JP2000235277A - Dry toner and method for formation of image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a dry toner having excellent lubricating and cleaning properties which hardly causes melt sticking on a blade or a photoreceptor by allowing a siloxane-modified polycarbonate resin to be present on the surface of toner particles. SOLUTION: In the dry toner containing at least a binder resin, coloring agent and wax, a siloxane-modified polycarbonate resin is allowed to be present on the surface of the toner particles. In this method, it is required that at least a binder resin, coloring agent and wax component are incorporated and that the siloxane-modified polycarbonate resin is required to be prevent continuously or discontinuously on the surface of the toner particles. As for the siloxane- modified polycarbonate resin, for example, a siloxane-modified polycarbonate produced by the reaction of a siloxane-modified divalent phenol and carbonate precursor by a soln. method or fusing method, or a siloxane-modified divalent phenol, or a divalent phenol not modified with siloxane can be used.

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. . A full-color image is formed by fixing the transfer material having the four color toner images by the action of heat and pressure by a fixing roller.

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 this 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 such 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, a toner generally contains a binder resin, which is a thermoplastic resin, and a colorant as essential components, and various kinds of binders are used for the purpose of improving developability, fixability, storage stability, environmental stability, etc. of the toner. Methods for improving resins have been proposed.
For example, with respect to the toner obtained by the above polymerization method, a method of covering the outer shell of a resin having a relatively low glass transition temperature (Tg) with a resin having a relatively high Tg in order to achieve both low-temperature fixability and storage stability. It has been proposed (for example, JP-A-5-197203). However, in this case, a polar resin having a relatively high Tg, such as polyester, having a high hygroscopicity is often used. Even though both low-temperature fixability and storage stability can be achieved, the charge stability due to environmental fluctuations is not sufficient. In some cases, problems occurred.

On the other hand, 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. One means for improving the durability of the toner is to increase 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 the siloxane-modified polycarbonate-based resin can be suitably used, and the effect of impurities contained in the polycarbonate copolymer on the electrophotographic properties and the like is not described at all. Further, the publication discloses a method for producing a toner by a spray drying method and a pulverizing method in Examples.
There is no description at all regarding differences in transferability of the toner image coming from the shape of the obtained toner from the electrostatic image carrier to the transfer material, differences in charging uniformity, and the like.

JP-A-63-208863 discloses a method of using a polycarbonate terpolymer having a specific structure having a glass transition temperature of about 50 ° C. as a binder resin for 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. In addition, there is no description that the siloxane-modified polycarbonate-based resin can be suitably used, and the effect of impurities contained in the polycarbonate copolymer on the electrophotographic properties and the like is not described at all.

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 discloses 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 that a siloxane-modified polycarbonate-based resin can be suitably used or the shape of the toner.

Furthermore, Japanese Patent Publication No. 57-6585 discloses a tough polymer having a Tg or melting temperature (Tm) of more than about 50 ° C. and a number average molecular weight of 10,000 to 100,000, and a soft weight having a Tg of less than 20 ° C. A-B consisting of coalescence
A toner for pressure fixing using an A-type block copolymer as a binder resin is disclosed. An example of the publication describes a method for obtaining a toner using an ABA block copolymer composed of polydimethylsiloxane-bisphenol A polycarbonate-polydimethylsiloxane as a binder resin. If the toner is manufactured according to the publication, a toner suitable for pressure fixing can be obtained.However, the toner is designed for pressure fixing, and has a high molecular weight of the block copolymer and contains a wax component. Therefore, it is difficult to apply the present invention to a fixing device such as a hot roll fixing device in which a heating element and a toner come into contact with each other. Also,
In this publication, a method for producing a toner by a spray drying method is disclosed in Examples, but there is no description that a toner having a specific circularity is excellent in transferability and charging uniformity.

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.

Among various problems in the conventional technology for both sides of color, one of the most important issues is paper curl generated after fixing one side. 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 of 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, a full-color copying machine uses four photoconductors and a belt-shaped transfer belt, and develops an electrostatic latent image formed on each photoconductor 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 in 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 describes that a toner 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 the respective color toners be sufficiently mixed in the 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.

[0034]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a dry toner excellent in lubricity and cleaning properties and hardly fused to a blade or a photoreceptor, and an image forming method using the toner. Things.

[0035]

The present invention provides a dry toner containing at least a binder resin, a colorant and a wax, wherein a siloxane-modified polycarbonate resin is present on the surface of the toner particles. Dry toner.

