JPH11149182A - Toner and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a toner for developing an electrostatic charge image having high durability and high transfer efficiency by specifying the amt. of a component having repeating units of polycarbonate resin in the structure contained in a component having a specified mol.wt. or below. SOLUTION: The toner contains a bonding resin contg. 0.1-50.0wt.% polycarbonate resin and 50.0-99.9 wt.% the other resin based on the weight of the bonding resin. A component having repeating units of the polycarbonate resin in the structure contained in a component having a mol.wt. of <=1,000 in the mol.wt. distribution of a THF-soluble component by gel permeation chromatography is contained in the toner by <=15.0 wt.% based on the weight of the toner. The toner has high durability and high transfer efficiency.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for forming a toner image in an image forming method such as electrophotography, electrostatic printing, magnetic recording and toner jet, and an image forming method using the toner. Things. Especially,
The present invention relates to a toner for developing an electrostatic image, which is used in a fixing method of heating and fixing a visible image formed by a toner to a recording material, 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.
It is known in a number of ways, as described in Japanese Patent Publication No. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means, and then the latent image is developed using toner, and if necessary, using direct or indirect means. After a toner image is transferred to a recording material such as paper, the image is fixed by heating, pressing, or solvent vapor to obtain a copy. The untransferred toner remaining on the photoreceptor without being transferred is cleaned by various methods, and the above steps are repeated.

An example of a general method for forming a full-color image will be described. A photosensitive member (electrostatic latent image carrier) of a photosensitive drum is uniformly charged by a primary charger and modulated by a magenta image signal of a document. Image exposure is performed by the laser light thus formed, 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, thereby forming a magenta toner image. Next, the magenta toner image developed on the photosensitive drum by the transfer charger is transferred to the conveyed recording material using direct or indirect means.

After the development of the electrostatic latent image, the photosensitive drum is neutralized by a neutralizing charger, cleaned by cleaning means, charged again by a primary charger, and similarly charged with cyan toner. The image formation and the transfer of the cyan toner image to the recording material to which the above-described magenta toner image has been transferred are performed, and the same operation is sequentially performed for the yellow color and the black color to transfer the four color toner images to the recording material. The recording material having the four color toner images is fixed by the action of heat and pressure by a fixing roller to form a full color image.

In recent years, such an apparatus has begun to be used not only as a copy machine for office work for copying an original document, but also as a laser beam printer as an output of a computer or a personal copy for an individual. .

In addition to the fields represented by such laser beam printers and personal copies, the development of plain paper facsimile machines using a basic engine is also rapidly developing.

[0007] For this reason, miniaturization, weight reduction, high speed, high image quality, and high reliability have been strictly pursued, and machines have been constructed with simpler elements in various aspects. It has become to. As a result, the performance required of the toner has become 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 along with various copying needs, and further higher image quality and higher resolution 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.

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 a plurality of toner layers of magenta, cyan, yellow, and black 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 the toner from adhering to the surface of the fixing roller, for example, the roller surface is coated with a material having excellent releasability with respect to the toner such as silicone rubber or fluorine resin, and furthermore, the surface is prevented from being offset, and In order to prevent the surface of the roller from being fatigued, the surface of the roller is coated with a thin film of a liquid having high releasability such as silicone oil or fluorine oil. However, although this method is extremely effective in preventing toner offset,
Since a device for supplying the liquid for preventing offset is required,
In addition to the problem that the fixing device becomes complicated, this oil application causes delamination between the layers constituting the fixing roller and consequently shortens the service life of the fixing roller. Follow me.

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

The incorporation of a wax as a release agent in a toner is disclosed in, for example, Japanese Patent Publication No. 52-3304, Japanese Patent Publication No. 52-3305, and Japanese Patent Publication No. 57-52574.

JP-A-3-50559 and JP-A-2-50559
No. 79860, JP-A-1-109359, JP-A-62-14166, JP-A-61-27355
No. 4, JP-A-61-94062, JP-A-61-94062
-138259, JP-A-60-252361, JP-A-60-252360 and JP-A-60-252.
Japanese Patent No. 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, but deteriorate the anti-blocking property, and are used in copying machines and the like. When the toner is exposed to heat due to a rise in temperature in the apparatus, or when the toner is left for a long period of time, the wax migrates to the surface of the toner to deteriorate the developability.

Accordingly, there has been great expectation for the development of a new toner with respect to the above problems.

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. It is possible to form a so-called core / shell structure in which a non-polar component does not easily exist in the surface layer portion and is easily present in the surface layer portion which is an interface with the polymer.

The toner produced by the polymerization method can achieve both low-temperature fixing properties, anti-blocking properties and high-temperature offset resistance, and contradictory performance, by incorporating a wax component as a release agent. High temperature offset can be prevented without applying a mold release agent.

The toner for developing an electrostatic image generally contains a binder resin, which is a thermoplastic resin, and a colorant as essential components. Various toners are used for improving the developing property, fixing property, storage stability and environmental stability of the toner. A method for improving the binder resin has been proposed. For example, regarding the toner obtained by the above polymerization method,
In order to achieve both low-temperature fixability and storage stability, a method has been devised in which the outer shell of a resin having a relatively low glass transition temperature (Tg) is covered with a resin having a relatively high Tg (see, for example, JP-A-5-197203). No.). However, the resin having a relatively high Tg used in this case is often a polar resin having a hygroscopic property such as polyester, and even though both low-temperature fixability and storage stability can be achieved, charging due to environmental fluctuations is possible. In some cases, there was a problem with stability.

Further, when a large number of toners are printed out, the external additive is buried in the toner surface and deteriorates.
It is generally known that an image is adversely affected. 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 (weathering resistance), etc., polycarbonate is generally widely known and used for various purposes. Regarding toners, 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. . Furthermore, there is no description on the influence of impurities contained in the polycarbonate copolymer on the electrophotographic properties. Further, in this publication, a method for producing a toner by a spray drying method and a pulverization method is disclosed in Examples, but the toner image coming from the shape of the obtained toner is transferred from the electrostatic image carrier to the transfer material. There is no description about the difference in transferability or the difference in charge uniformity.

JP-A-63-208863 discloses a method in which a polycarbonate terpolymer having a specific structure having a glass transition temperature of about 50 ° C. is used as a binder resin for a flash fixing toner. . 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 the polycarbonate terpolymer having a low glass transition temperature is used as the binder resin, the blocking resistance and the durability have not reached a satisfactory level,
Further, since the toner is designed for flash fixing, it is difficult to apply the fixing device to a heating device such as a hot roll fixing device in which the toner is in contact with a heating element.

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. Highly cross-linked or linear binder resin,
Alternatively, it is described that a polycarbonate copolymer can be used as 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.

Japanese Patent Application Laid-Open No. 5-273772 discloses an image forming method using a developing roller in which a large number of minute closed electric fields are formed in the vicinity of the surface, and the Izod impact value of the toner formed into a plate is 2 to 500 kg / cm / cm. It is disclosed that the use of a certain toner can prevent filming on a developing roller.
It is described that a mixture of an acrylic resin and a polycarbonate can be used as a binder resin.

However, there is no specific description of polycarbonate in this publication, and in the molecular weight distribution measured by GPC, for components having a repeating unit of polycarbonate contained in components having a molecular weight of 1,000 or less, and for the molecular weight of the polycarbonate. Has not been considered.

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

As described above, in recent years, there has been a great demand from users for copying originals on both sides or duplexing originals on one side, and for that purpose, a two-sided image having higher image quality and higher reliability is required. Have been.

One of the most important issues is paper curl that occurs after fixing one surface, among various adverse effects in the conventional technology for both sides of color. If the paper curl is large, the conveyance 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 toner transferred to the transfer material is small. is there. This requires an improvement in the coloring power of the toner itself. Since an image that passes through the fixing device twice is generated on both sides, further improvement in high-temperature offset resistance is also required.

Conventionally, in a full-color copying machine, an electrostatic latent image formed on each photoconductor using four photoconductors and a belt-shaped transfer belt is developed using cyan, magenta, yellow, and black toners. After transferring the transfer material between the belt and the transfer member and transferring it between straight passes, a full-color image is formed, or the transfer material is wound around the surface of the transfer member facing the photoreceptor by electrostatic force or mechanical action such as a gripper. A method of performing a development-transfer process four times to obtain a full-color image as a result is generally used.

In recent years, there has been an increasing need to develop a variety of materials, such as thick paper, cards, and postcards, as well as ordinary paper and overhead projector films (OHP) as full-color transfer materials. In the above-described method using four photoconductors, the transfer material is transported straight, so that the application range to various transfer materials is wide. However, it is necessary to accurately superimpose a plurality of toner images on a predetermined transfer material position. There is a problem that it is difficult to obtain a high-quality image with good reproducibility even with a slight difference in registration, and there is a problem that a transfer material transport mechanism is complicated and reliability and the number of parts are increased. Furthermore, when using a thick weighed paper by the method of adsorbing and winding the transfer material on the surface of the transfer member, poor adhesion of the rear end of the transfer material occurs 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 when transferring the toner to the transfer material, so that the system is made of polyurethane in which a conductivity-imparting material is dispersed. The resulting surface layer locally causes a breakdown, and unfavorable image disturbance occurs in a halftone image with a small amount of toner applied. Further, in a high-humidity environment in which the relative humidity exceeds 60% RH, the transfer current leaks as the resistance of the transfer material is reduced, and a transfer failure is likely to occur. Is 40% RH
Even in the following low-humidity environment, transfer failure may occur due to 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, in this publication, a sticky intermediate transfer member is used.
It only states that toner of 0 μm or less can be efficiently transferred. Usually, in a system using an intermediate transfer member, it is necessary to transfer the 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. In comparison, it is necessary to increase the toner transfer efficiency 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 ordinary toner is used, the surface of the photoconductor or the surface of the photoconductor 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 is used. The fusion of the toner and the filming on the surface of the intermediate transfer member occur to deteriorate the transfer efficiency, and in the case of full color, the toner images of four colors are not transferred uniformly, so that problems in color unevenness and color balance are likely to occur, It has been difficult to stably output a high-quality full-color image.

Further, as a toner mounted on a normal full-color copying machine, it is necessary that each color toner is sufficiently mixed in a fixing process, and therefore, improvement of 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 color toner as compared with the black toner. For the ordinary black toner, a release agent having relatively high crystallinity represented by polyethylene wax or polypropylene wax is used in order to improve the 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. Therefore, the silicone oil is uniformly applied to the heat fixing roller without adding a release agent as a component of the color toner, thereby improving the high-temperature offset resistance. 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-59-15739
JP-A-59-5046 and JP-A-59-5046 do not propose a device for the toner or the intermediate transfer member in this regard.

[0037]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner and an image forming method which solve the conventional problems.

An object of the present invention is to provide a toner for developing an electrostatic image having high durability and transfer efficiency, and an image forming method using the toner.

An object of the present invention is to provide a toner for developing an electrostatic image, which has a small variation in charging characteristics due to the environment and has a high transfer efficiency, and an image forming method using the toner.

[0040]

The above object is achieved by the following constitution of the present invention.

The present invention relates to a toner containing at least a binder resin, a colorant and a wax, wherein the binder resin comprises:
The toner contains 0.1 to 50.0% by weight of a polycarbonate resin and 50.0 to 99.9% by weight of a resin other than the polycarbonate resin based on the weight of the binder resin, and the toner is made of tetrahydrofuran (THF). 14. In a molecular weight distribution by gel permeation chromatography (GPC) of a dissolved component, a component having a repeating unit of a polycarbonate-based resin contained in a component having a molecular weight of 1,000 or less in its structure, based on the weight of the toner. 0
The present invention relates to a toner characterized in that the toner is contained in an amount of not more than% by weight.

