml of ion-exchanged water from which impure solids and the like have been removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant thereto. Further, 0.02 g of the measurement sample is added and uniformly dispersed. As a means for dispersing, an ultrasonic disperser UH-50 type (manufactured by SMT Co., Ltd.) equipped with a titanium alloy chip of 5φ as a vibrator is used for a dispersion treatment for 5 minutes to prepare a dispersion for measurement. At this time, the dispersion is appropriately cooled so that the temperature of the dispersion does not become 40 ° C. or higher.

For the measurement of the shape of the toner particles, the above-mentioned flow type particle image measuring device was used.
The concentration of the dispersion liquid is readjusted so as to be 100 to 10,000 particles / μl, and 1,000 or more toner particles are measured. After the measurement, using this data, the equivalent circle diameter and circularity frequency distribution of the toner are obtained.

Examples of the wax component used in the toner of the present invention include paraffin wax and derivatives thereof,
Microcrystalline wax and its derivatives, Fischer-Tropsch wax and its derivatives, polyolefin wax and its derivatives, carnauba wax and its derivatives, and derivatives include oxides, block copolymers with vinyl monomers, and graft-modified products . In addition, various types such as higher fatty acids and metal salts thereof, higher fatty alcohols, higher fatty esters, fatty amide waxes, ketones, hydrogenated castor oil and derivatives thereof, vegetable waxes, animal waxes, mineral waxes, petrolactam, etc. Things.

These wax components were found to be 40 to 40% at the time of temperature rise in a DSC curve measured by a differential scanning calorimeter.
It has a maximum endothermic peak in the region of 130 ° C. By having the maximum endothermic peak in the above temperature range, it greatly contributes to low-temperature fixing, and also effectively expresses the releasability. When the maximum endothermic peak is less than 40 ° C., the self-cohesive force of the wax component becomes weak, and as a result, the high-temperature offset resistance deteriorates and the gloss becomes too high. On the other hand, if the maximum endothermic peak exceeds 130 ° C., the fixing temperature becomes high, and it becomes difficult to appropriately smooth the fixed image surface. Not preferred. Further, when granulation / polymerization is performed in an aqueous medium to directly obtain a toner by a polymerization method,
If the maximum endothermic peak temperature is high, problems such as precipitation of a wax component mainly during granulation are not preferred.

The maximum endothermic peak temperature of the wax component is measured according to “ASTM D 3418-8”. For the measurement, for example, DSC-7 manufactured by PerkinElmer is used. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the heat quantity correction uses the heat of fusion of indium. An aluminum pan is used as a measurement sample, an empty pan is set as a control, and the measurement is performed at a heating rate of 10 ° C./min.

In the present invention, the amount of these wax components to be added is not particularly limited.
The range is preferably from 30 to 30% by weight.

The coloring agents used in the present invention include the following yellow coloring agents, magenta coloring agents and cyan coloring agents. Carbon blacks, magnetic substances, or the following yellow coloring agents / magenta coloring agents are used as black coloring agents. A mixture of a coloring agent and a cyan coloring agent and adjusted to black is used.

Examples of the yellow colorant include condensed azo compounds, isoindolinone compounds, anthraquinone compounds,
An azo metal complex, a methine compound, a compound represented by an allylamide compound, or the like is used. Specifically, C.I. I.
Pigment Yellow 12, 13, 14, 15, 17, 6
2, 74, 83, 93, 94, 95, 109, 110,
111, 128, 129, 147, 168, 180 and the like are preferably used.

Examples of the magenta coloring agent include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds and the like. Specifically, C.I.
I. Pigment Red 2, 3, 5, 6, 7, 23, 4
8: 2, 48: 3, 48: 4, 57: 1, 81: 1, 1
44, 146, 166, 169, 177, 184, 18
5, 202, 206, 220, 221, 254 are particularly preferred.

As the cyan coloring agent, 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, etc. can be particularly preferably used.

These colorants can be used alone or as a mixture or in the form of a solid solution. The colorant has a hue,
It is selected from the viewpoints of chroma, lightness, weather resistance, OHP transparency, and dispersibility in toner particles. The amount of the coloring agent is preferably 1 to 20 parts by weight based on 100 parts by weight of the resin component.

Further, the toner of the present invention uses a magnetic material as a black colorant, and can be used as a magnetic toner. Magnetic materials that can be used at this time include magnetite, hematite, iron oxides such as ferrite, metals such as iron, cobalt, and nickel, or aluminum, cobalt, copper, lead, magnesium, tin, zinc, and the like of these metals. Antimony, beryllium, bismuth, cadmium,
Alloys of metals such as calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof.

The magnetic material used in the present invention is more preferably a surface-modified magnetic material. When the magnetic material is used in a polymerization toner, the surface is modified with a surface modifier which is a substance having no polymerization inhibition. Those that have been treated are preferred. Examples of such a surface modifier include a silane coupling agent,
Titanium coupling agents and the like can be exemplified.

These magnetic materials have an average particle size of 2 μm or less,
Preferably, it is about 0.1 to 0.5 μm. The amount of the magnetic substance contained in the toner particles is 20 to 200 parts by weight, particularly preferably 40 to 200 parts by weight, per 100 parts by weight of the resin.
It is 150 parts by weight. In addition, a magnetic material having a coercive force (Hc) of 20 to 300 Oersted, a saturation magnetization (σs) of 50 to 200 emu / g, and a residual magnetization (σr) of 2 to 20 emu / g when 10 K Oersted is applied is preferable.

The charge control agents used in the present invention include:
Known charge control agents can be used, and in particular, a charge control agent which has a high charge speed and can stably maintain a constant charge amount is preferable. Further, when the toner particles are directly polymerized, a charge control agent having no polymerization inhibition and having no solubilized substance in an aqueous dispersion medium is particularly preferable. Specific examples of the compound include a metal compound of an aromatic carboxylic acid such as salicylic acid, naphthoic acid, and dicarboxylic acid as a negative charge control agent; a polymer compound having a sulfonic acid or carboxylic acid group in a side chain; a boron compound; Compound; silicon compound; curryxarene and the like. Examples of the positive charge control agent include a quaternary ammonium salt; a polymer compound having the quaternary ammonium salt in a side chain; a guanidine compound; and an imidazole compound. The charge control agent is preferably used in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the resin. However, in the present invention, the addition of a charge control agent is not essential, and in the case of using a two-component developing method, utilizing triboelectric charging with a carrier, in the case of using a non-magnetic one-component blade coating developing method, By positively utilizing frictional charging with the blade member and the sleeve member, it is not always necessary to include a charge control agent in the toner particles.

In the toner according to the present invention, it is essential that a polycarbonate resin containing a halogen atom in its molecular structure is present on the surface of the toner particles. Various methods may be mentioned as a method for producing the toner of the present invention,
For example, in the case of manufacturing by a pulverization method, a binder resin containing a polycarbonate resin containing a halogen atom in a molecular structure, a wax component, a colorant and / or a magnetic substance, a charge control agent or other additives, and the like are used. Mix well with a mixer such as Henschel mixer or ball mill,
The mixture is melted and kneaded using a heat kneader such as a pressure kneader or an extruder, and after cooling and solidifying, the solid is made to strike a target mechanically or under a jet stream to pulverize the solid to a desired toner particle size. Thereafter, smoothing and sphering of the toner particles are performed as necessary. Next, the particle size distribution is sharpened through a classification process. Further, the toner of the present invention can be obtained by sufficiently mixing the classified powder with a fluidizing agent such as fine-particle silica using a mixer such as a Henschel mixer. Further, even with the same pulverization method, a binder resin (which may or may not contain a polycarbonate resin containing a halogen atom in its molecular structure), a wax component, a coloring agent and / or a magnetic substance Using a charge control agent or other additives as a raw material, the process is also performed until finely pulverized in the same manner as described above, and then a polycarbonate resin containing fine halogen atoms in the structure of the surface of the pulverized particles is used as a Henschel mixer. Adhering using a mixer,
Further, in the same manner as described above, smoothing and spheroidizing, classification, and toner formation of toner particles can be performed.