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 by providing a siloxane-modified polycarbonate resin continuously or discontinuously on the surface of toner particles, excellent lubricity and cleaning properties can be obtained, and blades and photoreceptors can be used. It has been found that a toner that is extremely unlikely to be fused can be obtained, and the present invention has been completed.

[0038]

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.
Alternatively, it is essential that the toner particles exist discontinuously on the surface of the toner particles.

In the present invention, the siloxane is represented by the following general formula (I), and the siloxane-modified polycarbonate resin has a structure of the general formula (I) contained in at least a part of the polycarbonate resin. Is what you have.

[0040]

Embedded image [In the formula, n is an integer of 1 to 1000, and R ¹ and R ² each represent hydrogen, halogen, or an alkyl group or an aryl group which may have a substituent. ]

The siloxane-modified polycarbonate resin, which is an essential component in the present invention, has a repeating unit represented by the following general formula (II) in the molecular structure.

[0042]

Embedded image Wherein R ³ is an organic group. ]

The siloxane-modified polycarbonate resin represented by the general formula (II) has various structures. For example, a siloxane-modified dihydric phenol is reacted with a carbonate precursor by a solution method or a melting method. Known siloxane-modified polycarbonate, siloxane-modified dihydric phenol, non-siloxane-modified dihydric phenol, and any known copolymer produced by reacting with a carbonate precursor by a solution method or a melt method. Block copolymer polycarbonate produced by reacting polycarbonate, polycarbonate or polycarbonate oligomer with one-terminal or both-terminal reactive siloxane, a dihydric phenol and a carbonate precursor in the presence of a polymerization terminator containing siloxane in the molecular structure. React Such terminated siloxane-modified polycarbonate produced as an example.

As an example of the siloxane-modified dihydric phenol, the following general formulas (III) to (V)

[0045]

Embedded image Wherein, R ⁴ represents an organic group, hydrogen, halogen or an optionally substituted alkyl group or an aryl group containing a siloxane structure represented by the general formula (I), the R ⁴ is more In the above case, they may be the same or different, and m is a number from 0 to 4. And X is
A single bond, an organic group containing a siloxane structure represented by the general formula (I), an aliphatic hydrocarbon group or an aromatic hydrocarbon group which may have a halogen or a substituent, -S-, -SO-,
_{-SO 2 -, - O -,} - CO- bonds shows the like represented by the bond. However, at least one of R ^{4 and} X is an organic group having a siloxane structure represented by the general formula (I). ] And the like.

Examples of the dihydric phenol not modified with siloxane include the following general formulas (VI) to (VI).
II)

[0047]

Embedded image [Wherein, R ⁵ is a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic substituent. When a plurality of R ⁵ are present, they may be the same or different, and m is , 0-4. Then, Y represents a single bond, a halogen or an aliphatic substituted hydrocarbon group or an aromatic hydrocarbon group, -S -, - SO -, - SO 2 -, - O -, - CO-
Indicates a bond represented by a 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 the dihydric phenol represented by II) with a carbonate precursor such as phosgene or a carbonate compound, the siloxane-modified polycarbonate resin used in the present invention can be easily produced. That is, for example, in a solvent such as methylene chloride,
By reaction with siloxane-modified dihydric phenols, (if necessary) non-siloxane-modified dihydric phenols and carbonate precursors such as phosgene in the presence of known acid acceptors and molecular weight regulators, or It is prepared by transesterification with a siloxane-modified dihydric phenol, (optionally) a non-siloxane-modified dihydric phenol, and a carbonate precursor such as diphenyl carbonate.

There are various siloxane-modified dihydric phenols represented by the above general formulas (II) to (IV), and specific examples include the following general formulas (IX) to (IX).
(XIII)

[0050]

Embedded image

[0051]

Embedded image [Wherein, R ⁶ , R ⁷ , R ⁸ and R ⁹ each represent hydrogen, halogen or an aliphatic hydrocarbon group or an aromatic hydrocarbon group which may have a substituent, and these groups are the same. Or may be different. a is 1 to 1000,
b is a positive integer, c is an integer from 0 to 4, Z is hydrogen, halogen or an aliphatic hydrocarbon group which may have a substituent,
Represents an aromatic hydrocarbon group. These dihydric phenols may be used alone or in combination of two or more.