According to the present invention, there is provided a charging step of externally applying a voltage to a charging member to charge an electrostatic latent image carrier; a latent image forming step of forming an electrostatic latent image on the charged electrostatic latent image carrier. A developing step of developing the electrostatic latent image formed on the latent image carrier with toner to form a toner image; and transferring the toner image formed on the electrostatic latent image carrier via an intermediate transfer member or An image forming method comprising: a transfer step of transferring the toner image onto the recording material without intervention; and a fixing step of heating and fixing the toner image transferred onto the recording material to the recording material. And a binder, and the binder resin contains 0.1 to 50.0% by weight of a polycarbonate-based resin and 50.0 to 99.9% of a resin other than the polycarbonate-based resin based on the weight of the binder resin. % By weight, and the toner Rahidorofuran (THF) soluble matter by gel permeation chromatography (GPC)
Wherein the component having a repeating unit of the polycarbonate resin contained in the component having a molecular weight of 1000 or less is contained in the structure in an amount of 15.0% by weight or less based on the weight of the toner. Image forming method.

As a result of intensive studies, the present inventors have used a polycarbonate resin as a part of the binder resin, and
By controlling the content of a specific compound contained in the toner, it has been found that a toner having good durability and transfer efficiency can be obtained, and the present invention has been completed.

[0044]

BEST MODE FOR CARRYING OUT THE INVENTION The toner according to the present invention comprises at least a binder resin, a colorant, and a wax component, and it is essential that a polycarbonate resin is contained as the binder resin.

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

[0046]

[Outside 1] [Wherein, R represents an organic group. ]

The general formula (I) has various structures. For example, any known polycarbonate produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method may be used. The following general formula (II) can be mentioned as an example.

[0048]

[Outside 2] [In the formula, R ² is a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic substituent. When a plurality of R ² are present, they may be the same or different, and m is a number of 0 to 4, Z is a single bond, an aliphatic hydrocarbon group, an aromatic substituent, -S -, - SO -, - SO 2 -, - O- or -C
The bond represented by O- is shown. A polymer having a repeating unit having a structure represented by the following formula:

Although various polycarbonate resins can be used, the polycarbonate resins generally have the general formula (III) to
(V)

[0050]

[Outside 3] [In the formula, R ² is a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic substituent. When a plurality of R ² are present, they may be the same or different, and m is a number of 0 to 4, Z is a single bond, an aliphatic hydrocarbon group, an aromatic substituent, -S -, - SO -, - SO 2 -, - O- or -C
The bond represented by O- is shown. And a polycarbonate precursor such as a phosgene or carbonate compound.

That is, for example, by reacting a dihydric phenol with a carbonate precursor such as phosgene in a solvent such as methylene chloride in the presence of a known acid acceptor or molecular weight regulator, or by reacting a dihydric phenol with diphenyl It is produced by a transesterification reaction with a carbonate precursor such as carbonate.

There are various dihydric phenols represented by the general formulas (III) to (V).
In addition to 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) Nonan,
Dihydroxyarylalkanes such as 1,10-bis (4-hydroxyphenyl) decane and 1,1-bis (4-hydroxyphenyl) cyclodecane; bis (4-hydroxyphenyl) sulfone and bis (3,5-dimethyl-4) Dihydroxyaryl sulfones such as -hydroxyphenyl) sulfone; dihydroxyaryl ethers such as bis (4-hydroxyphenyl) ether and bis (3,5-dimethyl-4-hydroxyphenyl) ether; 4,4'-dihydroxybenzophenone and Dihydroxyaryl ketones such as 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybenzophenol; bis (4-hydroxyphenyl) sulfide,
Dihydroxyaryl sulfides such as bis (3-methyl-4-hydroxyphenyl) sulfide and bis (3,5-dimethyl-4-hydroxyphenyl) sulfide; dihydroxyaryl sulfoxides such as bis (4-hydroxyphenyl) sulfoxide; Dihydroxydiphenyls such as 4,4'-dihydroxydiphenyl; dihydroxybenzenes such as hydroquinone, solcinol and methylhydroquinone; and dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene and 2,6-dihydroxynaphthalene. These dihydric phenols may be used alone or in combination of two or more.

Examples of the carbonate compound include diaryl carbonates such as diphenyl carbonate; and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

As the polycarbonate resin used in the present invention, a homopolymer using one of these dihydric phenols, a copolymer using two or more of these dihydric phenols, or a blended product is used. Further, it may be a thermoplastic random branched polycarbonate resin obtained by reacting a polyfunctional aromatic compound with the above-mentioned dihydric phenol and / or carbonate precursor.

In order to adjust the glass transition temperature and the viscoelasticity of the polycarbonate resin, a part of the above dihydric phenol is replaced with ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol,
1,3-propylene glycol, 1,4-butanediol, neopentyglycol, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (2-hydroxyethyl) benzene, 1,4-cyclohexanedimethanol, Modified polycarbonate in the form of polyethylene glycol, propylene glycol, hydrogenated bisphenol A and its derivatives, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, polyhydric alcohols such as glycerin, trimethylolpropane and pentaerythritol A system resin is also preferably used. In this case, it is possible to produce by the above-mentioned method by simply substituting a part of the dihydric phenol, but as an example of another production method, dihydric phenol and aliphatic or aromatic bischloroformate Is reacted in a methylene chloride solvent using pyridine as a catalyst. Of course, synthesis by other production methods is also possible.

Further, in the present invention, as the polycarbonate resin, the above-mentioned polycarbonate and polystyrene, styrene- (meth) acryl copolymer, polyester, polyurethane, epoxy resin, polyolefin,
Block copolymers with monomers to match other polymers such as polyamides, polysulfones, polycyanoaryl ethers, polyarylene sulfides and alkyl (meth) acrylate monomers, (meth) acrylate monomers, maleate monomers, or It is also possible to use a graft-modified copolymer obtained by grafting a styrene monomer.

The toner according to the present invention has a THF soluble content of G
In the molecular weight distribution by PC, it is essential that the content of the component having the repeating unit of the polycarbonate resin contained in the component having a molecular weight of 1000 or less in the structure is 15.0% by weight or less based on the toner. It is.

In general, the kind of impurities contained in the polycarbonate resin differs depending on the kind of the polycarbonate resin and the production method, and the raw materials, by-products, by-products and decomposition products of the polycarbonate resin are used. There are various compounds such as, polymerization catalysts, polymerization terminators, polymerization solvents and antioxidants. In one example, chlorinated aliphatic and aromatic hydrocarbons (eg, dichloromethane), phosgene, phenol, t-butylphenol,
Organic amines, sodium chloride, aromatic compounds having two or more hydroxyl groups in one molecule (for example, 2,2-bis (3-
A dihydric phenol used as a monomer of a polycarbonate resin such as methyl-4-hydroxyphenyl) propane; an aliphatic compound having two or more hydroxyl groups in one molecule (for example, 1,4-butanediol; Diols used as monomers of the polycarbonate resin, polycarbonate oligomers, compounds in which a compound having two or more hydroxyl groups in one molecule and a polymerization terminator are ester-bonded via carbonic acid (for example, dihydric phenol and p
A compound in which tertiary butylphenol is ester-bonded via carbonic acid) mono- and / or diformates of an aromatic compound having two or more hydroxyl groups in one molecule (for example, phenylene bischloroformate); There are mono- and / or diformates (for example, ethylene bischloroformate), diaryl carbonate (for example, diphenyl carbonate) and dialkyl carbonate (for example, dimethyl carbonate) of an aliphatic compound having two or more hydroxyl groups.

Among these impurities, compounds having a low boiling point such as dichloromethane and water-soluble compounds such as sodium chloride can be easily removed in the production process of the polycarbonate-based resin. Usually remains in the polycarbonate resin in many cases. Among these high-boiling low-molecular-weight impurities, monomers having two or more hydroxyl groups in one molecule (for example, dihydric phenols) used in the production of the polycarbonate resin and repeating units of the polycarbonate resin Containing a large amount of a component having a molecular weight of 1,000 or less in the structure (a compound in which a polymerization stopper such as a polycarbonate oligomer or a compound having two or more hydroxyl groups in one molecule and a monohydric phenol is ester-bonded via carbonic acid) is used. When manufactured, the charge amount of the toner decreases (image density decreases and fog increases), the environmental stability of the toner decreases, coloring due to oxidation of phenolic impurities by air (discoloration of the image), impurity odor during fixing, and impurity crystals Of binder resin in melt kneading process, which is one of the toner production processes in the pulverization method, Unexpected crosslinking, a polymerization inhibiting function of phenolic impurities during the production of the polymerization toner, it causes various serious problem was found by analysis and image evaluation of the toner made by the present inventors.

The toner of the present invention has a molecular weight distribution of 100
The content of the component contained in the structure of the repeating unit of the polycarbonate resin contained in the component of 0 or less (that is, the component having a molecular weight of 1000 or less having the repeating unit of the polycarbonate resin in the structure) is defined as To 15.0% by weight or less. As mentioned above,
Compounds that adversely affect various performance and characteristics of toner
Not only the component having a molecular weight of 1000 or less having a repeating unit of the polycarbonate resin in the structure, but also applies to the monomer of the polycarbonate resin, the content of the monomer, the repeating unit of the polycarbonate resin in the structure Is proportional to the content of the component having a molecular weight of 1000 or less, and if the content of the component having a molecular weight of 1000 or less having a repeating unit of the polycarbonate resin is set to 15.0% by weight or less based on the toner, It has been found from various studies by the present inventors that the above problems do not occur. Further, in order to further enhance the performance and characteristics of the toner, the content of a component having a molecular weight of 1000 or less and having a repeating unit of a polycarbonate resin is adjusted to 1 content.
The content is more preferably not more than 0.0% by weight, particularly preferably 5.0% by weight. Of course, even if various analyzes of the toner are performed, a polycarbonate resin purified by reprecipitation so that a component having a molecular weight of 1000 or less having a repeating unit of the polycarbonate resin in the structure is not detected at all is used as a binder resin. Is most desirable.

In the case where the toner contains more than 15.0% by weight of a component having a repeating unit of a polycarbonate resin contained in a component having a molecular weight of 1000 or less in a molecular weight distribution measured by GPC, the durability of the toner increases. , The storage stability is deteriorated, and the image density change when a large number of sheets are printed out is increased. In addition, the transfer efficiency fluctuates and the fog increases due to environmental changes.

In the present invention, in the molecular weight distribution of the THF-soluble component by GPC, the qualitative and quantitative analysis of the component having a repeating unit of the polycarbonate resin contained in the component having a molecular weight of 1,000 or less in the structure is performed by various methods. Can be implemented. For example, a toner is analyzed for its magnetic resonance spectrum ( ¹ H-NMR, ¹³ C-NMR), infrared absorption spectrum (IR), Raman spectrum, ultraviolet absorption spectrum (UV), mass spectrum (MS), etc., and elemental analysis. , GPC, gas chromatography (GC), liquid chromatography (HPLC), or other chemical analysis. If analysis is difficult with the toner itself, the toner may be subjected to Soxhlet extraction with a solvent that dissolves the binder resin, such as tetrahydrofuran or toluene, and the filtrate may be concentrated by an evaporator, followed by the above analysis. Furthermore, a sample in which components having a molecular weight of 1000 or less are dispersed by liquid chromatography or GPC,
Various analysis means can be employed, such as performing the above analysis on a sample extracted with a single or mixed solvent. These analysis means can be used alone or in combination as needed.