Further, a polycarbonate resin containing a halogen atom directly in a molecular structure is continuously produced by a polymerization method.
Alternatively, in the case of producing a toner having a discontinuous surface, a polycarbonate resin containing a halogen atom in its molecular structure is added to the polymerization system.
No. 31, JP-A-59-53856 and JP-A-5-53856
No. 9-61842, a method of directly producing a toner by using a suspension polymerization method, a method of directly producing a toner by using an aqueous organic solvent in which a monomer is soluble and a polymer obtained is insoluble. The toner of the present invention can be obtained by a dispersion polymerization method such as described below, or an emulsion polymerization method represented by a soap-free polymerization method in which a toner is produced by directly polymerizing in the presence of a water-soluble polymerization initiator. In addition, a polycarbonate resin containing no polycarbonate resin containing a halogen atom in a molecular structure is produced by a polymerization method, and then a polycarbonate resin containing a fine particle halogen atom in a molecular structure on the surface of the polymer particle. And a method of smoothing and spheroidizing the toner particles.
As another method, a spherical toner is prepared by atomizing a molten mixture containing a polycarbonate resin containing a halogen atom in its molecular structure into the air using a disk or a multi-fluid nozzle described in JP-B-56-13945. And the like.

Among the toner production methods described above, the toner produced by the melt spray method tends to have a wide particle size distribution. On the other hand, in the dispersion polymerization method, the obtained toner shows an extremely sharp particle size distribution, but the production equipment is complicated from the viewpoint of narrow selection of materials to be used and the use of organic solvents in terms of waste solvent treatment and solvent flammability. It is easy to be complicated. In addition, the emulsion polymerization method has an advantage that the particle size distribution of the toner is relatively uniform, but the particle size of the generated particles is generally very small, and it is difficult to use the toner as it is. Furthermore, the terminal of the used water-soluble polymerization initiator and the emulsifier may be present on the surface of the toner particles, and may deteriorate the environmental characteristics. On the other hand, a manufacturing method in which a pulverization method or a polymerization method is combined with a smoothing and sphering treatment of a toner particle, and a polycarbonate resin containing a halogen atom directly in a molecular structure by a polymerization method is present on the surface of the toner particle. In the method for producing the above, it is easy to make the circularity and the circularity standard deviation fall within a desired range, and it can be said that this is a preferable production method. Further, a production method in which a polymerization method is combined with smoothing and sphering treatment of toner particles, and a toner in which a polycarbonate resin containing a halogen atom directly in a molecular structure is present on the surface of toner particles by a polymerization method. In the method, it is extremely easy to control the circularity and the standard deviation of the circularity to a desired range. Further, in the observation of the tomographic plane of the toner using a transmission electron microscope (TEM), the halogen atom is included in the molecular structure. Is contained on the surface of the toner particles, and a binder resin and a wax component obtained from a vinyl monomer are present therein, and the wax component is substantially spherical in the binder resin. And / or dispersed in spindle-shaped islands,
There is little change in charging characteristics due to the environment, transferability, developability,
This is a more preferable production method because a toner having excellent low-temperature fixability and blocking resistance can be obtained. Further, a method of producing a toner in which a polycarbonate resin containing a halogen atom directly in a molecular structure is present on the surface of a toner particle by a polymerization method, in addition to the above-described advantages, for example, a halogen atom having a high melting temperature is used. Even if the polycarbonate resin contained in the molecular structure is used, the polycarbonate resin containing the halogen atom in the molecular structure may be dissolved and used in the monomer composition to be used. There are also many types of polycarbonate resins containing a halogen atom in the molecular structure that can be used, and this is a particularly preferable production method.

In the present invention, as a specific method for observing the tomographic plane of the toner, a cured product obtained by sufficiently dispersing toner particles in a cold-setting epoxy resin and then curing the resulting mixture at 40 ° C. for 2 days. Is stained using ruthenium tetroxide and, if necessary, osmium tetroxide, and then a flaky sample is cut out using a microtome provided with diamond teeth, and the tomographic plane of the toner is observed using a transmission electron microscope. In the present invention, it is preferable to use a ruthenium tetroxide dyeing method in order to obtain a contrast between the materials by utilizing a slight difference in crystallinity between the wax component to be used and the binder resin constituting the outer shell. FIG. 6 shows a typical example.
a, 6b and 6c.

When the toner particles (1), (4) and (5) obtained in Examples 1, 4 and 5 described below were observed on a tomographic plane with a TEM, the toner particles (1) showed halogen particles. The polycarbonate resin containing atoms in the molecular structure is continuously present on the surface of the toner particles (FIG. 6).
a) In the case of toner particles (4), a polycarbonate resin containing a halogen atom in the molecular structure was discontinuously present on the surface of the toner (FIG. 6B). Further, in the case of the toner particles (5), a polycarbonate resin containing a halogen atom in the molecular structure is continuously present on the surface of the toner, and a binder obtained from a vinyl monomer is contained therein. It was observed that a resin, a polycarbonate-based resin containing a halogen atom in its molecular structure, and a wax component were present, and that the wax component was substantially dispersed in the binder resin in a spherical and spindle-shaped island shape (FIG. 6c).

When a polymerization method is used as a method for producing a toner, the particle size distribution and the particle size of the toner particles are controlled by changing the type and amount of a poorly water-soluble inorganic salt or a dispersant that acts as a protective colloid. The desired toner particles can be obtained by controlling the mechanical conditions (eg, the peripheral speed of the rotor, the number of passes, the stirring conditions such as the shape of the stirring blade and the shape of the container), or the solid content concentration in the aqueous solution. .

When a toner is produced by the direct polymerization method, examples of the polymerization initiator used include 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile,
Azo-based or diazo-based polymerization initiators such as azobisisobutyronitrile; peroxide-based polymerization initiators such as benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide and lauroyl peroxide Is used. The amount of the polymerization initiator varies depending on the desired degree of polymerization, but is generally used in an amount of 0.5 to 20% by weight based on the polymerizable monomer. The type of the polymerization initiator varies slightly depending on the polymerization method, but is used alone or in combination with reference to the 10-hour half-life temperature.

For controlling the degree of polymerization, known crosslinking agents, chain transfer agents, polymerization inhibitors and the like may be further added and used.

When a suspension polymerization method using a dispersion stabilizer is used as a method for producing a toner, the dispersion stabilizer used may be
As inorganic compounds, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite , Silica, alumina and the like. As organic compounds,
Polyvinyl alcohol, gelatin, methylcellulose,
Examples include methylhydroxypropylcellulose, ethylcellulose, sodium salts of carboxymethylcellulose, polyacrylic acid and its salts, starch and the like. These can be used by dispersing them in an aqueous phase. It is preferable to use 0.2 to 20 parts by weight of these dispersion stabilizers based on 100 parts by weight of the polymerizable monomer.

When an inorganic compound is used as the dispersion stabilizer, a commercially available one may be used as it is, but fine particles of the inorganic compound may be produced in a dispersion medium in order to obtain fine particles. For example, in the case of tricalcium phosphate,
It is preferable to mix an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high-speed stirring.