Further, there are various siloxane-unmodified dihydric phenols represented by the general formulas (VI) to (VIII), and 2,2-bis (4-hydroxyphenyl) propane [commonly known as bisphenol] A], 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-hydroxyphenyl) butane; 1,4-bis (4-hydroxyphenyl) butane 2,2-bis (4-hydroxyphenyl) pentane; 4-methyl-2,2-bis (4-hydroxyphenyl) pentane; 1,1-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; dihydroxyarylalkanes such as 1,1-bis (4-hydroxyphenyl) cyclodecane; bis (4-hydroxyphenyl) sulfone; bis (3,5-dimethyl-4) Dihydroxyarylsulfones such as -hydroxyphenyl) sulfone; bis (4-
Hydroxyphenyl) ether; dihydroxyaryl ethers such as bis (3,5-dimethyl-4-hydroxyphenyl) ether; 4,4′-dihydroxybenzophenone; 3,3 ′, 5,5′-tetramethyl-4,
Dihydroxy aryl ketones such as 4'-dihydroxybenzophenone; bis (4-hydroxyphenyl) sulfide; dihydroxy such as bis (3-methyl-4-hydroxyphenyl sulfide; bis (3,5-dimethyl-4-hydroxyphenyl) sulfide Aryl sulfides, dihydroxyaryl sulfoxides such as bis (4-hydroxyphenyl) sulfoxide, 4,
Dihydroxydiphenyls such as 4'-dihydroxydiphenyl;hydroquinone;solcinol; dihydroxybenzenes such as methylhydroquinone; 1,5-dihydroxynaphthalene; dihydroxynaphthalenes such as 2,6-dihydroxynaphthalene. Each of these dihydric phenols may be used alone,
Two or more kinds may be used in combination.

As described above, the siloxane-modified polycarbonate resin used in the present invention necessarily contains an organic group having a siloxane structure represented by the general formula (I) in its repeating unit. Not,
For example, a polymer having an organic group containing a siloxane structure only at the terminal of the polymer chain may be used by using a siloxane-modified polymerization terminator. The polymerization terminator that can be used at this time is not particularly limited, and examples thereof include a monohydric phenol represented by the following general formula.

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image [Wherein, n is an integer of 1 to 1000, w is an integer of 1 to 500, and (n + w) ≦ 1000. ]

In the present invention, a siloxane-modified polycarbonate-based resin can also be obtained by reacting a reactive siloxane with a polycarbonate having a reactive functional group in the molecular structure. Examples of the functional siloxane include any known amino-modified polydimethylsiloxane, epoxy-modified polydimethylsiloxane, carboxy-modified polydimethylsiloxane, carbinol-modified polydimethylsiloxane, (meth) acryl-modified polydimethylsiloxane, and mercapto-modified polydimethylsiloxane. Things can be used.

The siloxane-modified polycarbonate resin used in the present invention may be a homopolymer, a copolymer, or a blend. Further, the polyfunctional aromatic compound is converted to the above-mentioned dihydric phenol and / or
Alternatively, it may be a thermoplastic random branched polycarbonate resin obtained by reacting with a carbonate precursor.

In order to adjust the glass transition temperature and the viscoelasticity of the siloxane-modified polycarbonate resin, a part of the dihydric phenol is replaced with ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, Propylene glycol, 1,4
-Butanediol, neopentyl glycol, 1,4-
Bis (hydroxymethyl) cyclohexane, 1,4-bis (2-hydroxyethyl) benzene, 1,4-cyclohexanedimethanol, polyethylene glycol, propylene glycol, hydrogenated product of 2,2-bis (4-hydroxyphenyl) propane And its derivatives, 2,2
-Ethylene oxide adduct of bis (4-hydroxyphenyl) propane, propylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane, and polyhydric alcohols such as glycerin, trimethylolpropane, and pentaerythritol. Shaped modified polycarbonate resins are also preferably used. In this case, it is also 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. Also,
In the present invention, those obtained by modifying these polyhydric alcohols with siloxane may be used. In this case, the above-mentioned dihydric phenols may or may not contain a siloxane structure.

Further, in the present invention, as the siloxane-modified polycarbonate resin, the above-mentioned siloxane-modified polycarbonate and polystyrene, styrene- (meth) acryl copolymer, polyester, polyurethane,
Block copolymers with epoxy resins, polyolefins, polyamides, polysulfones, polycyanoaryl ethers, polyarylene sulfides, etc. and alkyl (meth)
It is also possible to use a graft-modified copolymer obtained by grafting acrylate, (meth) acrylic acid, maleic acid, styrene-based monomer and the like.