Further, components having a molecular weight of 1000 or less in the toner are separated by GPC, and the separated components are completely hydrolyzed with, for example, an alkali, and then subjected to ¹ H-NMR, ¹³ C-NMR.
-There is also a method of performing qualitative and quantitative analysis of monomers having two or more hydroxyl groups in one molecule (for example, dihydric phenols) used in the production of the polycarbonate resin by analytical means such as NMR and IR. . At this time, the content of the monomer determined is such that a polycarbonate oligomer having a molecular weight of 1000 or less or a compound having two or more hydroxyl groups in one molecule and a polymerization terminator such as a monohydric phenol are ester-bonded via carbonic acid. It is the sum of the monomer produced by hydrolysis of the compound and the residual monomer (at the time of polymerization) originally contained in the polycarbonate resin. The value obtained by converting the content of this sum into the content of the polycarbonate oligomer (after separately qualifying and quantifying the polymerization terminator) and the content of the compound in which the monomer and the polymerization terminator are ester-bonded via carbonic acid is obtained. , 15.0% by weight based on toner
If it is less than or equal to 1, as a result, the content of the compound having a GPC molecular weight of 1000 or less having a repeating unit of a polycarbonate resin in the structure cannot exceed 15.0% by weight, and is one of the methods for analyzing a toner according to the present invention. It can be adopted as a means.

The molecular weight distribution of the THF-soluble component of the toner 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) at room temperature for 24 hours is used.
The solution is filtered through a μm solvent-resistant membrane filter to obtain a sample solution, which is measured under the following conditions. The sample was prepared in such a manner that the concentration of the component soluble in THF was 0.4 to 0.6% by weight.
Adjust the amount of THF so that Apparatus: High-speed GPC HLC8120 GPC (manufactured by Tosoh Corporation) Column: Shodex KF-801, 802, 80
7, 804, 805, 806, 807 (manufactured by 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, a standard polystyrene resin (TSK Standard Polystyrene F-850, F-450, F-288, F-288, manufactured by Tosoh Corporation) was used.
128, F-80, F-40, F-20, F-10, F
-4, F-2, F-1, A-5000, A-2500,
A-1000, A-500) are used.

The molecular weight of the polycarbonate resin used in the present invention is not particularly limited, but the molecular weight distribution measured by gel permeation chromatography (GPC) described below has a peak molecular weight of 100.
It is preferably in the range of 0 to 500,000, and more preferably in the range of 2000 to 100,000. When the peak molecular weight is lower than 1,000, the charging characteristics may be adversely affected, and the molecular weight is 5,000.
If it is higher than 00, 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, the content of the polycarbonate resin is 0.1 to 50 based on the weight of the binder resin.
% By weight, preferably 0.2 to 40% by weight, more preferably 0.5 to 30% by weight, and the content of another resin used in combination with the polycarbonate resin as a binder resin is preferably 60 to 99.8. % By weight, more preferably 70%
It is preferably from 9 to 99.5% by weight and from 50 to 99.9% by weight. The toner is used in combination with a high molecular weight resin or a crosslinked resin having a peak molecular weight exceeding 5,000,000 and a peak molecular weight of 100.
By using a low molecular weight resin of about 0 to 50,000 together as a binder resin, the viscoelasticity of the toner is designed,
Prevention of low-temperature and high-temperature offsets is preferably performed. 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, which causes a problem. Is generated. 0.1% by weight of polycarbonate resin in binder resin
When it is less than the above, the excellent durability and transfer efficiency, which are the effects of the present invention, cannot be achieved.

Other resins used in combination with the polycarbonate resin in the present invention include generally used styrene-acrylic resins, polyester resins, styrene-butadiene resins and epoxy resins.
In particular, styrene-acrylic resins, polyester resins and epoxy resins are preferably used. These resins may be produced by any known method. For example, styrene-acrylic resins can be obtained by polymerizing monomers for forming them. Specifically, styrene, o (m-, p-)-methylstyrene, m
Styrene monomers such as (p-)-ethylstyrene,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, ( (Meth) acrylate monomers such as behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate, butadiene, isoprene, cyclohexene, Ene monomers such as (meth) acrylonitrile and acrylamide are preferably used. These may be used alone or generally in the published Polymer Handbook, 2nd edition III-p 139-192 (Jo
hn Wiley & Sons) is used by appropriately mixing monomers so that the theoretical glass transition temperature (Tg) thereof is 40 to 75 ° C. Theoretical glass transition temperature is 40 ℃
If the temperature is lower than 75 ° C., problems tend to occur in terms of storage stability and durability stability of the toner. On the other hand, if the temperature 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 property of each color toner at the time of fixing is reduced, and the color reproducibility is poor.
This is not preferable because the transparency of the HP image is reduced.

In the present invention, it is more preferable that the polycarbonate resin is present on the surface of the toner particles, because the durability of the toner can be further improved.

In the toner of the present invention, it is preferable that the polycarbonate resin is present on the surface of the toner particles. However, confirmation of the presence of the polycarbonate resin on the surface of the toner particles is carried out using any analytical means. be able to. As an example, first, a tomographic surface of the toner particles is observed by a TEM to check whether or not the surface of the toner particles has a contrast. When a polycarbonate-based resin is present on the surface, a contrast is obtained at that portion. Then, photoacoustic spectroscopy (PAS = Photoa
cosmetic spectroscopy)
By changing the scanning speed of the movable mirror, the composition of the surface of the obtained toner particles can be determined by infrared absorption spectrum (IR).
Analyze by / PAS. If the contrast is observed continuously or discontinuously on the surface of the toner particles by the TEM observation, and the polycarbonate-based resin is confirmed by IR / PAS analysis, the polycarbonate-based resin is present on the surface of the toner particles. Can be determined. IR / PAS
In addition, the composition analysis of the toner particle surface combining Raman spectroscopy and the above PAS, ESCA (ElectronS
pectroscopy for Chemical
Analysis), elemental analysis of the toner particle surface,
There are various analysis means such as 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.

When the toner of the present invention is produced by the polymerization method described later, the molecular weight distribution of the obtained toner particles in the THF
Has a main peak in the region of 10,000, and has a weight average molecular weight (M
w) and the number average molecular weight (Mn) ratio (Mw / Mn) 2-3
It is preferred to have 00.

The toner according to the present invention has a shape factor SF-1 measured by an image analyzer of 100 to 160, and
The value of the shape factor SF-2 is preferably from 100 to 140, and more preferably the value of the shape factor SF-1 is from 100 to 140, and the value of the shape factor SF-2 is from 100 to 120. Further, it is particularly preferable that the value of (SF-2) / (SF-1) is 1.0 or less.

In the present invention, SF-1 indicating the shape factor is used.
Means, for example, FE-SEM (S-800) manufactured by Hitachi, Ltd.
A sample of 100 toner images magnified to 500 times using a camera is sampled at random, and the image information is transmitted through an interface to, for example, an image analyzer (Luzex manufactured by Nicole).
III) is introduced and analyzed, and a value calculated by the following equation is defined as a shape factor SF-1.

[0074]

[Outside 4] [Where MXLNG represents the absolute maximum length of the toner, and
Shows the projected area of the EA toner].

Further, the shape factor SF-2 refers to a value calculated by the following equation.

[0076]

[Outside 5] [Where PERI indicates the circumference of the toner and AREA indicates the projected area of the toner].

The shape coefficient SF-1 indicates the degree of roundness of the toner, and the shape coefficient SF-2 indicates the degree of unevenness of the toner.

Conventionally, toner shape factors SF-1 and S
When F-2 is small, cleaning failure is likely to occur, or the external additive is likely to be buried in the toner surface when used for a long period of time, and as a result, image quality is often deteriorated. . However, in the present invention, since 0.1 to 50% by weight of the binder resin is a polycarbonate resin, the durability of the toner is very good, and as a result, it is possible to prevent image quality deterioration. is there. When SF-1 exceeds 160, the shape of the toner becomes indefinite. Therefore, when the transfer from the electrostatic image bearing member to the transfer material, from the electrostatic image bearing member to the intermediate transfer member, and from the intermediate transfer member to the transfer material, It is not preferable because the transfer efficiency of the toner image may be lowered. If SF-2 exceeds 140, the charge distribution of the toner becomes broad, and the toner surface is liable to be crushed in the developing device, which may cause a reduction in image density and image fog.

In order to increase the transfer efficiency of the toner image, the shape factor SF-2 of the toner is 100 to 140,
The value of (SF-1) / (SF-2) is preferably 1.0 or less. The shape factor SF-2 of the toner exceeds 140 (S
When the value of (F-1) / (SF-2) exceeds 1.0, the surface of the toner is not smooth, and the toner has many irregularities. At the time of transfer and at the time of transfer from the intermediate transfer member to the transfer material, the transfer efficiency tends to decrease.

In particular, the above tendency becomes obvious when a full-color copying machine that develops / transfers a plurality of toner images is used. That is, in the generation of a full-color image, it is difficult to uniformly transfer the toner images of four colors. Further, when an intermediate transfer member is used, problems are likely to occur in terms of color unevenness and color balance. It is difficult to output stably.

Further, when ordinary irregular toner is used, the gap between the photosensitive member and the cleaning member, between the intermediate transfer member and the cleaning member, and / or between the photosensitive member and the intermediate transfer member is reduced. In some cases, toner fusion or filming may occur on the surface of the photoreceptor or the surface of the intermediate transfer member due to force or rubbing force, which may hinder matching with the image forming apparatus.

In the present invention, an intermediate transfer member can be provided to correspond to various kinds of transfer materials. In this case, since the transfer step is performed substantially twice, the transfer efficiency is significantly reduced, which causes a problem that the use efficiency of the toner is reduced. In digital full-color copiers and printers, color image documents are pre-filtered by B (blue) filters and G (green) filters.
After color separation using a filter and an R (red) filter, a dot latent image of 20 to 70 μm is formed on the photoreceptor, and Y
It is necessary to reproduce a multicolor image faithful to a document by using the primary color mixing action by using the respective color toners of (yellow) toner, M (magenta) toner, C (cyan) toner, and B (black) toner. At this time, since a large amount of Y toner, M toner, C toner, and B toner is applied on the photoreceptor or the intermediate transfer member in accordance with the color information of the document or the CRT, each color used in the present invention is used. The toner is required to have extremely high transferability, and in order to realize the transferability, toner particles having a shape factor SF-1 and SF-2 of the toner satisfying the above conditions are preferable.

In order to faithfully develop minute latent image dots for higher image quality, the toner has a weight average diameter of 2 μm to 2 μm.
It is 10 μm, preferably 2 μm to 9 μm, more preferably 4 μm to 8 μm, and the coefficient of variation (A) in the number distribution is preferably 35% or less. In the case of the toner having a weight average diameter of less than 2 μm, a large amount of toner remains untransferred on a photoreceptor or an intermediate transfer member due to a decrease in transfer efficiency, and further, it is likely to cause non-uniform unevenness of an image due to fogging or poor transfer. Is not preferred as the toner used in When the weight average diameter of the toner exceeds 10 μm,
Fusing to members such as the photoreceptor surface and an intermediate transfer material is likely to occur. When the variation coefficient in the number distribution of the toner exceeds 35%, the tendency is further enhanced.

The particle size distribution of the toner can be measured by various methods. In the present invention, the measurement was performed using a Coulter counter.

For example, a Coulter counter TA-II type (manufactured by Coulter) is used as a measuring device, and an interface (manufactured by Nikkaki) for outputting a number distribution and a volume distribution and a personal computer are maintained.
Prepare an aqueous solution of about 1% NaCl using graded sodium chloride. For example, ISOTON II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, 0.1 to 5 ml of a surfactant (preferably an alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and the measurement sample is further added to 2 to 20 ml.
Add mg. The electrolytic solution in which the sample was suspended was subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and as an aperture of, for example, 100 μm,
Using an m aperture, the particle size distribution of the particles of 2 to 40 μm based on the number is measured, and the values according to the present invention are determined.

The variation coefficient A in the toner number distribution is calculated from the following equation.

Coefficient of variation A = [S / D ₁ ] × 100 [where S represents a standard deviation value in the number distribution of toner particles, and D ₁ represents the number average particle diameter of toner particles (μm)]
Is shown).