For fine dispersion of these dispersion stabilizers,
0.001 to 0.1 parts by weight of a surfactant may be used in combination. This is to promote the intended action of the dispersion stabilizer, for example, sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate. ,
And calcium oleate.

When a direct polymerization method is used as a method for producing the toner used in the present invention, the following production method is possible.

A monomer composition obtained by adding a wax component, a colorant, a charge control agent, a polymerization initiator, and other additives to a polymerizable monomer and uniformly dissolving or dispersing the mixture using a homogenizer, an ultrasonic disperser, or the like. The product is dispersed in an aqueous phase containing a dispersion stabilizer using a conventional stirrer, homomixer, homogenizer or the like. Preferably, the granulation is performed by adjusting the stirring speed and the stirring time so that the droplets of the monomer composition have the desired size of the toner particles. Thereafter, by the action of the dispersion stabilizer, the particles may be stirred to such an extent that the particle state is maintained and the particles are prevented from settling. Polymerization temperature is 40 ° C
As described above, it is generally preferable to carry out polymerization at a temperature of 50 to 90 ° C. The temperature may be raised in the latter half of the polymerization reaction.
For the purpose of improving the durability in the image forming method of the present invention, in order to remove unreacted polymerizable monomers, by-products, etc., in the latter half of the reaction, or after the reaction, a part of the aqueous medium is distilled off from the reaction system. You may. After completion of the reaction, the generated toner particles are collected by washing and filtration, and dried. In the suspension polymerization method, usually, 30 parts of water is added to 100 parts by weight of the monomer composition.
It is preferable to use 0 to 3000 parts by weight as the dispersion medium.

In the toner of the present invention, it is essential that a polycarbonate resin containing a halogen atom in the molecular structure is present on the surface of the toner particle. Confirmation of the presence of the contained polycarbonate resin can be carried out using any analytical means. As an example, first, a tomographic surface of the toner particles is observed by a TEM to check whether or not the surface of the toner particles has a contrast. When a polycarbonate-based resin containing a halogen atom in its structure is present on the surface, a contrast is formed in that portion. Then, photoacoustic spectroscopy (PAS = Photoac)
organic Spectroscopy)
By changing the scanning speed of the movable mirror, the composition of the surface of the obtained toner particles can be determined by infrared absorption spectrum (IR).
Analyze by / PAS. If contrast is observed continuously or discontinuously on the surface of the toner particles by the TEM observation, and a polycarbonate resin containing a halogen atom in the structure is confirmed by IR / PAS analysis, the surface of the toner particles is It can be determined that a polycarbonate resin containing a halogen atom in the structure is present.
In addition to the IR / PAS, Raman spectroscopy and the PAS
Analysis of toner particle surface, ESCA
(Electron Spectroscopy fo
There are various analysis means such as elemental analysis of the toner particle surface by r chemical analysis, elemental analysis of the toner particle surface by an electron microscope equipped with an energy dispersive X-ray spectrometer or an electron beam energy analyzer.
These analysis means are used alone or in combination as needed.

In the toner of the present invention, charging stability,
In order to improve developability, fluidity and durability, it is preferable to use an inorganic fine powder mixed with toner particles as an additive.

Examples of the inorganic fine powder used in the present invention include:
Examples include silica fine powder, titanium oxide, and alumina fine powder. Among them, the specific surface area by nitrogen adsorption measured by the BET method is 30 m ² / g or more (particularly 50 to 400 m ² / g).
Those within the range give good results. It is preferable to use 0.01 to 8 parts by weight, preferably 0.1 to 5 parts by weight of the inorganic fine powder with respect to 100 parts by weight of the toner.

The inorganic fine powder used in the present invention may contain a silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, a silane coupling agent, and a functional group for the purpose of hydrophobicity and charge control as required. It is also preferable to be treated with a treating agent such as a silane coupling agent having the above or another organosilicon compound.

As other additives, lubricants such as Teflon (registered trademark), zinc stearate, and polyvinylidene fluoride (in particular, polyvinylidene fluoride are preferable); abrasives such as cerium oxide, silicon carbide, and strontium titanate (in particular, Strontium titanate is preferred);
Anti-caking agents; conductivity-imparting agents such as carbon black, zinc oxide, antimony oxide and tin oxide; and developability improvers such as white fine particles and black fine particles having a polarity opposite to that of the toner particles.

Next, an image forming method to which the toner of the present invention is applied will be described below with reference to the accompanying drawings.

The toner of the present invention can be applied to various developing systems. As an example, FIG. 1 shows an example of an apparatus for developing an electrostatic image formed on an electrostatic latent image carrier by one-component development, but is not necessarily limited thereto.

In FIG. 1, reference numeral 25 denotes an electrostatic latent image carrier (photosensitive drum), and a latent image is formed by an electrophotographic process means or an electrostatic recording means. Reference numeral 24 denotes a toner carrier (developing sleeve), which is formed of a non-magnetic sleeve made of aluminum, stainless steel, or the like.

The substantially right half peripheral surface of the developing sleeve 24 is always in contact with the toner reservoir in the toner container 21, and the toner near the developing sleeve surface is brought into contact with the developing sleeve surface by the magnetic force of the magnetic generating means in the sleeve. Adhered and held by electrostatic force.

In the present invention, the surface roughness Ra of the toner carrier is
(Μm) is set to 1.5 or less. Preferably it is 1.0 or less. More preferably, it is 0.5 or less.

By setting the surface roughness Ra to 1.5 or less, the ability of the toner carrier to transport toner particles is suppressed.
Since the toner layer on the toner carrier is made thinner and the number of times of contact between the toner carrier and the toner is increased, the chargeability of the toner is also improved, so that the image quality is synergistically improved.

When the surface roughness Ra of the toner carrier exceeds 1.5, not only is it difficult to reduce the thickness of the toner layer on the toner carrier, but also the chargeability of the toner is not improved. Can not hope.

In the present invention, the surface roughness Ra of the toner carrier is measured using a surface roughness measuring device (Surfcoder SE-30H, manufactured by Kosaka Laboratories Co., Ltd.) based on JIS surface roughness "JISB 0601". Corresponds to the center line average roughness measured. Specifically, a 2.5 mm portion is extracted from the roughness curve in the direction of the center line as the measurement length a,
The center line of the extracted portion is the X axis, and the direction of the vertical magnification is Y.
When an axis and a roughness curve are represented by y = f (x), a value obtained by the following equation is represented by a micrometer (μm).

[0112]

(Equation 4)

As the toner carrier used in the present invention, a cylindrical or belt-like member made of, for example, stainless steel, aluminum or the like is preferably used. If necessary, the surface may be coated with metal, resin, etc.
A resin in which fine particles such as a resin, metals, carbon black, and a charge control agent are dispersed may be coated.

According to the present invention, the surface moving speed of the toner carrier is set to be 1.05 to 3 times the surface moving speed of the electrostatic latent image carrier.
By setting the ratio to 0, the toner layer on the toner carrier receives an appropriate stirring effect, so that the faithful reproduction of the electrostatic latent image is further improved.

When the surface moving speed of the toner carrier is less than 1.05 times the surface moving speed of the electrostatic latent image carrier, the stirring effect of the toner layer becomes insufficient, and good image formation is achieved. Can not hope. Further, when developing an image requiring a large amount of toner over a wide area, such as a solid black image, the amount of toner supplied to the electrostatic latent image is insufficient, and the image density is reduced. Conversely, when the ratio exceeds 3.0 times, in addition to the various problems caused by the excessive charging of the toner as described above, deterioration of the toner due to mechanical stress and adhesion of the toner to the toner carrier are generated and accelerated. Is not preferred.