The molecular weight of the siloxane-modified polycarbonate resin used in the present invention is not particularly limited, but the peak molecular weight measured by gel permeation chromatography (GPC) described below is 1000 to 1000.
Those in the range of 500,000 are preferred, and more preferably 2,000 to 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 the siloxane-modified polycarbonate resin is present on the surface of the toner particles, and at least a part of the binder resin in the toner particles must be the siloxane-modified polycarbonate resin. It is. Although the binder resin may be a toner composed of only a siloxane-modified polycarbonate resin, as described above, in consideration of the adjustment of the viscoelasticity of the toner and the low-temperature fixability, the resin may be continuously or unfavorably formed. It is continuously present on the surface of the toner particles, and is 0.1% of the binder resin.
Preferably, about 50% by weight is a siloxane-modified polycarbonate resin. At this time, another resin is used as a binder resin together with the siloxane-modified polycarbonate resin.
0-99.9% by weight is used in combination. 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-based resin not modified with siloxane is used as a binder resin together with a siloxane-modified polycarbonate-based resin, the total amount thereof is preferably not more than 50% by weight of the total binder resin. When the content of the siloxane-modified polycarbonate resin 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.

Other resins used in combination with the siloxane-modified polycarbonate resin in the present invention include commonly used styrene- (meth) acrylic copolymers, polyester resins, epoxy resins, and styrene resins.
Various resins such as butadiene copolymer are exemplified. These resins may be produced by any known method. For example, styrene- (meth) acrylic copolymers can be obtained by polymerizing monomers for forming them. 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 the image, particularly, the development of a character image or a line pattern is improved. 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 fluctuations 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 need to maintain a sufficient toner coating amount 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 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. In the present invention, the flow type particle image measurement is used. The measurement was performed using an apparatus FPIA-1000 (manufactured by Toa Medical Electronics Co., Ltd.), and calculated using the following equation.

[0076]

(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.

[0080]

(Equation 2)

[0081]

[0082]

(Equation 3)

As a specific measuring 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 dispersing agent 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.

The shape of the toner particles was measured using the above-mentioned flow type particle image measuring apparatus, and the toner particle concentration at the time of measurement was 30%.
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.

[0086] These wax components showed a value of 40 to 40 when the temperature was raised 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 D3418-8”. 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 was used as a measurement sample, an empty pan was set as a control, and the measurement was 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. The black coloring agents include carbon black, magnetic materials, and the following yellow coloring agents / magenta 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 and perylene compounds. 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, it is hydrophobized by 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 the siloxane-modified polycarbonate resin is present on the surface of the toner particles. There are various methods for producing the toner of the present invention. For example, when the toner is produced by a pulverization method, a binder resin containing a siloxane-modified polycarbonate resin, a wax component, a colorant and / or
Alternatively, a magnetic substance, a charge control agent or other additives, etc. are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, melt-kneaded using a hot kneader such as a pressure kneader or an extruder, and solidified after cooling and solidification. Is impinged on the target mechanically or under a jet stream to pulverize 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 siloxane-modified polycarbonate resin), a wax component, a colorant and / or a magnetic substance, a charge control agent or other Using the additives and the like as raw materials, perform fine pulverization in the same manner as described above, and then attach fine-particle siloxane-modified polycarbonate-based resin to the surface of the pulverized particles using a mixer such as a Henschel mixer, and further perform the same as above. In addition, smoothing and sphering, classification, and toner formation of toner particles can be performed.

When a siloxane-modified polycarbonate resin is directly or continuously provided on the surface by a polymerization method, the siloxane-modified polycarbonate resin is added to the polymerization system. Kosho 3
JP-A-6-10231, JP-A-59-53856, JP-A-59-61842, a method for directly producing a toner by using a suspension polymerization method,
Typical examples include a dispersion polymerization method in which a toner is directly produced using an aqueous organic solvent in which the polymer obtained is soluble and insoluble in a polymer, or a soap-free polymerization method in which a toner is produced by directly polymerizing in the presence of a water-soluble polymerization initiator. The toner of the present invention can be obtained by the emulsion polymerization method or the like. Further, polymer particles containing no siloxane-modified polycarbonate-based resin are produced by a polymerization method, and then fine-particle siloxane-modified polycarbonate-based resin is adhered to the surface of the polymer particles, followed by smoothing and spheroidizing the toner particles. Can also be adopted. As another method, there is exemplified a method of atomizing a molten mixture containing a siloxane-modified polycarbonate resin into the air using a disk or a multi-fluid nozzle described in Japanese Patent Publication No. 56-13945 to obtain a spherical toner. You.