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, higher fatty acids and their metal salts, higher fatty alcohols, higher fatty esters, fatty amide waxes, ketones, Hydrogenated castor oil and derivatives thereof, vegetable waxes, animal waxes, mineral waxes, petrolactam. Derivatives include oxides, block copolymers with vinyl monomers, and graft-modified products.

These wax components were found to be 40 to 40% at the time of temperature rise in a DSC curve measured by a differential scanning calorimeter.
It has a maximum endothermic peak in the region of 130 ° C, preferably 50 to 100 ° 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 the toner is directly obtained by a polymerization method by performing granulation / polymerization in an aqueous medium, if the maximum endothermic peak temperature is high, a problem such as precipitation of a wax component mainly during granulation is not preferred.

The maximum endothermic peak temperature of the wax component is measured according to “ASTM D 3418-8”. For the measurement, for example, DSC-7 manufactured by PerkinElmer is used. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the heat quantity correction uses the heat of fusion of indium. An aluminum pan was used as a measurement sample, an empty pan was set as a control, and the temperature was raised from 10 ° C. to 180 ° C. at a rate of 10 ° C./min to perform measurement.

In the present invention, the addition amount of these wax components is not particularly limited, but is generally preferably 0.1 to 50% by weight, more preferably 0.5 to 0.5% by weight, based on the toner.
~ 30% by weight is preferred. The content of the wax component is 0.
When the amount is less than 1% by weight, the effect of suppressing offset is hardly sufficiently exhibited, and when the amount is more than 50% by weight, long-term storability is reduced, and dispersibility of other toner materials is reduced. Degradation may occur.

The coloring agents used in the present invention include the following yellow coloring agents, magenta coloring agents and cyan coloring agents. As black coloring agents, carbon black, magnetic substances or the following yellow coloring agents / magenta coloring agents / A mixture of a cyan colorant and a black color is used.

Examples of the yellow colorant include condensed azo compounds, isoindolinone compounds, anthraquinone compounds,
A compound represented by an azo metal complex, a methine compound or an allylamide compound 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 and 180 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 can be used particularly preferably.

These colorants can be used alone or as a mixture or in the form of a solid solution. The colorant is 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 oxide such as ferrite, iron, cobalt, nickel or a metal such as these or aluminum, cobalt, copper, lead, magnesium, tin,
Alloys with metals such as zinc, antimony, beryllium, bismuth, cadmium, 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 can be exemplified.

These magnetic materials have an average particle size of 2 μm or less, preferably about 0.1 to 0.5 μm. The amount of the magnetic substance contained in the toner particles is preferably 20 to 200 parts by weight, particularly preferably 40 to 1 part by weight, per 100 parts by weight of the resin.
50 parts by weight. The magnetic characteristics when 10K Oersted is applied are as follows: coercive force (Hc) 20-300 Oersted, saturation magnetization (σs) 50-200 emu / g, remanent magnetization (σr)
A magnetic material of 2 to 20 emu / g is preferred.

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 soluble matter in an aqueous dispersion medium is particularly preferable. Specific compounds include:
Metal compounds of aromatic carboxylic acids such as salicylic acid, naphthoic acid and dicarboxylic acid as negative charge control agents; Metal salts or metal complexes of azo dyes or azo pigments; High molecular type having sulfonic acid or carboxylic acid groups in side chains Compounds; boron compounds; urea compounds; silicon compounds; 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 contained in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the resin in the toner. 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, and 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.

Various methods can be used for producing the toner according to the present invention. For example, when the toner is produced by a pulverization method, a binder resin containing a polycarbonate resin, a wax component, a colorant and / or a magnetic substance, A charge control agent or other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, and are melt-kneaded using a hot kneader such as a pressure kneader or an extruder.
After cooling and solidification, the solid is made to strike the target mechanically or under a jet stream to pulverize the solid to a desired toner particle size.
Thereafter, smoothing and sphering of the toner particles are performed as necessary. Next, the particle size distribution is sharpened through a classification process. Further, the toner of the present invention can be obtained by sufficiently mixing the classified powder with a fluidizing agent such as fine silica particles and a mixer such as a Henschel mixer.
When the production method by the above-mentioned pulverization method is adopted, a polycarbonate resin and another resin are dissolved in an organic solvent such as xylene (if necessary, heated), mixed uniformly, and then the binder resin mixture from which the solvent is removed is used as a raw material. When it is used, even if it is a polycarbonate resin having a high glass transition temperature, the dispersion in the toner becomes good, which is a particularly preferable production method.

Further, as another method for producing a toner, there is a method in which an ultrafine powdered polycarbonate resin is added to a classifying powder together with a fluidizing agent and mixed well to fix the polycarbonate resin on the toner surface. in this case,
The binder resin in the classified powder may contain a polycarbonate resin or may not contain a polycarbonate resin at all. Further, after fixing, the toner particles may be subjected to a smoothing and spheroidizing treatment.

Further, when the toner of the present invention is produced by a polymerization method, a polycarbonate resin is added to a polymerization system, and JP-B-36-10231 and JP-A-59-5 are disclosed.
No. 3,856, JP-A-59-61842, a method of directly producing a toner by using a suspension polymerization method, an aqueous organic solvent in which the obtained polymer is soluble and insoluble in the monomer. The toner of the present invention can be obtained by a dispersion polymerization method for producing a toner directly using a solvent or an emulsion polymerization method represented by a soap-free polymerization method for producing a toner by directly polymerizing in the presence of a water-soluble polymerization initiator. A method of producing polymer particles containing no polycarbonate-based resin by a polymerization method, and then attaching a fine-particle polycarbonate-based resin to the surface of the polymer particles, and optionally performing a smoothing and spheroidizing treatment of the particles. Can be adopted. As another method, there is exemplified a method described in Japanese Patent Publication No. 56-13945, in which a toner raw material mixture containing a polycarbonate resin is atomized into air using a disk or a multi-fluid nozzle to obtain a spherical toner.

Among the toner production methods described above, the melt spray method is capable of keeping the SF-1 value, which is the spherical coefficient of the toner particles measured by Luzex, in the range of 100 to 160, but the particle size of the obtained toner particles is small. Distribution tends to be wide. On the other hand, in the dispersion polymerization method, the obtained toner particles have an extremely sharp particle size distribution.However, the selection of materials to be used is narrow, and the use of an organic solvent requires a manufacturing apparatus from the viewpoint of waste solvent treatment and solvent flammability. It is complicated and easy to be complicated. The emulsion polymerization method has an advantage that the particle size distribution of the toner particles is relatively uniform, but generally the particle size of the produced particles is very fine, and it is difficult to use the toner particles as they are. 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, the production method by smoothing and spheroidizing the toner particles and the production method by the polymerization method
The value of F-1 is 100-160, and the value of SF-2 is 100-
It is easy to fall within the range of 140, which can be said to be a preferable manufacturing method.

In particular, a production method in which a polymerization method is combined with a smoothing and sphering treatment of toner particles and a method in which a polycarbonate resin is directly produced on the surface of toner particles by a polymerization method are SF-1. Value of 100 to
140, the value of SF-2 is 100 to 120, (SF-2)
/ (SF-1) is easily controlled to 1.0 or less. Further, in the observation of the tomographic surface of the toner using a transmission electron microscope (TEM), the polycarbonate-based resin adheres to the surface of the toner particles. And a binder resin and a wax component obtained from a vinyl monomer are present therein, and the wax component is substantially spherical and / or in the binder resin.
In addition, since it is dispersed in the form of spindle-shaped islands, fluctuations in charging characteristics due to the environment are small, and transferability, developability, low-temperature fixability,
This is a more preferable production method because a toner having excellent blocking resistance can be obtained.

The method for producing a toner in which a polycarbonate resin is present directly on the surface of toner particles by a polymerization method is not limited to the above-mentioned advantages. Since the polycarbonate resin may be used by dissolving it in the body composition, the production method is easy, and there are many types of polycarbonate resins that can be used, which is a particularly preferable production method.

The polycarbonate resin contained in the toner of the present invention may be contained in any shape and state in the toner, and may be in a state of being dissolved in another binder resin or in a state of phase separation. It may be. For example, when the polycarbonate resin is melt-kneaded with the other binder resin by the above-mentioned pulverization method, the polycarbonate resin does not necessarily have to be melted in the melt-kneading step, and the melted kneading resin is not required to be melted. May be dispersed. In such a case, the polycarbonate resin in the toner is dispersed in another binder resin used in combination. If the polycarbonate resin and other binder resin are previously melt-mixed uniformly using an organic solvent such as xylene, the problem is that the polycarbonate resin is finely dispersed in the other resin, or in some cases, is compatibilized. However, if such a homogenizing operation is not performed and the polycarbonate resin powder and other binder resin are kneaded and kneaded at a temperature lower than the melting temperature of the polycarbonate resin, the polycarbonate resin powder Is dispersed in the toner. For example, a polycarbonate resin finely pulverized to 1 μm or less, preferably 0.5 μm or less is preferably used.

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 the same in an atmosphere at 40 ° C. for 2 days. Is stained using ruthenium tetroxide and, if necessary, osmium tetroxide, and then a flaky sample is cut out using a microtome provided with diamond teeth, and the tomographic plane of the toner is observed using a transmission electron microscope. In the present invention, it is preferable to use a ruthenium tetroxide dyeing method in order to obtain a contrast between the materials by utilizing a slight difference in crystallinity between the wax component to be used and the binder resin constituting the outer shell. Figure 1 shows a typical example
a, 1b and 1c.

The toner particles (13), (15) and (17) obtained in Examples 12, 14 and 16 described below
Observation of the tomographic plane by EM revealed that in the case of the toner particles (13), the polycarbonate resin was present on the surface of the toner particles (FIG. 1a), and in the case of the toner particles (15), they were discontinuous. A polycarbonate resin was present on the surface of the toner (FIG. 1b). The toner particles (1
In the case of 7), the polycarbonate-based resin is continuously present on the surface of the toner, and the binder resin, the polycarbonate-based resin and the wax component obtained from the vinyl-based monomer are present therein. It was observed that the components were dispersed substantially in spherical and spindle-shaped islands in the binder resin (FIG. 1c).

When a polymerization method is used as a toner production method, 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 having a protective colloid action. Predetermined toner particles can be obtained by controlling the mechanical conditions (for example, the peripheral speed of the rotor, the number of passes, the stirring conditions such as the shape of the stirring blade, and the shape of the container), or the solid content concentration in the aqueous solution.

When a toner is produced by the direct polymerization method, for example, 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 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.

In order to control 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 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 and alumina. As organic compounds,
Polyvinyl alcohol, gelatin, methylcellulose,
Methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salts and starch. 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.

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

When the direct polymerization method is used as the 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, usually, 30 parts of water is added to 100 parts by weight of the monomer composition.
It is preferable to use 0 to 3000 parts by weight as the dispersion medium.

The toner of the present invention has a binder resin content of 0.1 to 5%.
It is essential that 0% by weight is a polycarbonate resin, but qualitative and quantitative analysis of the polycarbonate resin can be carried out by various methods. For example, the toner is subjected to the magnetic resonance spectrum ( ¹ H-NMR, ¹³ C-NM
R), infrared absorption spectrum (IR), Raman spectrum, ultraviolet absorption spectrum (UV), mass spectrum (M
It may be analyzed by various methods such as spectrum analysis, elemental analysis, and other chemical analysis as in S). If the analysis is difficult with the toner itself, the toner may be subjected to Soxhlet extraction with a solvent that dissolves the binder resin such as tetrahydrofuran or toluene, the filtrate may be concentrated with an evaporator, and the above analysis may be performed. Furthermore, various analysis means can be adopted, such as performing the above analysis on a sample collected by GPC or a sample separated and extracted with a single or mixed solvent. These analysis means can be used alone or in combination as needed.