The toner T is stored in the hopper 21, and is supplied onto the developing sleeve by the supply member 22. As the supply member, a supply roller made of a porous material such as a foamed material such as a flexible polyurethane foam is preferably used. The supply roller is rotated with respect to the developing sleeve in a forward or reverse direction at a relative speed other than 0, and the toner is supplied to the developing sleeve and the toner (undeveloped toner) after development on the sleeve is also removed. .
At this time, the contact width of the supply roller with the developing sleeve is determined in consideration of the balance between toner supply and stripping.
0 to 10.0 mm is preferable, and 4.0 to 6.0 mm is more preferable. On the other hand, excessive stress on the toner is unavoidable, and the aggregation of the toner due to the deterioration of the toner is increased, or the fusion and fixation of the toner to the developing sleeve, the supply roller and the like are easily caused. Since the toner is excellent in fluidity and releasability and has durability stability, it is preferably used in a developing method having the supply member. In addition, nylon,
A brush member made of resin fiber such as rayon may be used. Note that these supply members are extremely effective in a one-component developing method using a non-magnetic one-component toner that cannot utilize a magnetic binding force, but may be used in a one-component developing method using a magnetic one-component toner.

The toner supplied on the developing sleeve is thinly and uniformly applied by the regulating member. The toner thinning regulating member is a doctor blade such as a metal blade or a magnetic blade disposed at a predetermined interval from the developing sleeve. Alternatively, instead of the doctor blade, a rigid roller or sleeve using metal, resin, ceramics, or the like may be used, and a magnetic generating means may be used inside the roller or sleeve.

An elastic member such as an elastic blade or an elastic roller for press-applying the toner may be used as a regulating member for thinning the toner. For example, in FIG. 1, the elastic blade 23 has its base, which is the upper side, fixed and held on the developer container 21 side, and has the lower side thereof in the forward or reverse direction of the developing sleeve 24 against the elasticity of the blade. In the bent state, the inner side of the blade (in the opposite direction, the outer side)
Is brought into contact with the surface of the sleeve 24 with an appropriate elastic pressure. According to such an apparatus, a dense toner layer that is stable against environmental fluctuations can be obtained. Although the reason is not necessarily clear, it is presumed that the elastic body forcibly rubs against the surface of the developing sleeve, so that the charging is always performed in the same state regardless of a change in behavior due to a change in toner environment.

On the other hand, the toner tends to be excessively charged and the toner is easily fused on the developing sleeve or the elastic blade. However, the toner used in the present invention has excellent releasability and stable frictional charging. It is preferably used.

It is preferable to select a material of a triboelectric series suitable for charging the toner to a desired polarity for the elastic material, and a rubber elastic material such as silicone rubber, urethane rubber, NBR, or a synthetic material such as polyethylene terephthalate. Metal elastic bodies such as resin elastic bodies, stainless steel, steel, and phosphor bronze can be used. Further, a composite thereof may be used.

When durability is required for the elastic body and the toner carrier, it is preferable that a resin or rubber is bonded to the metal elastic body so as to contact the sleeve contact portion, or the metal elastic body is coated.

Further, an organic substance or an inorganic substance may be added to the elastic body, may be melted and mixed, or may be dispersed. For example, the chargeability of the toner can be controlled by adding a metal oxide, metal powder, ceramics, carbon allotrope, whisker, inorganic fiber, dye, pigment, surfactant or the like. Particularly, when the elastic body is a molded body such as rubber or resin, fine particles of metal oxide such as silica, alumina, titania, tin oxide, zirconia, and zinc oxide, carbon black, a charge control agent generally used for toner And the like.

Further, by applying a DC electric field and / or an AC electric field to the developing blade as the regulating member, the supply roller as the supplying member, and the brush member, the regulating member on the developing sleeve can be loosened by the toner. Improves uniform thin layer coating properties and uniform charging properties,
In the supply member, the supply / stripping of the toner is performed more smoothly, so that a sufficient image density can be achieved and a high quality image can be obtained.

The contact pressure between the elastic body and the toner carrier is:
The linear pressure in the generatrix direction of the toner carrier is 0.1 kg / m
Above, preferably 0.3 to 25 kg / m, more preferably 0.5 to 12 kg / m is effective. As a result, it is possible to effectively loosen the collection of toner, and it is possible to instantaneously raise the charge amount of the toner. If the contact pressure is less than 0.1 kg / m, it becomes difficult to apply the toner uniformly, and the charge amount distribution of the toner becomes broad, causing fogging and scattering. The contact pressure is 25 kg /
When m exceeds m, a large pressure is applied to the toner, and the toner is undesirably deteriorated and aggregates of the toner are generated. Further, a large torque is required to drive the toner carrier, which is not preferable.

The gap α between the electrostatic latent image carrier and the toner carrier
Is preferably set to 50 to 500 μm, and the gap between the doctor blade and the toner carrier is preferably set to 50 to 400 μm.

The thickness of the toner layer on the toner carrier is most preferably smaller than the gap α between the electrostatic latent image carrier and the toner carrier. Among them, the layer thickness of the toner layer may be restricted to such an extent that a part of the toner layer contacts the electrostatic latent image carrier.

On the other hand, a bias power supply 2
By applying an alternating electric field between the toner carrying member and the electrostatic latent image carrying member by 6, the movement of the toner from the toner carrying member to the electrostatic latent image carrying member is facilitated, and a higher quality image can be obtained. Vpp of the alternating electric field is 100 V or more, preferably 20 V
0-3000V, more preferably 300-2000V
It is better to use it. F is 500 to 5000 Hz;
Preferably it is used at 1000 to 3000 Hz, more preferably at 1500 to 3000 Hz. In this case, a waveform such as a rectangular wave, a sine wave, a sawtooth wave, and a triangular wave can be applied. Also, asymmetrical AC biases having different positive and reverse voltages and times can be used. It is also preferable to superimpose a DC bias.

The electrostatic latent image carrier 25 is composed of a-Se, Cds,
A photosensitive drum or a photosensitive belt having a photoconductive insulating material layer such as ZnO ₂ , OPC, or a-Si. The electrostatic latent image carrier 1 is rotated in a direction indicated by an arrow by a driving device (not shown).

As the electrostatic latent image carrier 25, a photosensitive member having an amorphous silicon photosensitive layer or an organic photosensitive layer is preferably used.

The organic photosensitive layer may be a single layer in which the photosensitive layer contains a charge generating substance and a substance having a charge transport function in the same layer, or a functional separation comprising the charge transport layer and the charge generation layer as components. It may be a type photosensitive layer. A laminated photosensitive layer having a structure in which a charge generation layer and then a charge transport layer are laminated on a conductive substrate in this order is one of preferred examples.

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

In the charging step, there are a system that is not in contact with the electrostatic latent image carrier 25 using a corona charger, and a contact system that uses a roller or the like, and both systems are used. For efficient uniform charging, simplification, and low ozone generation, a contact type is preferably used.

[0133]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples.

(Production Example of Binder Resin) 200 parts by weight of xylene was placed in a reaction vessel and heated to the reflux temperature. 85 parts by weight of styrene, 15 parts by weight of n-butyl acrylate,
After dropping a mixed solution of 1.5 parts by weight of di-tert-butyl peroxide, the solution polymerization was completed in 10 hours under reflux of xylene to obtain a low molecular weight resin solution.

On the other hand, 70 parts by weight of styrene, 25 parts by weight of butyl acrylate, 5 parts by weight of monobutyl maleate, 0.2 parts by weight of polyvinyl alcohol, 200 parts by weight of degassed water,
0.1 parts by weight of benzoyl peroxide was mixed, suspended and dispersed.
The above suspension and dispersion solution is heated to 85 under a nitrogen atmosphere.
C. for 24 hours to complete the polymerization to obtain a high molecular weight resin.