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, in a production method in which a pulverization method or a polymerization method is combined with smoothing and spheronization treatment of toner particles, and in a method of producing a toner in which a siloxane-modified polycarbonate resin is directly present on the surface of toner particles by a polymerization method, It is easy to keep the circularity and the circularity standard deviation in a desired range, and it can be said that this is a preferable manufacturing method. Further, a production method combining a polymerization method and a smoothing and spheroidizing treatment of toner particles, and a method for producing a toner in which a siloxane-modified polycarbonate-based resin is directly present on the surface of toner particles by a polymerization method, have a circularity or a circular shape. It is extremely easy to control the degree standard deviation to the desired range.
Observation of the tomographic surface of the toner using a transmission electron microscope (TEM) revealed that a siloxane-modified polycarbonate resin was present on the surface of the toner particles, and a binder resin and a wax obtained from a vinyl monomer were contained therein. Component is present and the wax component is substantially spherical and / or in the binder resin.
Or, since it is dispersed in the form of spindle-shaped islands, fluctuations in charging characteristics due to the environment are small, and a toner excellent in transferability, developability, low-temperature fixability, anti-blocking properties, and the like can be obtained. is there. Further, the method of producing a toner in which a siloxane-modified polycarbonate-based resin is directly present on the surface of a toner particle by a polymerization method uses, in addition to the above-described advantages, even a siloxane-modified polycarbonate-based resin having a high melting temperature, for example. Since the siloxane-modified polycarbonate resin may be used by dissolving it in the monomer composition to be used, it is easy as a production method,
In addition, there are many types of siloxane-modified polycarbonate-based resins 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 the toner particles in an epoxy resin curable at room temperature and then curing for 2 days in an atmosphere at 40 ° C. 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 to be described later were observed on a tomographic plane with a TEM, the toner particles (1) showed siloxane The modified polycarbonate resin was present on the surface of the toner particles (FIG. 6a), and in the case of toner particles (4), the siloxane-modified polycarbonate resin was discontinuously present on the surface of the toner (FIG. 6b). ). In the case of the toner particles (5), the siloxane-modified polycarbonate-based resin is continuously present on the surface of the toner, and a binder resin obtained from a vinyl-based monomer and a siloxane-modified polycarbonate-based resin are contained therein. And the presence of a wax component, and the wax component was observed to be substantially dispersed in the binder resin in the form of spherical and spindle-shaped islands (FIG. 6c).

When a polymerization method is used as a method for producing the 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 a direct polymerization method, examples of a 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 to be used is as follows.
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.

In the case where a direct polymerization method is used as a method for producing the toner used in the present invention, the following production methods are 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, water is usually added to 100 parts by weight of the monomer composition in water.
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 the siloxane-modified polycarbonate-based resin is present on the surface of the toner particles. It can be implemented using 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 siloxane-modified polycarbonate-based resin is present on the surface, contrast is obtained at that portion. Then, photoacoustic spectroscopy (PAS = Photoaco
By changing the scanning speed of the movable mirror using a conventional spectroscopy, the composition of the surface of the obtained toner particles can be determined by using an infrared absorption spectrum (IR) /
Analyze by PAS. Contrast is observed continuously or discontinuously on the toner particle surface by the TEM observation,
If the siloxane-modified polycarbonate-based resin is confirmed by the IR / PAS analysis, it can be determined that the siloxane-modified polycarbonate-based resin is present on the surface of the toner particles. In addition to IR / PAS, the composition analysis of the toner particle surface by combining Raman spectroscopy and the above PAS, ESCA (Electron Spectrosc)
opy for Chemical Analysis
There are various analysis means such as elemental analysis of the toner particle surface by s), 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.

The inorganic fine powder used in the present invention includes:
Examples thereof 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, a functional group for the purpose of hydrophobization and charge control, if necessary. 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 and / or. 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, it becomes difficult not only to reduce the thickness of the toner layer on the toner carrier but also to improve the image quality because 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 by using a surface roughness measuring device (Surfcoder SE-30H, manufactured by Kosaka Laboratory 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).

[0124]

(Equation 4)

As the toner carrier used in the present invention, for example, a cylindrical or belt-like member made of 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.

In the present invention, the surface moving speed of the toner carrier is set to be 1.05 to 3.
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. Also, when developing an image that requires a large amount of toner over a large 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 supplied by the supply member 22 onto the developing sleeve. 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. However, the toner is used in the developing method of the present invention. 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 onto 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.

Further, 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 easily fuses on the developing sleeve and the elastic blade. However, the toner used in the present invention has excellent releasability and stable triboelectricity. 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.