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

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

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

Other additives include lubricants such as Teflon, zinc stearate, and polyvinylidene fluoride (in particular, polyvinylidene fluoride); abrasives such as cerium oxide, silicon carbide, and strontium titanate; Strontium acid is preferred); cake ring agent;
And a conductivity improver such as carbon black, zinc oxide, antimony oxide and tin oxide; and a developability improver such as white fine particles and black fine particles having a polarity opposite to that of the toner particles.

In the present invention, in the case of a toner produced by stirring and mixing the inorganic fine particles and other additives with the toner particles, the measurement of various physical properties of the toner particles can be performed by measuring these inorganic fine particles and other additives. This can be performed using the toner particles after removing the additives. The method for removing these inorganic fine particles and other additives is not particularly limited. For example, the method can be carried out by washing the toner with water as follows.

The toner is added to water to which a surfactant such as sodium dodecylbenzenesulfonate has been added, and the mixture is sufficiently stirred and mixed. By this operation, inorganic fine particles having a relatively large particle size and other additives are released from the toner, and the toner particles and the inorganic fine particles and other additives are separately dispersed in water. Next, the toner particles are isolated from the mixed dispersion.
As an isolation method, for example, by performing a filtration operation using a filter paper having an appropriate aperture, separation can be performed as a solution containing toner particles on the filter paper and an inorganic fine particle and other additives in the filtrate. As another isolation method, a method of isolating toner particles by wet classification of the mixed dispersion may be employed.

In the present invention, the toner can be used as a one-component developer or as a two-component developer in combination with a carrier. Examples of the carrier include those in which iron powder, magnetite powder, ferrite powder, glass beads, and magnetic powder are dispersed in a resin. These carriers may be coated on the surface with a resin if necessary, and as the resin used in this case, a fluorine-containing resin, a phenol resin, a styrene resin, an acrylic resin, a styrene-acryl copolymer, Polyolefin resins, silicone resins and the like can be mentioned. These coating resins may be used alone or in combination of two or more. Good results are obtained when the mixing ratio of the toner and the carrier is 1 to 15% by weight, preferably 2 to 13% by weight, as the toner concentration in the developer.

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.

In the apparatus system shown in FIG. 2, developers having a cyan toner and a developer having a magenta toner are respectively provided to the developing machines 4-1, 4-2, 4-3, and 4-4.
A developer having a yellow toner and a developer having a black toner are introduced, and an electrostatic charge image formed on an electrostatic latent image carrier (for example, a photosensitive drum) 1 by a magnetic brush development method or a non-magnetic-component method is used. After development, toner images of each color are formed on the photosensitive drum 1.

The toner of the present invention can be mixed with a magnetic carrier and developed using, for example, a two-component developing system as shown in FIG. Specifically, the magnetic brush is applied to the photosensitive drum 1 while applying an alternating electric field.
It is preferable to carry out development in a state in which the film is in contact with No. 3.
Developer carrier (developing sleeve) 11 and photosensitive drum 13
(S-D distance) B of 100 to 1000 [mu] m is favorable for preventing carrier adhesion and improving dot reproducibility. If it is smaller than 100 μm, the supply of the developer tends to be insufficient, and the image density becomes low.
If m exceeds m, the lines of magnetic force from the magnet S1 are widened and the density of the magnetic brush is reduced, so that dot reproducibility is poor, the force for restraining the carrier is weakened, and carrier adhesion is likely to occur.

The voltage between the peaks of the alternating electric field (Vpp) is
Preferably, the voltage is 500 to 5000 V, and the frequency (f) is preferably 500 to 10000 Hz, more preferably 500 to 3000 Hz, and each can be appropriately selected and used for the process. In this case, a triangle, a rectangular wave, a sine wave, or a waveform with a changed duty ratio can be selected and used as the waveform. If the peak-to-peak voltage is lower than 500 V, it may be difficult to obtain a sufficient image density, and it may not be possible to satisfactorily collect fog toner in the non-image area. If the peak-to-peak voltage exceeds 5000 V, a magnetic brush may be encountered, disturbing the electrostatic image and causing image degradation.

When the frequency (f) is lower than 500 Hz, although it is related to the process speed, the charge may be injected into the carrier, so that the image quality may be deteriorated due to the adhesion of the carrier or the disturbance of the latent image. Frequency (f) 10000
If the frequency exceeds 100 Hz, the toner cannot follow the electric field, and the image quality is likely to deteriorate.

By using a two-component developer having a well-charged toner, the fog removal voltage (Vback)
And the primary charge of the photoconductor can be reduced, so that the life of the photoconductor can be extended. Vbac
k is preferably 150 V or less, more preferably 100 V or less, depending on the developing system.

As the contrast potential, 200 V to 500 V is preferably used so that a sufficient image density can be obtained.

In order to obtain a sufficient image density, achieve excellent dot reproducibility, and perform development without carrier adhesion, the contact width (developing nip C) of the magnetic brush on the developing sleeve 11 with the photosensitive drum 13 is preferably set. 3 to 8 mm. If the developing nip C is smaller than 3 mm, it is difficult to sufficiently satisfy a sufficient image density and dot reproducibility,
If the width is larger than 8 mm, packing of the developer occurs to stop the operation of the machine, and it is difficult to sufficiently suppress the adhesion of the carrier. As a method of adjusting the development nip,
The nip width is appropriately adjusted by adjusting the distance A between the developer regulating member 18 and the developing sleeve 11 or adjusting the distance B between the developing sleeve 11 and the photosensitive drum 13.

In the output of a full-color image in which halftone is particularly important, three or more developing units for magenta, cyan, and yellow are used, and the developer and the developing method of the present invention are used. By combining with a developing system that forms a latent image, it is possible to develop the dot latent image faithfully without being affected by the magnetic brush and disturbing the latent image. In the transfer step, a high transfer rate can be achieved by using the toner of the present invention, so that high image quality can be achieved in both the halftone portion and the solid portion.

Further, by using the toner of the present invention together with the initial improvement of the image quality, the effect of the present invention without image quality deterioration can be sufficiently exerted even when copying a large number of sheets.

The toner of the present invention can be suitably used for a developing means of a one-component developing system. An example of an apparatus for developing an electrostatic latent image formed on an electrostatic latent image carrier with a one-component developer is shown, but the invention is not necessarily limited thereto.

In FIG. 4, 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 by a non-magnetic sleeve made of aluminum or stainless steel.

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

In the present invention, the surface roughness Ra (μm) of the toner carrier is preferably set to 1.5 or less, more preferably 1.0 or less, further preferably 0.5 or less. Good to be.

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

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

In the present invention, the surface roughness Ra of the toner carrier is measured using a surface roughness measuring device (Surfcoder SE-30H, manufactured by Kosaka Laboratory Co., Ltd.) based on JIS surface roughness "JIS B0601". It corresponds to the measured center line average roughness. 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).

[0143]

[Outside 6]

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

According to the present invention, the surface moving speed of the toner carrier is set to be 1.05 to 3 times the surface moving speed of the electrostatic latent image carrier.
By setting it to be 0 times, 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.

If the surface moving speed of the toner carrier is less than 1.05 times the surface moving speed of the electrostatic latent image carrier,
When the toner layer has an insufficient stirring effect, it is difficult to form a good image, and when an image requiring a large amount of toner over a wide area such as a solid black image is developed, an electrostatic latent The amount of toner supplied to the image is insufficient, and the image density is reduced. When the surface moving speed of the toner carrier exceeds 3.0, in addition to the various problems caused by excessive charging of the toner as described above, deterioration of the toner due to mechanical stress and toner sticking to the toner carrier occur. This is not preferred.

The toner T is stored in the hopper 21 and is supplied onto the developing sleeve 24 by the supply member 22. As the supply member, a supply roller made of a porous material such as a foamed material such as a flexible polyurethane foam is preferably used. The supply roller is rotated with respect to the developing sleeve in a forward or reverse direction at a relative speed other than 0, and the toner is supplied to the developing sleeve and the stripped toner (undeveloped toner) on the sleeve is also developed. At this time, the contact width of the supply roller to the developing sleeve is preferably 2.0 to 10.0 mm in consideration of the balance between toner supply and stripping, and 4.0 to 6.0 mm.
mm is more preferable. On the other hand, excessive stress on the toner is inevitable, and the aggregation of the toner due to the deterioration of the toner is increased, or the fusion and fixation of the toner on the developing sleeve and the supply roller are apt to occur. It is excellent in fluidity and releasability, and has durability stability, so that it is preferably used in a developing method having the supply member. As the supply member, a brush member made of a resin fiber such as nylon or rayon may be used. Incidentally, these supply members are extremely effective in a non-magnetic one-component developing method using a non-magnetic one-component toner which cannot utilize a magnetic binding force, but are used in a magnetic one-component developing method using a magnetic one-component toner. Is also good.

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 gap from the developing sleeve. Alternatively, instead of the doctor blade, a rigid roller or a sleeve made of metal, resin, ceramic, or the like may be used, and a magnet generating means may be provided inside the roller or the sleeve.

An elastic member such as an elastic blade or an elastic roller for press-applying toner may be used as a regulating member for thinning the toner. For example, in FIG.
3 is a hopper (developer container) at the base on the upper side.
The developing sleeve 24 is flexed in the forward or reverse direction against the elasticity of the blade at the lower side, and the inner surface side of the blade (the outer surface side at twice the reverse direction) is sleeved. 24 is brought into contact with the surface with moderate elastic pressure. According to such an apparatus, a dense toner layer that is stable against environmental fluctuations can be obtained. Although the reason for this is not necessarily clear, it is assumed that the elastic body forcibly rubs against the surface of the developing sleeve, so that charging is always performed in the same state regardless of a change in behavior due to an environmental change of the toner.

On the other hand, the toner tends to be excessively charged and the toner is easily fused to the developing sleeve or the elastic blade. However, the toner used in the present invention is preferable because of excellent releasability and stable triboelectric charging. Used.

As the elastic body, it is preferable to select a material of a triboelectric series suitable for charging the toner to a desired polarity. Rubber elastic bodies such as silicone rubber, urethane rubber and NBR; synthetic materials such as polyethylene terephthalate Resin elastic body: Metal elastic bodies such as stainless steel, steel, phosphor bronze, and composites thereof can be used.

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

An organic substance or an inorganic substance may be added to the elastic body, may be melt-mixed, or may be dispersed. For example, metal oxides, metal powders, ceramics, carbon allotropes,
The chargeability of the toner can be controlled by adding whiskers, inorganic fibers, dyes, pigments or surfactants. In particular, when the elastic body is a molded article of rubber or resin, silica, alumina, titania, tin oxide, metal oxide fine powder such as zirconia and zinc oxide, carbon black, a charge control agent generally used for toner are used. It is also preferable to include them.

Further, a DC electric field and / or a brush are applied to the developing blade serving as the regulating member, the supply roller serving as the supply member, and the brush member.
Alternatively, even when an AC electric field is applied, the uniform thin layer coating property and the uniform charging property are further improved in the regulated portion on the developing sleeve due to the loosening action on the toner, and the toner supply / stripping is performed in the supply portion. Is achieved more smoothly, and 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, the aggregation of the toner can be effectively released, and the charge amount of the toner can be instantaneously increased. If the contact pressure is less than 0.1 kg / m, it becomes difficult to apply the toner uniformly. The distribution of the charge amount of the toner becomes broad and causes fogging and scattering. If the contact pressure is too high, a large pressure is applied to the toner, and the toner may be deteriorated or a toner aggregate may be generated. Further, a large torque is required to drive the toner carrier, which is preferable. Absent.

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 layer 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.