30 parts by weight of the high-molecular-weight resin are put into a solution containing 70 parts by weight of the low-molecular-weight resin at the time of completion of the solution polymerization, completely dissolved in the solvent and mixed, and then the solvent is distilled off. Thus, a binder resin (1) was obtained.

When the binder resin (1) was analyzed, the peak molecular weight on the low molecular weight side was 13,000, the peak molecular weight on the high molecular weight side was 700,000, and the weight average molecular weight (Mw) was 360.
000, number average molecular weight (Mn) is 6000, Mw / Mn
Was 60. The glass transition temperature (Tg) is 60
° C.

Example 1 100 parts by weight of binder resin (1) 5 parts by weight of carbon black (BET specific surface area = 101 m ² / g) 1.5 parts of negative charge control agent (azo acid-based iron complex) 1.5 6 parts by weight of paraffin wax with maximum endothermic peak of 80 ° C

The above materials were mixed in a blender, melt-kneaded in a biaxial extruder heated to 130 ° C., and the cooled kneaded material was coarsely pulverized by a hammer mill, and the coarsely pulverized material was finely pulverized by a jet mill. did.

Next, 100 parts by weight of the finely pulverized particles and 2,2-bis (4-hydroxyphenyl) -1,1
1,1,3,3,3-hexafluoropropane polycarbonate resin (1) [peak molecular weight 4000, Mw
5000, Mn1400] by dry mixing with a Henschel mixer to obtain particles in which fine powder of a polycarbonate resin (1) containing a halogen atom in the structure adheres to the surface of the finely pulverized particles. Further, the particles were subjected to surface modification by using a device for applying a mechanical impact by rotating a rotor. Next, the obtained particles were classified to obtain a classified powder (1).

When the tomographic surface of the classified powder (1) was observed by TEM, contrast was continuously observed on the toner surface. Further, by using PAS and changing the scan speed of the movable mirror, the composition analysis of the obtained particle surface can be performed by F
As a result of T-IR / PAS, a spectrum derived from the polycarbonate-based resin (1) containing a halogen atom in the structure was obtained, and the surface of the particle was continuously coated with a polycarbonate containing a halogen atom in the structure. It was confirmed that the system resin was present. Table 1 shows the analysis results of the classified powder (1).

Example 2 As a polycarbonate resin containing a halogen atom in its molecular structure, 1,1-bis (4-hydroxyphenyl) -2,3,4,5,6-pentachlorocyclohexane polycarbonate resin (2) [Peak molecular weight 4500, Mw 5500, Mn1
200], except that the classified powder (2) and the toner (2) were prepared in the same manner as in Example 1. Table 1 shows the analysis results of the classified powder (2).

<Example 3> As a polycarbonate resin containing a halogen atom in its molecular structure, 1,1-bis (4-hydroxyphenyl) cyclohexane and 2,2-bis (4-hydroxyphenyl) cyclohexane were used.
Bis (4-hydroxyphenyl) -1,1,1,3
Copolymerized polycarbonate resin (3) obtained from 3,3-hexafluoropropane [copolymerization ratio 80:20 (weight ratio), peak molecular weight 6000, Mw 8000, Mn 20
00], a classification powder (3) and a toner (3) were prepared in the same manner as in Example 1. Table 1 shows the analysis results of the classified powder (3).

Example 4 As a polycarbonate resin containing a halogen atom in its molecular structure, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane and 1
-Phenyl-1,1-bis (4-hydroxyphenyl)
Copolymerized polycarbonate resin (4) obtained from -2,2,2-trifluorethane [copolymerization ratio 80:20 (weight ratio), peak molecular weight 4000, Mw 6000, Mn1
500], and a classified powder (4) and a toner (4) were prepared in the same manner as in Example 1. Table 1 shows the analysis results of the classified powder (4).

<Example 5> 650 g of ion-exchanged water was placed in a four-neck 2-liter separable flask equipped with a high-speed stirrer TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.).
500 g of a mol / liter-Na ₃ PO ₄ aqueous solution was charged, the rotation speed was adjusted to 12,000 rpm, and the mixture was heated to 70 ° C. To this, 70 parts by weight of a 1.0 mol / liter CaCl ₂ aqueous solution was gradually added to prepare an aqueous continuous phase containing a minute hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ).

On the other hand, as a dispersoid: 85 parts by weight of styrene 15 parts by weight of n-butyl acrylate 0.3 part by weight of divinylbenzene (purity 55%) 8 parts by weight of carbon black (BET specific surface area = 114 m ² / g) -Negative charge control agent (azo-based iron complex) 1.5 parts by weight The above mixture was dispersed using an attritor (manufactured by Mitsui Miike Kako) for 3 hours.-A polycarbonate resin containing a halogen atom in its structure ( 1) 4 parts by weight ・ 3 parts by weight of a polypropylene wax having a maximum endothermic peak of 108 ° C. 3 parts by weight ・ 10 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) are added, and the mixture is heated to 80 ° C. to obtain a polymerizable monomer. A body composition was prepared.

Next, the polymerizable monomer composition was charged into the aqueous dispersion medium, and the mixture was stirred for 15 minutes at a liquid temperature of 80 ° C. while maintaining the rotation speed of a high-speed stirrer at 10,000 rpm in a nitrogen atmosphere. The hydrophilic monomer composition was granulated. Then, the suspension was changed to a propeller type stirring blade and maintained at 80 ° C. for 10 hours while stirring at 50 rpm to obtain a suspension.

After that, the suspension was cooled, and then dilute hydrochloric acid was added to remove the dispersion stabilizer. Further, washing with water was repeated several times, followed by drying to obtain polymer particles (5).

1.0 g of the polymer particles (5) was precisely weighed and charged in a cylindrical filter paper, and tetrahydrofuran (THF) 200 m
1 for 20 hours, and the thimble filter paper was extracted at 40 ° C.
The residue was dried in vacuo for 12 hours and the weight of the residue was measured. The THF-insoluble content was calculated to be 30% by weight based on the polymer particles.

Example 6 The procedure of Example 5 was repeated, except that the polycarbonate resin (2) containing a halogen atom in the structure was used as the polycarbonate resin containing a halogen atom in the structure. Inventive polymer particles (6) and toner (6) were prepared. Table 1 shows the analysis results of the polymer particles (6).

<Example 7> The same procedure as in Example 5 was carried out except that a polycarbonate resin (3) containing a halogen atom in the structure was used as the polycarbonate resin containing a halogen atom in the structure. Inventive polymer particles (7) and toner (7) were prepared. Table 1 shows the analysis results of the polymer particles (7).

Example 8 In a polymerizable monomer composition, an unsaturated polyester (polyester obtained by condensing propoxylated bisphenol A and fumaric acid, peak molecular weight 1)
0000) was added in the same manner as in Example 5 except that 1 part by weight of polymer particles (8) and (8) were prepared. Table 1 shows the analysis results of the polymer particles (8).

Comparative Example 1 Example 1 was repeated except that a polycarbonate resin containing a halogen atom in the structure was not used.
In the same manner as in the above, comparative classification powder (9) and comparative toner (9) were prepared. Table 1 shows the analysis results of the classified powder (9).

Comparative Example 2 Example 5 was repeated except that a polycarbonate resin containing a halogen atom in the structure was not used.
In the same manner as in the above, comparative polymer particles (10) and comparative toner (10) were prepared. Table 1 shows the analysis results of the polymer particles (10).

[0155]

[Table 1]

<Example 9 and Comparative Example 3> Example 1 above
The evaluation was performed as follows using the toner (1) and the comparative toner (9) manufactured in Comparative Example 1.