If the elastic body and the toner carrier are required to have durability, it is preferable that the elastic body and the resin or rubber are bonded to the sleeve contact portion or applied by coating.

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 serving as the regulating member, the supply roller serving 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.

A 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 source 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 of 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 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.

[0145]

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 and acrylic acid-n-
After dropping a mixture of 15 parts by weight of butyl and 1.5 parts by weight of di-tert-butyl peroxide, 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 was 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 was 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 700000, 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.

The siloxane-modified polycarbonate resin
Production Example 1 600 ml of an 8.8 w / v% aqueous sodium hydroxide solution
In addition, 102 g of 1,1-bis (4-hydroxyphenyl) cyclohexane and a dihydric phenol of the general formula (IX) (R ⁶ and R ⁷ are each a methyl group, a = 41, b = 3,
11.3 g of ortho bond at c = 0) and 0.1 g of hydrosulfite were added and dissolved. To this was added 360 ml of methylene chloride, 14 g of pt-butylphenol was added while stirring at 15 ° C., and then 53 g of phosgene was blown in over 60 minutes. After the completion of the blowing, the mixture was vigorously stirred to emulsify the reaction solution.
l of triethylamine was added, and the mixture was stirred for about 1 hour to carry out polymerization. The polymer solution was separated into an aqueous layer and an organic layer, the organic layer was neutralized with phosphoric acid, and the washing was repeated until the pH of the washing solution became neutral. Then, 470 ml of isopropanol was added to precipitate a polymer. The precipitate was filtered and dried to obtain a white powdery siloxane-modified polycarbonate resin (1).

When the siloxane-modified polycarbonate resin (1) was analyzed by GPC, the peak molecular weight was 7
000, the weight average molecular weight (Mw) was 8,000, and the number average molecular weight (Mn) was 2,000.

The siloxane-modified polycarbonate resin
Production Example 2 The above-mentioned siloxane-modified polycarbonate except that the dihydric phenol of the general formula (IX) is a para-bond with R ⁶ and R ⁷ each being a methyl group, a = 20, b = 2, c = 0. A siloxane-modified polycarbonate resin (2) was obtained in the same manner as in Production Example 1 of the resin.

When the siloxane-modified polycarbonate resin (2) was analyzed by GPC, the peak molecular weight was 5
000, the weight average molecular weight (Mw) was 6,500, and the number average molecular weight (Mn) was 1,700.

The siloxane-modified polycarbonate resin
Production Example 3 pt without using the dihydric phenol of the general formula (IX)
-Instead of butylphenol, the following structure

[0155]

Embedded image A siloxane-modified polycarbonate-based resin (3) was obtained in the same manner as in Production Example 1 of the siloxane-modified polycarbonate-based resin except that 64.0 g of the siloxane-modified polymerization terminator was used.

The siloxane-modified polycarbonate resin (3) was analyzed by GPC and found to have a peak molecular weight of 8
000, the weight average molecular weight (Mw) was 10,000, and the number average molecular weight (Mn) was 2600.

Example 1 100 parts by weight of binder resin (1) 8 parts by weight of carbon black (BET specific surface area = 114 m ² / g) 1.5 parts of negative charge control agent (azo acid-based iron complex) 1.5 4 parts by weight of low molecular weight polyethylene having a maximum endothermic peak of 107 ° 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 20 parts by weight of the finely powdered siloxane-modified polycarbonate (1) were dry-mixed with a Henschel mixer, and siloxane-modified polycarbonate resin ( The particles to which the fine powder of 1) was attached were obtained. 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 plane 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 siloxane-modified polycarbonate resin (1) was obtained, and it was confirmed that the siloxane-modified polycarbonate resin was continuously present on the surface of the particles.

100 parts by weight of the classified powder (1) and 2 parts by weight of hydrophobic silica fine powder (BET: 200 m ² / g) were dry-mixed with a Henschel mixer to obtain a toner (1) of the present invention. Further, 6 parts by weight of the toner (1) and 94 parts by weight of a resin-coated magnetic ferrite carrier (average diameter: 50 μm) were mixed to prepare a two-component developer (1) for magnetic brush development.

<Example 2> A classification powder (2) of the present invention was prepared in the same manner as in Example 1 except that the siloxane-modified polycarbonate resin (2) was used instead of the siloxane-modified polycarbonate resin (1). ), Toner (2)
And a developer (2) were prepared. Table 1 shows the analysis results of the classified powder (2).