By applying an alternating electric field between the toner carrier and the electrostatic latent image by the bias power supply 26, the movement of the toner from the toner carrier to the electrostatic latent image carrier is facilitated. Images can be obtained. Alternating electric field V
pp is 100 V or more, preferably 200 to 3000 V,
More preferably, it is good to use in 300-2000V.
The frequency f is preferably 500 to 5000 Hz, more preferably 1000 to 3000 Hz, and further preferably 150
It is good to use it at 0 to 3000 Hz. In this case, a rectangular wave, a sine wave, a sawtooth wave, and a triangular wave can be applied to the waveform, and an asymmetrical AC bias having different positive and negative voltages and different times can also be used. It is also preferable to use a developing bias in which an AC bias is superimposed on a DC bias.
The electrostatic latent image carrier 1 is made of a-Se, Cds, ZnO ₂ , O
A photosensitive drum or a photosensitive belt having a photoconductive insulating material layer such as PC or a-Si. The electrostatic latent image carrier 1 is rotated in the direction of the arrow by a driving device (not shown).

As the electrostatic latent image bearing member 1, a photosensitive member having an amorphous silicon photosensitive layer or an organic photosensitive layer is preferably used.

As the organic photosensitive layer, the photosensitive layer contains a charge generating substance and a substance having charge transport performance in the same layer.
It may be a single-layer type or a function-separated type photosensitive layer having a charge transport layer as a component of the charge transport 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.

Examples of the binder resin for the organic photosensitive layer include polycarbonate resin, polyester resin, and acrylic resin.
It is preferably used because it has good transferability and cleaning properties, and it is difficult to cause poor cleaning, fusion of toner to a photoreceptor, and filming of an external additive.

In the charging step, a non-contact type charging system which is not in contact with the electrostatic latent image carrier 1 using a corona charger,
There is a contact type charging system using a contact charging member such as a charging roller which comes into contact with the electrostatic latent image carrier 1, and any of them is used. For efficient uniform charging, simplification and low ozone generation, a contact charging type as shown in FIG. 2 is preferably used.

The charging roller 2 basically has a core 2b at the center and a conductive elastic layer 2a formed on the outer periphery thereof. The charging roller 2 is pressed against the surface of the electrostatic latent image carrier 1 with a pressing force, and is driven to rotate as the electrostatic latent image carrier 1 rotates.

A preferable process condition when the charging roller is used is that the contact pressure of the roller is 5 to 500 g / cm.
When applying a charging bias in which an AC voltage is superimposed on a DC voltage, the AC voltage is 0.5 to 5 kVpp, the AC frequency is 50 Hz to 5 kHz, and the DC voltage is ± 0.2 to ± 1.5.
When applying a charging bias of only DC voltage, the DC voltage is preferably ± 0.2 to ± 5 kV.

Other charging means include a method using a charging blade and a method using a conductive brush. These contact charging means are effective in that high voltage is not required and generation of ozone is reduced.

As the material of the charging roller and the charging blade as the contact charging means, conductive rubber is preferable, and a release coating may be provided on the surface thereof. As the release coating, a nylon resin, PVDF (polyvinylidene fluoride), PVDC (polyvinylidene chloride) or the like can be applied. The toner image on the electrostatic latent image carrier is primarily transferred to the intermediate transfer body 5 to which a voltage (for example, ± 0.1 to 5 kV) is applied. The surface of the electrostatic latent image carrier is cleaned by cleaning means 9 having a cleaning blade 8.

The intermediate transfer member 5 is made of a pipe-shaped conductive core 5.
b and a medium resistance elastic layer 5a formed on the outer peripheral surface thereof. The metal core 5b may be formed by applying a conductive plating to a plastic pipe.

The medium-resistance elastic layer 5a is made of silicone rubber, Teflon rubber, chloroprene rubber, urethane rubber,
EPDM (terpolymer of ethylene propylene diene)
A conductive material such as carbon black, zinc oxide, tin oxide, or silicon carbide is mixed and dispersed in an elastic material such as to adjust the electric resistance (volume resistivity) to a medium resistance of 10 ⁵ to 10 ¹¹ Ω · cm. It is a solid or foamed layer.

The intermediate transfer member 5 is arranged so as to be supported in parallel with the electrostatic latent image carrier 1 and in contact with the lower surface of the electrostatic latent image carrier 1. It rotates in the counterclockwise direction of the arrow at the same peripheral speed as.

The first color toner image formed and carried on the surface of the electrostatic latent image carrier 1 is formed by the electrostatic latent image carrier 1 and the intermediate transfer member 5.
In the process of passing through the transfer nip portion where
The intermediate transfer is sequentially performed on the outer surface of the intermediate transfer body 5 by the electric field formed in the transfer nip area by the applied transfer bias.

If necessary, the surface of the intermediate transfer member 5 is cleaned by the detachable cleaning means 10 after the primary transfer of the toner image to the recording material. When there is a toner image on the intermediate transfer member, the cleaning unit 10 is separated from the surface of the intermediate transfer member so as not to disturb the toner image.

A transfer means is provided in parallel with the intermediate transfer member 5 and is brought into contact with the lower surface of the intermediate transfer member 5, and the transfer means 7 is, for example, a transfer roller or a transfer belt. It rotates clockwise with the same peripheral speed as the arrow. The transfer unit 7 may be disposed so as to directly contact the intermediate transfer member 5, or a belt may be disposed so as to contact between the intermediate transfer member 5 and the transfer unit 7.

In the case of the transfer roller, the basic structure is a core metal 7b at the center and a conductive elastic layer 7a forming the outer periphery thereof.

For the intermediate transfer member and the transfer roller, general materials can be used. By setting the volume resistivity of the elastic layer of the transfer roller smaller than the volume resistivity of the elastic layer of the intermediate transfer body, the voltage applied to the transfer roller can be reduced, and a good toner image can be formed on the transfer material. In addition, it is possible to prevent the transfer material from being wound around the intermediate transfer member. In particular, it is particularly preferable that the volume resistivity of the elastic layer of the intermediate transfer member is at least 10 times the volume resistivity of the elastic layer of the transfer roller.

For example, the conductive elastic layer 7b of the transfer roller 7
Is a polyurethane in which a conductive material such as carbon is dispersed, and an ethylene-propylene-diene terpolymer (EPD).
It is made of an elastic material having a volume resistance of about 10 ⁶ to 10 ¹⁰ Ωcm as in M). A bias is applied to the metal core 7a from a constant voltage power supply. The bias condition is ± 0.
2 to ± 10 kV is preferred.

The toner image on the recording material 6 is fixed by a heat and pressure fixing unit. As a heating and pressing fixing means, a heating roller having a built-in heating element such as a halogen heater and a pressing roller of an elastic body pressed against the heating roller with a pressing force as a basic configuration, or a heating roller through a film. A method of heating and fixing (FIGS. 5 and 6) can be cited, but the toner of the present invention is excellent in fixability and anti-offset properties, and thus shows good matching with the above-mentioned heating and pressing fixing means.

The toner of the present invention has a high transfer efficiency in the transfer step, a small amount of untransferred toner, and an excellent cleaning property. Therefore, filming hardly occurs on the electrostatic latent image carrier. Further, even when a multi-sheet durability test is performed, the toner of the present invention has less embedding of the external additive on the surface of the toner particles than the conventional toner, so that good image quality can be maintained for a long time. Therefore, an image forming apparatus having a so-called reuse mechanism that removes the transfer residual toner on the electrostatic latent image carrier and the intermediate transfer member shown in FIG. 5 by a cleaning unit such as a cleaning blade and reuses the collected transfer residual toner again. It can be preferably used for an apparatus.

In FIG. 5, reference numeral 40 denotes a photosensitive drum serving as an electrostatic latent image carrier, and 49 denotes a photosensitive drum 40.
Is a transfer roller as a transfer member for transferring a toner image formed on the surface of the photosensitive drum 40 to the recording material 50; 41 is an elastic blade 42 as a cleaning blade for removing toner remaining on the surface of the photosensitive drum 40 after the transfer. It is a cleaner for scraping and collecting. Reference numeral 43 denotes a cleaner screw for transporting the toner collected by the cleaner 41 between the cleaners 43, and reference numeral 44 internally includes a transport screw for transporting the toner transported by the cleaner screw 43 to the toner hopper 45. Supply pipe. 46 is a developing device, and 48 is a developing sleeve as a developer carrying member for carrying and transporting the developer in the developing device. Reference numeral 47 denotes a charging roller for primary charging the photosensitive drum 40.

In this image forming apparatus, the photosensitive drum 40 is primarily charged by a primary charging roller 47, and an electrostatic latent image is formed by an exposure means (not shown). The toner image is formed by developing with a developer having a toner carried on the sleeve 48. The toner image formed on the photosensitive drum 40 is transferred to a recording material 50 by a transfer roller 49, and the recording material 50
The toner image transferred onto the recording material 50 is heated and pressed by a heat roller fixing device 51 as a heat fixing device.
On the other hand, the transfer residual toner remaining on the surface of the photoreceptor drum 40 after the transfer is scraped off by the elastic blade 42 and once collected by the cleaner 41, sent to the inside of the cleaner by the cleaner roller, and further conveyed through the cleaner screw 43. The supply pipe provided with the screw returns to the developing device 46 via the hopper 45 and is used again for developing the electrostatic latent image. The image forming apparatus shown in FIG.
As described above, the toner is loosened.

Further, the toner of the present invention is excellent in the durability of the toner by containing a specific polycarbonate resin. Therefore, the toner of the present invention can be used in an image forming method using a contact development system in which high durability of the toner is required. Can be applied.

[0181]

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 Resin (1) 200 parts by weight of xylene was charged into 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 2 parts by weight of di-tert-butyl peroxide, the mixture was refluxed under xylene.
The polymerization was completed in 7 hours, and a low molecular weight resin solution was obtained.

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 polymer resin.

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

When the obtained resin (1) was analyzed, G
In the molecular weight distribution by PC, the peak molecular weight on the low molecular weight side is 10,000 and the peak molecular weight on the high molecular weight side is 75,000.
0, the weight average molecular weight (Mw) was 360000, the number average molecular weight (Mn) was 6000, Mw / Mn was 60, and the glass transition temperature (Tg) was 60 ° C.

Production Example of Resin (2) 83 parts by weight of styrene, 17 parts by weight of butyl acrylate, 0.2 parts by weight of polyvinyl alcohol, 200 parts by weight of degassed water, and 3.0 parts by weight of AIBN were mixed and dispersed. The suspension was heated and maintained at 85 ° C. for 24 hours under a nitrogen atmosphere to complete the polymerization, thereby obtaining a resin (2).

When the obtained resin (2) was analyzed, G
In the molecular weight distribution by PC, the peak molecular weight is 400
The weight average molecular weight (Mw) was 42,000, the number average molecular weight (Mn) was 12000, Mw / Mn was 3.5, and the glass transition temperature (Tg) was 60 ° C.

Example 1 100 parts by weight of resin (1) 1,1-bis (4-hydroxyphenyl) cyclohexane polycarbonate (peak molecular weight: 5000, M
w: 6000, Mn: 1700) 10 parts by weight Carbon black (BET specific surface area = 85 m ² / g)
10 parts by weight ・ Negative charge control agent (salicylic acid-based iron complex) 2 parts by weight ・ Low molecular weight polyethylene having a maximum endothermic peak of 107 ° C. 5
Parts by weight

After uniformly dispersing and mixing the above-mentioned materials, melt-kneaded materials were finely pulverized, and the obtained particles were subjected to a surface modification treatment so as to be smoothed and spherical.

Next, the obtained particles were classified to prepare toner particles (1), and 100 parts by weight of the toner particles (1) and 2 parts by weight of hydrophobic silica fine powder (BET: 200 m ² / g) were mixed with a Henschel mixer. And dry-mixing was performed to obtain a toner (1). 6 parts by weight of the obtained 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.