The developing device of the image forming apparatus shown in FIG. 1 was set such that the moving speed of the toner carrier surface was 3.0 times the moving speed of the electrostatic latent image carrier surface. Next, each of the toner (1) and the comparative toner (10) is filled in the developing device, and the developing device is set in the image forming apparatus.
C., 85% RH) in a continuous mode in a single color (that is, a mode in which toner consumption is promoted without stopping the developing device) at a printout speed of 14 sheets / min (A4 size). A printout test was performed. Then, the obtained printout image was evaluated for items described below.

Table 2 shows the evaluation results.

The surface roughness Ra of the toner carrier used here was 1.5, the toner regulating blade adhered urethane rubber to a phosphor bronze base plate, and the contact surface with the toner carrier was made of nylon. The coated one was used.

[0160]

[Table 2]

<Examples 10 to 17 and Comparative Examples 4 and 5>
FIG. 2 is a schematic diagram illustrating an example of an image forming apparatus using an intermediate transfer belt.

FIG. 2 shows a color image forming apparatus (copier or laser beam printer) using an electrophotographic process.

Reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member (hereinafter, referred to as a photosensitive drum) as a first image carrier, which is driven to rotate at a predetermined peripheral speed (process speed) in the direction of an arrow.

The photosensitive drum 1 rotates in the primary charging device 2 during the rotation process.
, And is uniformly charged to a predetermined polarity and potential, and then subjected to exposure 3 by image exposure means 3 (not shown). In this way, an electrostatic latent image corresponding to the first color component image (for example, a yellow color component image) of the target color image is formed.

Next, the electrostatic latent image is developed into a first color yellow component image by a first developing unit (yellow developing unit 41). At this time, since the second to fourth developing devices, namely, the magenta developing device 42, the cyan developing device 43, and the black developing device 44 are not operating and do not act on the photosensitive drum 1, the first developing device is not used. The color yellow component image is not affected by the second to fourth developing units.

The intermediate transfer belt 40 is driven to rotate at the same peripheral speed as the photosensitive drum 1 in the direction of the arrow.

The first color yellow component image formed on the photosensitive drum 1 is transferred to the photosensitive drum 1 and the intermediate transfer belt 40.
In the process of passing through the nip portion of the intermediate transfer belt 40, the electric power is sequentially transferred to the outer peripheral surface of the intermediate transfer belt 40 by the electric field formed by the primary transfer bias applied to the intermediate transfer belt 40 from the bias power supply 49 via the primary transfer roller 62 ( Primary transfer).

After the transfer of the first color yellow toner image corresponding to the intermediate transfer belt 40, the surface of the photosensitive drum 1 is cleaned by the first cleaning device 53.

Similarly, the magenta toner image of the second color, the cyan toner image of the third color, and the black toner image of the fourth color are sequentially transferred onto the intermediate transfer belt 40 in a superimposed manner to correspond to the target color image. Thus, a combined color toner image is formed.

Reference numeral 63 denotes a secondary transfer roller, which corresponds to the secondary transfer opposing roller 64 and is supported in parallel with the intermediate transfer belt 40.
Are disposed on the lower surface of the device so as to be separated therefrom.

A primary transfer bias for transferring a toner image from the photosensitive drum 1 to the intermediate transfer belt 40 is applied from a bias power supply 49 with a polarity opposite to that of the toner. The applied voltage is in a range of, for example, +100 V to +2 kV.

In the primary transfer process of the toner images of the first to third colors from the photosensitive drum 1 to the intermediate transfer belt 40, the secondary transfer roller 63 and the transfer residual toner charging member 52 may be separated from the intermediate transfer belt 40. It is possible.

The full-color image transferred onto the intermediate transfer belt 40 is
The transfer material P, which is the second image carrier, is fed from the paper feed roller 51 to the contact portion between the intermediate transfer belt 40 and the secondary transfer roller 63 at a predetermined timing from the paper feed roller 51, and the secondary transfer bias is applied. Is applied to the secondary transfer roller 63 from the bias power supply 48, so that the secondary transfer is performed on the transfer material P. The transfer material P on which the toner image has been transferred is introduced into the fixing device 55 and is heated and fixed.

After the image transfer to the transfer material P is completed, the transfer residual toner cleaning device 52 is brought into contact with the intermediate transfer belt 40, and the surface of the intermediate transfer belt 40 is cleaned.

Using the above-described image forming apparatus, the moving speed of the surface of the toner carrier is smaller than the moving speed of the surface of the electrostatic latent image carrier.
3.0 times, and then each of the toners (1) to (8) and the comparative toners (9) and (10) is filled in the developing device, and the developing device is mounted on the image forming apparatus. I set it. Under high temperature and high humidity (40 ° C, 85% RH) environment, 15 sheets / min (A
(4 sizes) at 7000 printout speeds. Then, the obtained printout image was evaluated for items described below.

Table 3 shows the above evaluation results.

The surface roughness Ra of the toner carrier used here was 1.4, the toner regulating blade adhered urethane rubber to the phosphor bronze base plate, and the contact surface with the toner carrier was made of nylon. A well-recoated one was used.

[0178]

[Table 3]

<Embodiment 18 and Comparative Example 6> In this embodiment, a commercially available laser beam printer LBP-EX (manufactured by Canon Inc.) was remodeled with a reuse mechanism attached, and used again. That is, in FIG. 3, after the untransferred toner on the photosensitive drum 70 is scraped off by the elastic blade 72 of the cleaner 71 in contact with the photosensitive drum, the toner is sent to the inside of the cleaner by the cleaner roller, and further passed through the cleaner screw 73. Then, the toner was returned to the developing device 76 via a hopper 75 by a supply pipe 74 provided with a conveying screw, and a system utilizing the collected toner was attached again. As a primary charging roller 77, conductive carbon coated with nylon resin was dispersed. Using a rubber roller (diameter: 12 mm, contact pressure: 50 g / cm), the electrostatic latent image carrier was formed by laser exposure (600 dpi) to form a dark portion potential V _D = −700 V and a bright portion potential V _L = −200 V. The developing sleeve 78 having a surface roughness Ra of 1.1 coated with a resin in which carbon black is dispersed as a toner carrier has a surface roughness Ra of 1.1 with respect to the moving speed of the photosensitive drum surface.
The distance between the photosensitive drum and the developing sleeve (between SD) was set to 290 μm, and a urethane rubber blade was used as a toner regulating member in contact with the photosensitive drum. Further, an AC bias component was superimposed on a DC bias component as a developing bias.

As the heating and fixing device H, the fixing device shown in FIGS. 4 and 5 is used. The surface temperature of the heating element 31d of the heating element 31 is 190 ° C., and the heating element 21-silicone rubber foam is used as a lower layer. The total pressure between the sponge pressure roller 33 is 9 kg, the nip between the pressure roller and the film is 8 mm, and the fixing film 32 has a PTF on the contact surface with the transfer material.
A 60 μm thick heat-resistant polyimide film having a low-resistance release layer in which a conductive substance was dispersed in E (high molecular weight type) was used.

Next, each of the toner (6) and the comparative toner (10) was filled in the developing device, and the developing device was set in the image forming apparatus. Under high temperature and high humidity (40 ° C, 85% RH) environment, 1
At a printout speed of 6 sheets / minute (A4 size), the developing unit is paused for 10 seconds each time one sheet is printed out, and the deterioration of the toner is promoted by the preliminary operation of the developing device upon restarting. Mode), a 8000 printout test was performed. Then, the obtained printout image was evaluated for items described below.

Table 4 shows the above evaluation results.