<Example 3> A classified powder (3) of the present invention was prepared in the same manner as in Example 1 except that the siloxane-modified polycarbonate resin (3) was used instead of the siloxane-modified polycarbonate resin (1). ), Toner (3)
And a developer (3) were prepared. Table 1 shows the analysis results of the classified powder (3).

Example 4 Example 1 was repeated except that 5 parts by weight of the siloxane-modified polycarbonate resin (1) was used.
In the same manner as in the above, a classification powder (4), a toner (4) and a developer (4) of the present invention were prepared. 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 two-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 dispersoids: 85 parts by weight of styrene 15 parts by weight of n-butyl acrylate 0.3 parts 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 treated with an attritor (manufactured by Mitsui Miike Kako) 3
4 parts by weight of siloxane-modified polycarbonate resin (1) 3 parts by weight of paraffin wax having a maximum endothermic peak of 70 ° C. 10 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) The resulting mixture was heated to 60 ° C. to prepare a polymerizable monomer composition.

Next, the polymerizable monomer composition was charged into the aqueous dispersion medium, and the mixture was stirred for 15 minutes under a nitrogen atmosphere at a liquid temperature of 60 ° C. while maintaining the rotation speed of a high-speed stirrer at 12,000 rpm. The hydrophilic monomer composition was granulated. Then, the suspension was changed to a propeller type stirring blade and maintained at 60 ° 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 subjected to vacuum drying for 12 hours, and the weight of the residue was measured to calculate the THF-insoluble matter. The result was 20% by weight based on the polymer particles.

Example 6 The polymer particles of the present invention were prepared in the same manner as in Example 5 except that the siloxane-modified polycarbonate resin (2) was used instead of the siloxane-modified polycarbonate resin (1). 6) and Toner (6) were prepared. Table 1 shows the analysis results of the polymer particles (6).

Example 7 The polymer particles of the present invention were prepared in the same manner as in Example 5 except that the siloxane-modified polycarbonate resin (3) was used instead of the siloxane-modified polycarbonate resin (1). 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 A classifying powder for comparison (9) and a toner for comparison (9) were prepared in the same manner as in Example 1 except that the siloxane-modified polycarbonate resin was not used. Table 1 shows the analysis results of the classified powder (9).

Comparative Example 2 Comparative polymer particles (10) and comparative toner (10) were prepared in the same manner as in Example 5 except that the siloxane-modified polycarbonate resin was not used. Table 1 shows the analysis results of the polymer particles (10).

[0175]

[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, the developing device is set in the image forming apparatus, and the room temperature and the normal humidity (25
C., 60% RH), in a continuous mode in a single color (that is, a mode in which the consumption of toner is promoted without stopping the developing device) at a printout speed of 16 sheets / min (A4 size). A printout test was performed. Then, the obtained printout image was evaluated for items described below. Further, the fused state of the toner on the blade and the photosensitive member was also observed.

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.

[0180]

[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 rotated at a predetermined peripheral speed (process speed) in the direction of an arrow.

The photosensitive drum 1 rotates during the rotation process so that the primary charger 2
, 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 device (yellow developing device 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 between 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.

Thereafter, 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 superimposed on the intermediate transfer belt 40 and transferred to correspond to the target color image. Thus, a combined color toner image is formed.

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.

The primary transfer bias for transferring the 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 first to third color toner images 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 changed with respect to 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 normal temperature and normal humidity (25 ° C, 60% RH), 12 sheets / min (A
(4 sizes) at a printout speed of 10,000 printouts. Then, the obtained printout image was evaluated for items described below. Further, the fused state of the toner on the blade and the photosensitive member was also observed.

The results of the above evaluation are shown in Table 3.

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.

[0198]

[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 270 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 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 180 ° C. The total pressure between the sponge pressure roller 33 is 8 kg, the nip between the pressure roller and the film is 7 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 normal temperature and normal humidity (25 ° C, 60% RH) environment, 1
At a printout speed of 2 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 when restarting. Mode), a printout test of 10,000 sheets was performed. Then, the obtained printout image was evaluated for items described below. Further, the fused state of the toner on the blade and the photosensitive member was also observed.

Table 4 shows the evaluation results.

[0203]

[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 obtained printout image was evaluated for the items described below, and the state of fusion of the toner to the blade and the photosensitive member was also observed.

As a result, all the items were good.