As shown in Table 1, the toner particles (1)
The value of F-1 is 135, the value of SF-2 is 118, (SF-
2) The value of / (SF-1) is 0.87 and the weight average diameter is 7.
3 μm, the peak molecular weight on the high molecular weight side was 650,000, and the peak molecular weight on the low molecular weight side was 1,000,000.

As shown in Table 1, the toner (1) was THF
GPC molecular weight distribution of solubles
00 The following ingredients aliquoted by GPC, which ¹ H-N
When analyzed by MR, ¹³ C-NMR and IR,
The content of the component having the repeating unit of the polycarbonate resin in the structure contained in the component having a molecular weight of 1,000 or less was 1.0% by weight based on the toner.

[0193] The 1,1-
Bis (4-hydroxyphenyl) cyclohexane polycarbonate is purified by repeating reprecipitation using methylene chloride and isopropanol to reduce low molecular weight components and impurities.

Further, the storage stability of the toner particles (1) was evaluated in the following manner. As shown in Table 1, good results were obtained without impairing the fluidity of the toner particles. .

<Method of Evaluating Storage Stability> 5.0 g of the toner particles (1) was placed in a 50 ml plastic cup, and allowed to stand in a hot air dryer set at 50.0 ° C. 3
It was taken out after a day, allowed to cool to room temperature, and visually judged according to the following criteria. A: Fluidity is not impaired. B: The fluidity is reduced, but the fluidity is recovered by rotating the cup. C: Aggregation and coarsening of the classified powder are observed. D: Caking

Example 2 Instead of using 1,1-bis (4-hydroxyphenyl) cyclohexane polycarbonate as a polycarbonate resin, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane polycarbonate (peak molecular weight: 4500) , Mw: 5000, Mn: 1500) in the same manner as in Example 1, except that toner particles (2), toner (2) and developer (2) were prepared. Table 1 shows the analysis results and the evaluation results of the toner particles (2) and the toner (2).

The 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane polycarbonate used in the production of the toner particles (2) is repeatedly reprecipitated using methylene chloride and isopropanol to reduce low molecular weight components and impurities. Purified so that

Example 3 Instead of using 1,1-bis (4-hydroxyphenyl) cyclohexane polycarbonate as a polycarbonate resin, 2,2-bis (3-methyl-4-hydroxyphenyl) propane polycarbonate (peak molecular weight: (Mw: 4500, Mn: 1200) was used in the same manner as in Example 1 to prepare toner particles (3), toner (3), and developer (3). Table 1 shows the analysis results and the evaluation results of the toner particles (3) and the toner (3).

The 2,2- used in the production of the toner particles (3)
Bis (3-methyl-4-hydroxyphenyl) propane polycarbonate is purified by repeating reprecipitation using methylene chloride and isopropanol so that low molecular weight components and impurities are reduced.

Examples 4 and 5 In the same manner as in Example 1 except that the conditions for the surface modification treatment were changed, toner particles (4) and (5), toners (4) and (5), and developer (4 ) And (5) were prepared. Table 1 shows the analysis results and the evaluation results of the toner particles (4) and (5) and the toners (4) and (5).

Example 6 Toner particles (6), toner (6) and developer (6) were prepared in the same manner as in Example 1 except that the surface modification treatment was not performed. Toner particles (6) and toner (6)
Table 1 shows the analysis results and evaluation results.

Example 7 Toner particles (7), toner (7) and developer (7) were prepared in the same manner as in Example 1 except that the resin (1) was changed to the resin (2). Table 1 shows the analysis results and the evaluation results of the toner particles (7) and the toner (7).

Example 8 Toner particles (8) and toner particles (8) were prepared in the same manner as in Example 1 except that a compound of a monoazo dye and iron was used in place of the salicylic acid-based iron complex used in Example 1. (8) and a developer (8) were prepared. Table 1 shows the analysis results and the evaluation results of the toner particles (8) and the toner (8).

Comparative Example 1 Comparative toner particles (9), comparative toner (9) and comparative developer (9) were prepared in the same manner as in Example 1 except that no polycarbonate resin was used. Table 1 shows the analysis results and the evaluation results of the comparative toner particles (9) and the comparative toner (9).

Comparative Example 2 p-tert-butylphenol and 1,1-bis (4
Comparative toner particles (1) were prepared in the same manner as in Example 1 except that 25 parts by weight of a compound in which -hydroxyphenyl) cyclohexane was bonded to an ester via carbonic acid was further added.
0), comparative toner (10) and comparative developer (10)
Was prepared. Table 1 shows the analysis results and the evaluation results of the comparative toner particles (10) and the comparative toner (10).

Comparative Example 3 Bisphenol A-biphenol-diethylene glycol copolymerized polycarbonate (peak molecular weight: 1200
0, Mw: 13000, Mn: 4000, Tg: 50
℃) 100 parts by weight ・ Carbon black (BET specific surface area = 85 m ² / g)
10 parts by weight ・ Negative charge control agent (salicylic acid-based iron complex) 2 parts by weight ・ Low molecular weight polyethylene having a maximum endothermic peak of 107 ° C. 5
Parts by weight

The above materials were uniformly mixed and melted, and then pulverized. Thereafter, in the same manner as in Example 1, comparative toner particles (11), comparative toner (11) and comparative developer (11) were prepared. Table 1 shows the analysis results and the evaluation results of the toner particles (11) and the comparative toner (11).

The bisphenol A-biphenol-diethylene glycol copolymerized polycarbonate used in the production of the toner particles (11) was not purified by reprecipitation.

Comparative Example 4 Resin (1) 50 parts by weight 1,1-bis (4-hydroxyphenyl) cyclohexane polycarbonate (peak molecular weight: 3,000, M
w: 3500, Mn: 1000) 50 parts by weight Carbon black (BET specific surface area = 85 m ² / g)
10 parts by weight ・ Negative charge control agent (salicylic acid-based iron complex) 2 parts by weight ・ Low molecular weight polyethylene having a maximum endothermic peak of 107 ° C. 5
Parts by weight

After uniformly dispersing and mixing the above materials, the melt-kneaded product was finely pulverized, and the obtained particles were subjected to a surface modification treatment to be smoothed and spherical.

Then, the obtained particles were classified to prepare comparative toner particles (12), and the comparative toner particles (12) were prepared.
100 parts by weight and hydrophobic silica fine powder (BET: 200 m
² / g) of 2 parts by weight were dry-mixed with a Henschel mixer to obtain a comparative toner (12). 6 parts by weight of the obtained comparative toner (12) and 94 parts by weight of a resin-coated magnetic ferrite carrier (average diameter: 50 μm) were mixed to prepare a two-component developer for comparison (12). Toner particles (12)
Table 1 shows the analysis results and the evaluation results of the toner and the toner (12).

The 1,1 used in the production of the toner particles (12)
-Bis (4-hydroxyphenyl) cyclohexane polycarbonate was not purified by reprecipitation.

[0213]

[Table 1]

The toners (1) to (8) and the comparative toners (9) to (9) manufactured in Examples 1 to 8 and Comparative Examples 1 to 4 described above.
Evaluation was performed as follows using the developers (1) to (8) having (12) and the comparative developers (9) to (12).

An image forming apparatus used in this embodiment will be described. FIG. 2 is a schematic diagram of a cross section of the image forming apparatus applied to the present embodiment, and FIG. 3 is a development manufacturing diagram of the image forming apparatus.

The photosensitive drum 1 has a photosensitive layer 1b having an organic optical semiconductor on a base material 1a, and rotates in the direction of the arrow to oppose and rotate in contact with the charging roller 2 (conductive elastic layer 2a, core metal 2b). ) To charge the photosensitive drum 1 to a surface potential of about -600 V. The exposure 3 is turned on and off on the photoreceptor by a polygon mirror in accordance with digital image information, thereby forming an electrostatic image having an exposure portion potential of -100 V and a dark portion potential of -600 V. A black toner was formed on the photoreceptor 1 using a plurality of developing units 4-1 to obtain a toner image using a reversal developing method. The toner image is transferred onto the intermediate transfer member 5, and the transfer material toner on the photoreceptor 1 is collected by the cleaner member 8 into the remaining toner container 9.

The intermediate transfer member 5 was formed by coating a pipe-shaped core metal 5b with an elastic layer 5a in which a carbon black conductive member was sufficiently dispersed in nitrile-butadiene rubber (NBR). The hardness of the coat layer 5a is determined according to “JIS
K-6301 "and a volume resistivity of 10 ⁹ Ω · cm. The transfer current required for the transfer from the photoreceptor 1 to the intermediate transfer member 5 was about 5 μA, which was obtained by applying +500 V from the power supply to the cored bar 5b.

The transfer roller 7 has an outer diameter of 20 mm. The transfer roller 7 is formed by forming a carbon conductive member on a core bar 7 b having a diameter of 10 mm by foaming an ethylene-propylene-diene-based terpolymer (EPDM). It has an elastic layer 7a formed by coating a substance sufficiently dispersed in the body, and has a volume resistivity of 10 ⁶ Ω · cm.
The standard hardness indicated in “JIS K-6301” was 35 degrees. A voltage was applied to the transfer roller, and a transfer current of 15 μA was passed.

As the heat fixing device H, a heat roll type fixing device having no oil application function was used. At this time, the upper roller,
A lower roller having a surface layer of a fluororesin was used, and the diameter of the roller was 50 mm. Fixing temperature is 1
The nip width was set to 7 mm at 80 ° C.

Under the above set conditions, room temperature and normal humidity (25 ° C., 6
In a 0% RH environment, the developer (1) to (8) and the comparative developers (9) to (12) are replenished at a printout speed of 8 sheets (A4 size) / min in a single color. The printout test of 100 sheets was performed in the continuous mode (that is, the mode in which the consumption of the toner was promoted without stopping the developing device). Next, low temperature and low humidity (15 ° C, 10% R
H) In an environment, a printout test of 5000 images of the same print style was performed. Then, the obtained printout image was evaluated for items described below.

Further, regarding the matching of the image forming apparatus and the developer used at the same time, the end of the printout test was evaluated.

The above evaluation results are summarized in Tables 2 and 3.

[0223]

[Table 2]

[0224]

[Table 3]

Example 9 and Comparative Example 5 The developing device of the image forming apparatus shown in FIG. 3 was replaced with the developing device shown in FIG. 4, and the moving speed of the toner carrier surface was 3 times smaller than the moving speed of the electrostatic latent image carrier surface. And the toner (1) manufactured in Example 1 and the comparative toner (9) manufactured in Comparative Example 1 were successively replenished in a single-color intermittent mode (ie, 1 ×). 10 per printout
(The mode in which the developing unit is stopped for a second and the deterioration of the toner is promoted by the preparatory operation of the developing device at the time of restarting).

The surface roughness Ra of the toner carrier used here was
The toner regulating blade used was one in which urethane rubber was adhered to a phosphor bronze base plate and the contact surface with the toner carrier was coated with nylon. The evaluation results are summarized in Tables 4 and 5.

[0227]

[Table 4]

[0228]

[Table 5]

Example 10 and Comparative Example 6 In this example, a commercially available laser beam printer LBP-
EX (manufactured by Canon Inc.) was remodeled with a reuse mechanism attached to it and used again. That is, in FIG. 5, after the untransferred toner on the photosensitive drum 40 is scraped off by the elastic blade 42 of the cleaner 41 which is in contact with the photosensitive drum, the toner is sent into the cleaner by the cleaner roller, and the cleaner screw 43 is further moved. Thereafter, the toner is returned to the developing device 46 via the hopper 45 by the supply pipe 44 provided with the conveying screw, and a system utilizing the collected toner is attached again. As the primary charging roller 47, the conductive carbon coated with the nylon resin is dispersed. the rubber roller (diameter 12 mm, contact pressure 50 g / cm) using a dark portion potential V _D = -700 V, the light potential V _L = -200 V was formed by laser exposure (600 dpi) to the electrostatic latent image bearing member. A developing sleeve 48 having a surface roughness Ra of 1.1 coated with a resin in which carbon black is dispersed as a toner carrier is set to be 1.1 times the moving speed of the photosensitive drum surface. The gap between the photosensitive drum and the developing sleeve (between SD) was 270 μm, and a urethane rubber blade was used as a toner regulating member in contact with the developing sleeve. An AC bias component was superimposed on a DC bias component as a developing bias.