[0183]

[Table 4]

<Embodiment 19> Except that the toner reuse mechanism of FIG. 3 is removed, the toner (6) is operated in the continuous mode (that is, toner consumption is promoted without stopping the developing device) in the same manner as in Embodiment 18. Printout test was performed on 10,000 sheets.

The printout images obtained were evaluated for the following items. As a result, all the items were good.

The evaluation items described in the examples and comparative examples of the present invention and the evaluation criteria will be described.

[Evaluation of Printout Image] <1> Fog under High Humidity A predetermined number of printouts were made on plain paper for copying machines (85 g / m ² ) in a high-temperature and high-humidity environment, and a “Reflectometer” (Tokyo Denshoku) The fog density (%) was calculated from the difference between the whiteness of the white background portion of the printout image of the last page measured by the method described in US Pat. A: less than 1.5% B: 1.5% or more, less than 2.5% C: 2.5% or more, less than 4.0% D: 4.0% or more

<2> Change in Image Density A predetermined number of printouts are made on plain paper for copying machines (85 g / m ² ) in a high-temperature and high-humidity environment.
The image density of the printout image of the first and last pages was measured using a “Macbeth reflection densitometer” (manufactured by Macbeth), and the “absolute value of the density difference between the 100th and 1000th sheets”
And the “absolute value of the density difference between the 1000th sheet and the last page” were calculated and evaluated according to the following criteria. The image density was measured by measuring the relative density of a white background portion of the original density of 0.00 with respect to the printout image. A: less than 0.10 B: 0.10 or more, less than 0.15 C: 0.15 or more, less than 0.20 D: 0.20 or more

[0189]

According to the present invention, it is possible to provide a dry toner and an image forming method which are less likely to cause fog even under high humidity and have little change in density even when a large number of images are formed.

[Brief description of the drawings]

FIG. 1 is an enlarged cross-sectional view of a main part of a developing device for one-component development used in an embodiment of the present invention.

FIG. 2 is a schematic diagram of a color image output device using an intermediate transfer belt.

FIG. 3 is a schematic explanatory view of an image forming apparatus that reuses untransferred toner.

FIG. 4 is an exploded perspective view of a main part of the fixing device used in the embodiment of the present invention.

FIG. 5 is an enlarged cross-sectional view of a main part showing a film state when the fixing device used in the embodiment of the present invention is not driven.

FIG. 6 is a schematic view of a tomographic plane of the toner according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Photoconductor (electrostatic latent image carrier) 2 Charging roller 3 Exposure 30 Stay 31 Heating body 31a Heater substrate 31b Heating body 31c Surface protection layer 31d Temperature sensor 32 Fixing film 33 Pressure roller 34 Coil spring 35 Film end regulating flange 36 Power supply connector 37 Disconnecting member 38 Inlet guide 39 Outlet guide (separation guide) 40 Intermediate transfer member 41 Yellow developing device 42 Magenta developing device 43 Cyan developing device 44 Black developing device 51 Feed roller 52 Transfer residual toner cleaning Device 53 Cleaning Device 55 Fixer 62 Primary Transfer Roller 63 Secondary Transfer Roller 64 Secondary Transfer Opposing Roller 65 Intermediate Transfer Belt Support Roller 66 Intermediate Transfer Belt Support Roller P Transfer Material

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 15/08 504 G03G 9/08 21/10 325 331 333 333 365 21/00 326 (72) Inventor Keiji Kawamoto 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Satoshi Handa 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. F-term (reference) 2H003 BB11 CC05 EE12 2H005 AA01 AA06 AA08 AA15 AA21 CA04 CA07 CA08 CA13 CA14 CA15 DA06 DA07 EA05 EA06 EA07 FA07 FB01 2H034 CB01 2H077 AA37 AC04 AC16 AD02 AD06 AD13 AD17 AD18 AD23 AD24 AD31 AD36 AE04 BA03 EA11 EA16 FA01 FA12 FA19 FA22 FA22

Claims (45)