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

[Evaluation of Printout Image] <1> Image Density Printout was performed using plain paper for copying machines (75 g / m ² ), and the 10,000th printout image was evaluated by image density. The image density was measured by using a "Macbeth reflection densitometer" (manufactured by Macbeth Co., Ltd.) with respect to a printout image of a white background portion having a document density of 0.00. A: 1.40 or more B: 1.35 or more and less than 1.40 C: 1.00 or more and less than 1.35 D: less than 1.00

<2> Fog The 1000th sheet was printed out on ordinary paper for copying machines (75 g / m ² ) at room temperature and normal humidity, and the 1000th sheet was measured with a “Reflectometer” (manufactured by Tokyo Denshoku Co., Ltd.). The fog density (%) was calculated from the difference between the whiteness of the white portion of the printout image and the whiteness of the transfer paper, and the image fog was evaluated. 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

<3> Fusion of Toner to Blade and Photoconductor After the printout test, the occurrence of fusion of the toner to the blade edge portion and the surface of the photoconductor drum was visually evaluated. A: Not generated B: Slight fusion is observed C: Fused D: Remarkably fused

[0211]

According to the present invention, excellent lubricating properties and cleaning properties are maintained, high developing performance is maintained even when a large number of images are formed, and no adverse effects such as fusion to a blade or a photoreceptor occur. An industrially excellent dry toner and image forming method can be provided.

[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 Fixing Device 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

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 15/08 504 G03G 15/20 102 2H077 15/20 102 9/08 325 21/10 331 333 365 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 F-term in Canon Inc. (Ref.) AD17 AD18 AD23 AD24 AD36 AE04 DA20 EA13 EA14 FA13 FA19 FA22

Claims (45)

[Claims] 1. A dry toner containing at least a binder resin, a colorant and a wax, wherein a siloxane-modified polycarbonate resin is present on the surface of the toner particles. 2. The siloxane-modified polycarbonate resin has a main peak molecular weight determined by GPC of from 1,000 to 1,000.
2. The method according to claim 1, wherein the number is in the range of 500,000.
4. The dry toner according to item 1. 3. The siloxane-modified polycarbonate resin has a main peak molecular weight by GPC of 2,000 to
2. The method according to claim 1, wherein the number is in the range of 100,000.
4. The dry toner according to item 1. 4. The dry toner according to claim 1, wherein the content of the siloxane-modified polycarbonate resin is 0.1 to 50% by weight based on the binder resin. 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 a circle-based circularity-circularity based on the number of dry toners measured by a flow-type particle image measuring device, a circle-equivalent number-average particle diameter D1 (μ)
m) is 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 number 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.
6. The toner according to claim 1, 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 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 And 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 the siloxane-modified polycarbonate resin contains the toner particles. An image forming method characterized by being present on the surface of an image. 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: bringing a charging member into contact with the electrostatic latent image carrier, applying a voltage to the charging member from the outside,
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 siloxane-modified polycarbonate resin having a main peak molecular weight by GPC of 1,000.
The image forming method according to any one of claims 10 to 19, wherein the value is in the range of -500,000. 21. The siloxane-modified polycarbonate resin having a main peak molecular weight by GPC of 2,000.
The image forming method according to any one of claims 10 to 19, wherein the value is in the range of 100 to 100,000. 22. The content of the siloxane-modified polycarbonate-based resin is 0.1 to 50 based on the binder resin.
22. The image forming method according to claim 10, wherein the content is% by weight. 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 at least one resin 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 A transfer step of transferring the toner image on the intermediate transfer body to a transfer material, and a fixing step of heating and fixing the toner image on the transfer material. And a binder resin, a colorant and a wax, and wherein a siloxane-modified polycarbonate resin 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 main peak molecular weight of the siloxane-modified polycarbonate resin measured by GPC is 1000.
The image forming method according to any one of claims 28 to 37, wherein the value is in the range of -500,000. 39. The siloxane-modified polycarbonate resin having a main peak molecular weight by GPC of 2,000.
The image forming method according to any one of claims 28 to 37, wherein the value is in the range of 100000 to 100000. 40. The content of the siloxane-modified polycarbonate resin is 0.1 to 50 based on the binder resin.
The image forming method according to any one of claims 28 to 39, wherein the content is% by weight. 41. 50 to 99.9% by weight of the binder resin
But, styrene-acrylic resin, polyester resin,
The image forming method according to any one of claims 28 to 40, wherein one or more resins selected from epoxy resins are used. 42. A circle-equivalent number average particle diameter D1 of the toner in a scattergram of circular equivalent-circularity based on the number of dry toners measured by a flow-type particle image measuring apparatus.
43. 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 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 is obtained from a vinyl monomer inside. The binder resin to be used and a 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.