[Claims] 1. A dry toner containing at least a binder resin, a colorant and a wax, wherein a polycarbonate resin containing a halogen atom in a molecular structure is present on the surface of the toner particles. toner. 2. The dry toner according to claim 1, wherein the polycarbonate resin containing the halogen atom in the molecular structure has a main peak molecular weight by GPC of from 1,000 to 500,000. 3. The dry toner according to claim 1, wherein a main peak molecular weight by GPC of the polycarbonate resin containing the halogen atom in a molecular structure is in a range of 2,000 to 100,000. 4. The method according to claim 1, wherein the content of the polycarbonate resin containing the halogen atom in the molecular structure is 0.1 to 50% by weight based on the binder resin. A dry toner according to any one of the above. 5. 50 to 99.9% by weight of the binder resin
But, styrene-acrylic resin, polyester resin,
The dry toner according to any one of claims 1 to 4, wherein the dry toner is one or more resins selected from epoxy resins. 6. In a scattergram of the circle equivalent diameter-circularity based on the number of dry toners measured by a flow type particle image measuring apparatus, the circle equivalent number average particle diameter D1 (μ
m) is from 2 to 10 μm, the average circularity of the toner is 0.920 to 0.995, and the circularity standard deviation is 0.1 μm.
The dry toner according to any one of claims 1 to 5, wherein the dry toner is less than 060. 7. The circle-equivalent number average particle diameter D1 of the toner.
(Μm) is 2 to 10 μm, the average circularity of the toner is 0.950 to 0.995, and the circularity standard deviation is less than 0.050.
The dry toner according to any one of the above. 8. The circle-equivalent number average particle diameter D1 of the toner.
(Μm) is 2 to 10 μm, the average circularity of the toner is 0.970 to 0.995, and the circularity standard deviation is less than 0.040.
The dry toner according to any one of the above. 9. In a tomographic observation of the toner particles using a transmission electron microscope (TEM), the polycarbonate resin is present on the surface of the toner particles, and is obtained from a vinyl monomer inside. 9. A binder resin and a wax component to be present, wherein the wax component is dispersed in the binder resin in a substantially spherical and / or spindle-shaped island shape. Dry toner. 10. A charging step of applying a voltage to a charging member from outside to charge an electrostatic latent image carrier, and a latent image forming an electrostatic latent image on the charged electrostatic latent image carrier. A forming step, a developing step of developing the electrostatic image with dry toner to form a toner image on the electrostatic latent image carrier, and a transfer step of transferring the toner image on the electrostatic latent image carrier to a transfer material A fixing step of heating and fixing the toner image on the transfer material, wherein the dry toner contains at least a binder resin, a colorant and a wax, and contains a halogen atom in a molecular structure. An image forming method, wherein a polycarbonate resin is present on the surface of the toner particles. 11. In the developing step, the moving speed of the surface of the toner carrier in the developing area is 1.05 to 3.0 times the moving speed of the surface of the electrostatic latent image carrier. The image forming method according to claim 10, wherein the surface roughness Ra (μm) is 1.5 or less. 12. The image forming method according to claim 10, wherein a ferromagnetic metal blade is arranged at a minute interval so as to face the toner carrier. 13. The image forming method according to claim 10, wherein a blade made of an elastic material is brought into contact with the toner carrier. 14. An image according to claim 10, wherein said electrostatic latent image carrier and said toner carrier have a certain gap, and are developed while applying an alternating electric field. Forming method. 15. The charging step includes: applying a voltage to the charging member from outside by bringing the charging member into contact with the electrostatic latent image carrier;
11. The electrostatic latent image carrier is charged.
15. The image forming method according to any one of claims 1 to 14. 16. In a transfer step of electrostatically transferring the toner image on the electrostatic latent image carrier to a transfer material using a transfer device,
16. The image forming method according to claim 10, wherein the electrostatic latent image carrier and the transfer device are in contact with each other via the transfer material. 17. The method according to claim 10, wherein in the heat fixing step, the toner image is heat-fixed to the transfer material by a heat fixing device having no supply of an offset preventing liquid or having no fixing device cleaner. 17. The image forming method according to any one of claims 1 to 16. 18. The method according to claim 18, wherein the heating and fixing step comprises the steps of: fixing the toner image onto the transfer material by using a fixedly supported heating member and a pressing member which is in pressure contact with the heating member and closely adheres to the heating member via a film. The image forming method according to claim 10, wherein the image is fixed by heating. 19. An electrostatic latent image bearing member, wherein the untransferred residual toner on the electrostatic latent image carrier after the transfer is cleaned and collected, and the collected toner is supplied to a developing unit and held by the developing unit again. 19. The image forming method according to claim 10, further comprising a toner reuse mechanism for developing an electrostatic latent image on the carrier. 20. The polycarbonate resin containing a halogen atom in its molecular structure according to claim 10, wherein the main peak molecular weight by GPC is in the range of 1,000 to 500,000. Image forming method. 21. The polycarbonate-based resin containing a halogen atom in its molecular structure, wherein the main peak molecular weight by GPC of the polycarbonate-based resin is in the range of 2,000 to 100,000. Image forming method. 22. The method according to claim 10, wherein the content of the polycarbonate resin containing the halogen atom in the molecular structure is 0.1 to 50% by weight based on the binder resin. An image forming method according to any one of the above. 23. 50 to 99.9% by weight of the binder resin
But, styrene-acrylic resin, polyester resin,
23. The image forming method according to claim 10, wherein the resin is one or more resins selected from epoxy resins. 24. A circle-equivalent number-average particle diameter D1 of the toner in a scattergram of circularity-circularity based on the number of dry toners measured by a flow-type particle image measuring apparatus.
24. The toner according to claim 10, wherein (μm) is 2 to 10 μm, the average circularity of the toner is 0.920 to 0.995, and the circularity standard deviation is less than 0.060. The image forming method according to any one of the above. 25. The circle-equivalent number average particle diameter D1 of the toner.
24. The toner according to claim 10, wherein (μm) is 2 to 10 μm, the average circularity of the toner is 0.950 to 0.995, and the circularity standard deviation is less than 0.050. The image forming method according to any one of the above. 26. The circle-equivalent number average particle diameter D1 of the toner.
24. The toner according to claim 10, wherein (μm) is 2 to 10 μm, the average circularity of the toner is 0.970 to 0.995, and the circularity standard deviation is less than 0.040. The image forming method according to any one of the above. 27. In observing the tomographic plane of the toner particles using a transmission electron microscope (TEM), the polycarbonate resin is present on the surface of the toner particles, and the inside of the polycarbonate resin is obtained from a vinyl monomer. The binder resin and the wax component to be present are present, and the wax component is dispersed in the binder resin in a substantially spherical and / or spindle-shaped island shape. Image forming method. 28. A charging step of applying a voltage to a charging member from the outside to charge the electrostatic latent image carrier, and a latent image forming an electrostatic latent image on the charged electrostatic latent image carrier. A forming step, a developing step of developing the electrostatic image with dry toner to form a toner image on the electrostatic latent image carrier, and a first step of transferring the toner image on the electrostatic latent image carrier to the intermediate transfer body And a fixing step of heating and fixing the toner image on the transfer material, wherein the dry toner is An image forming method, wherein a polycarbonate resin containing at least a binder resin, a colorant and a wax and having a halogen atom in its molecular structure is present on the surface of the toner particles. 29. In the developing step, the moving speed of the surface of the toner carrier in the developing area is 1.05 to 3.0 times the moving speed of the surface of the electrostatic latent image carrier. 29. The image forming method according to claim 28, wherein the surface roughness Ra (μm) is 1.5 or less. 30. The image forming method according to claim 28, wherein a ferromagnetic metal blade is arranged at a minute interval so as to face the toner carrier. 31. The image forming method according to claim 28, wherein a blade made of an elastic body is brought into contact with the toner carrier. 32. The image according to claim 28, wherein the electrostatic latent image carrier and the toner carrier have a certain gap, and are developed while applying an alternating electric field. Forming method. 33. The charging step includes: bringing a charging member into contact with the electrostatic latent image carrier, applying a voltage to the charging member from the outside,
29. The electrostatic latent image carrier is charged.
33. The image forming method according to any one of the above items. 34. In a second transfer step of electrostatically transferring the toner image on the intermediate transfer member to a transfer material using a transfer device, the intermediate transfer member and the transfer device are interposed via the transfer material. The image forming method according to any one of claims 28 to 33, wherein the image forming apparatus is in contact with the image forming apparatus. 35. The method according to claim 28, wherein in the heat fixing step, the toner image is heat-fixed to the recording material by a heat fixing device having no supply of an offset preventing liquid or having no fixing device cleaner. 35. The image forming method according to any one of items 34 to 34. 36. The heating and fixing step, wherein a toner image is transferred onto a transfer material by a heating member fixed and supported, and a pressing member which opposes and presses the heating member and closely adheres to the heating member via a film. 35. The image forming method according to claim 28, wherein the image is fixed by heating. 37. An untransferred residual toner on the electrostatic latent image carrier after the transfer is cleaned and collected, and the collected toner is supplied to the developing unit and held again in the developing unit, and the electrostatic latent image is transferred to the developing unit. 37. The image forming method according to claim 28, further comprising a toner reuse mechanism for developing an electrostatic latent image on the carrier. 38. The polycarbonate according to claim 28, wherein the polycarbonate resin containing the halogen atom in the molecular structure has a main peak molecular weight determined by GPC in the range of 1,000 to 500,000. Image forming method. 39. The polycarbonate according to claim 28, wherein the polycarbonate-based resin containing a halogen atom in its molecular structure has a main peak molecular weight by GPC in the range of 2,000 to 100,000. Image forming method. 40. The method according to claim 28, wherein the content of the polycarbonate resin containing the halogen atom in the molecular structure is 0.1 to 50% by weight based on the binder resin. Or the image forming method described in 41. 50 to 99.9% by weight of the binder resin
But, styrene-acrylic resin, polyester resin,
41. The image forming method according to claim 28, wherein the resin is at least one resin selected from epoxy resins. 42. A circle-equivalent number average particle diameter D1 of the toner in a scattergram of circularity-circularity based on the number of dry toners measured by a flow-type particle image measuring apparatus.
42. The toner according to claim 28, wherein (μm) is 2 to 10 μm, the average circularity of the toner is 0.920 to 0.995, and the circularity standard deviation is less than 0.060. The image forming method according to any one of the above. 43. The circle-equivalent number average particle diameter D1 of the toner
42. The toner according to claim 28, wherein (μm) is 2 to 10 μm, the average circularity of the toner is 0.950 to 0.995, and the circularity standard deviation is less than 0.050. The image forming method according to any one of the above. 44. The circle-equivalent number average particle diameter D1 of the toner
42. The toner according to claim 28, wherein (μm) is 2 to 10 μm, the average circularity of the toner is 0.970 to 0.995, and the circularity standard deviation is less than 0.040. The image forming method according to any one of the above. 45. In a tomographic observation of the toner particles using a transmission electron microscope (TEM), the polycarbonate-based resin is present on the surface of the toner particles, and is obtained from a vinyl-based monomer therein. 45. The binder resin according to claim 28, wherein the binder resin and the wax component are present, and the wax component is dispersed in the binder resin in a substantially spherical and / or spindle-shaped island shape. Image forming method.