The fixing device shown in FIGS. 6 and 7 is used as the heat fixing device H. The surface temperature of the heating element 31d of the heating element 31 is 170 ° C., and the heating element 21 is a sponge having a silicone rubber foam as a lower layer. The total pressure between the pressure rollers 33 is 8k
g, the nip between the pressure roller and the film is 6 mm, and the fixing film 32 has a low-resistance release layer in which a conductive substance is dispersed in PTEF (high molecular weight type) on the contact surface with the transfer material. A 60 μm heat-resistant polyimide film was used.

Under the above set conditions, room temperature and normal humidity (25 ° C., 6
Under the environment of 0% RH, the toner (1) manufactured in Example 1 and the comparative toner (10) manufactured in Comparative Example 2 are successively supplied at a printout speed of 6 sheets (A4 size) / min. A 100-sheet printout test was performed in the intermittent mode (that is, a mode in which the developing device was stopped for 10 seconds each time one sheet was printed out and the deterioration of the toner was promoted by a preliminary operation at the time of restarting). Then, low temperature and low humidity (15
Temperature, 10% RH) Image 5000 of the same printing style under the environment
A printout test was performed on a single sheet. Then, the obtained printout image was evaluated for items described below.

The matching between the simultaneously used image forming apparatus and the toner was also evaluated.

The above evaluation results are summarized in Tables 6 and 7.

[0234]

[Table 6]

[0235]

[Table 7]

Embodiment 11 Except that the toner reuse mechanism shown in FIG. 5 is removed, the same procedure as in Embodiment 10 is carried out, and the toner (2) produced in Embodiment 2 is successively supplied while the toner (2) is successively supplied (that is, the developing unit is stopped). The printout test was conducted in a mode in which the consumption of toner was promoted without using the toner.

The obtained printout image was evaluated for the following items, and the matching with the used image forming apparatus was also evaluated. As a result, all items were good.

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

[Printout Image Evaluation] <1> Image Density The 100th printout image was evaluated by image density. The image density was measured using a “Macbeth reflection densitometer” (manufactured by Macbeth) with respect to the printout image of the white background portion where the original density was 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> Change in Image Density The image density of the 100th and 5000th images printed out in a low-temperature and low-humidity environment was measured, and the change in image density was calculated from the following equation. The image density was measured using a “Macbeth reflection densitometer” (manufactured by Macbeth) with respect to the printout image of the white background portion where the original density was 0.00. Image density change = density of the 100th sheet−density of the 5000th sheet A: less than 0.05 B: 0.05 or more, less than 0.10 C: 0.10 or more, less than 0.15 D: 0.15 or more

<3> Image fog The fog density (%) was calculated from the difference between the whiteness of the white background portion of the 100th printout image and the whiteness of the transfer paper at room temperature and normal humidity, and the image fog was evaluated. The fog density was measured with a "reflectometer" (manufactured by Tokyo Denshoku Co., Ltd.). 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

<4> Image Missing In the 100th printout image at normal temperature and normal humidity, the character missing of the “surprise” character pattern shown in FIG. 8A (the state shown in FIG. 8B) is shown. It was evaluated visually. A: Almost no occurrence. B: Slight hollowing is observed. C: A slight hollow is seen. D: A noticeable hollow is observed.

[Evaluation of Matching of Image Forming Apparatus] <1> Matching with Developing Sleeve After completion of the printout test, the state of fixation of residual toner on the surface of the developing sleeve was visually evaluated. A: Not generated. B: Almost no occurrence. C: There is some sticking. D: Many sticks.

<2> Matching with Photosensitive Drum After the printout test was completed, the occurrence of scratches on the surface of the photosensitive drum and the occurrence of sticking of residual toner were visually evaluated. A: Not generated. B: Slight scratching is observed. C: There are sticking and scratches. D: Many sticks.

<3> Matching with Intermediate Transfer Body After the print-out test was completed, the surface of the intermediate transfer body and the state of fixation of residual toner were visually evaluated. A: Not generated. B: Residual toner is observed on the surface. C: There are sticking and scratches. D: Many sticks.

<4> Matching with Fixing Device After the completion of the printout test, the surface of the fixing film and the state of fixation of residual toner were visually evaluated. A: Not generated. B: Slight sticking is observed. C: There are sticking and scratches. D: Many sticks.

Example 12 100 parts by weight of resin (1) Carbon black (BET specific surface area = 104 m ² /
g) 10 parts by weight-Negative charge control agent (salicylic acid-based iron complex) 2 parts by weight-Low molecular weight polyethylene having a maximum endothermic peak of 107 ° C 5
Parts by weight

The above materials were mixed in a blender, melted and kneaded with 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 1,1-bis (4-hydroxyphenyl) cyclohexane polycarbonate in the form of fine powder (peak molecular weight: 5000, M
w: 5600, Mn: 1600) 20 parts by weight were dry-mixed with a Henschel mixer, then immobilized at 40 ° C., and 1,1-bis (4-hydroxyphenyl) cyclohexane polycarbonate fine powder was applied to the surface of the finely pulverized particles. Was 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 into toner particles (13).

Observation of the tomographic plane of the toner particles (13) by TEM showed that contrast was continuously observed on the surface of the toner particles. The composition of the toner particle surface was analyzed by FT-IR / PAS by changing the scan speed of the movable mirror using PAS.
A spectrum derived from -bis (4-hydroxyphenyl) cyclohexane polycarbonate was obtained, and it was confirmed that the polycarbonate resin was continuously present on the surface of the toner particles.

100 parts by weight of the toner particles (13) 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 (13). 6 parts by weight and 94 parts by weight of a resin-coated magnetic ferrite carrier (average diameter: 50 μm) were mixed to prepare a two-component developer (13) for magnetic brush development.

The value of SF-1 of the toner particles (13) is 14
5, the value of SF-2 is 130, (SF-2) / (SF-
The value of 1) was 0.90, the weight average diameter was 6.9 μm, the peak molecular weight on the high molecular weight side was 700,000, and the peak molecular weight on the low molecular weight side was 1,000,000.

In the molecular weight distribution of the THF-soluble portion of the toner (13) by GPC, a component having a molecular weight of 1,000 or less was separated by GPC, and this was separated by ¹ H-NMR and ¹³ C-NM.
Analysis by R and IR revealed that the content of the component having a repeating unit of the polycarbonate resin contained in the component having a molecular weight of 1,000 or less in the structure was 1.2% by weight based on the toner. Was.

[0254] The 1,1-
Bis (4-hydroxyphenyl) cyclohexane polycarbonate is purified by repeating reprecipitation using dichloromethane and isopropanol so that low molecular weight components and impurities are reduced.

The toner particles (13) were evaluated for storage stability in the same manner as in Example 1. As a result, good results were obtained without impairing the fluidity of the toner particles. Table 8 shows the analysis results and the evaluation results of the toner particles (13) and the toner (13).

Example 13 Instead of using 1,1-bis (4-hydroxyphenyl) cyclohexane polycarbonate as a polycarbonate resin, bisphenol A-biphenol-hexamethylene glycol copolymerized polycarbonate (peak molecular weight 30,000, Mw 32,000, Mn 10,000,
(Tg 60 ° C.) Example 12 except that 20 parts by weight were used.
In the same manner as in the above, toner particles (14), toner (14) and developer (14) were prepared.

The bisphenol A-biphenol-hexamethine glycol copolymerized polycarbonate used in the production of the toner (14) was purified by repeating reprecipitation using dichloromethane and isopropanol to reduce low molecular weight components and impurities. is there.

Table 8 shows the analysis results and the evaluation results of the toner particles (14) and the toner (14).

Example 14 100 parts by weight of resin (1) Carbon black (BET specific surface area = 104 m ² /
g) 10 parts by weight-Negative charge control agent (salicylic acid-based iron complex) 2 parts by weight-Low molecular weight polyethylene having a maximum endothermic peak of 107 ° C 5
Parts by weight

The above materials were mixed in a blender, melted and kneaded with 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, the particles were subjected to a surface modification using a device for applying a mechanical impact by rotating a rotor, and then subjected to classification. Further, 100 parts by weight of the classified powder and bisphenol A polycarbonate in the form of fine powder (peak molecular weight:
5000, Mw: 5600, Mn: 1600) were dry-mixed with a Henschel mixer, immobilized at 40 ° C., and bisphenol A was added to the surface of the finely pulverized particles.
Toner particles with fine polycarbonate powder attached (15)
I got

When the tomographic plane of the toner particles (15) was observed by TEM, contrast was discontinuously observed on the surface of the toner particles. Further, when the composition analysis of the toner particle surface was performed by FT-IR / PAS by changing the scanning speed of the movable mirror using PAS, a spectrum derived from bisphenol A polycarbonate was obtained. It was confirmed that the polycarbonate resin was present discontinuously.

100 parts by weight of the toner particles (15) 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 (15). 6) parts by weight and 94 parts by weight of a resin-coated magnetic ferrite carrier (average diameter: 50 μm) were mixed to prepare a two-component developer (15) for magnetic brush development.

The bisphenol A polycarbonate used in the production of the toner (15) is purified by repeating reprecipitation using dichloromethane and isopropanol so that low molecular weight components and impurities are reduced.

Table 8 shows the analysis results and the evaluation results of the toner particles (15) and the toner (15).

Example 15 Instead of using bisphenol A polycarbonate as a polycarbonate resin, 2,2-bis (3-methyl-4-hydroxyphenyl) propane (peak molecular weight: 4000, Mw: 4500, Mn: 1200) was used. A toner particle (16), a toner (16) and a developer (16) were prepared in the same manner as in Example 14 except for the above.

The 2,2- used in the production of the toner (16)
Bis (3-methyl-4-hydroxyphenyl) propane polycarbonate is purified by repeating reprecipitation using dichloromethane and isopropanol to reduce low molecular weight components and impurities.

Table 8 shows the analysis results and the evaluation results of the toner particles (16) and the toner (16).

Example 16 650 g of ion-exchanged water and 0.1 mol / l-Na ₃ P were placed in a 2-liter 4-neck separable flask equipped with a high-speed stirrer TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.).
500 g of an O ₄ aqueous solution is charged, and the rotation speed is 12,000 rpm.
m and heated to 70 ° C. Here 1.0mol /
70 parts by weight of an aqueous solution of liter-CaCl ₂ was gradually added to prepare an aqueous continuous phase containing a small, slightly water-insoluble dispersion stabilizer Ca ₃ (PO ₄ ).

On the other hand, dispersoids include: styrene 83 parts by weight n-butyl acrylate 17 parts by weight Divinylbenzene (purity 55%) 0.3 part by weight Carbon black (BET specific surface area = 104 m ² /
g) 10 parts by weight-Negative charge control agent (salicylic acid-based iron complex) 2 parts by weight

The above mixture was dispersed for 3 hours using an attritor (manufactured by Mitsui Miike Kako). 1,1-bis (4-hydroxyphenyl) cyclohexane polycarbonate (peak molecular weight: 8,000, M
w: 8600, Mn: 2800) 5 parts by weight ・ 5 parts by weight of paraffin wax having a maximum endothermic peak of 70 ° C. ・ 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) is added and heated to 70 ° C. Then, a polymerizable monomer composition was prepared.

Next, the polymerizable monomer composition was put into the aqueous dispersion medium, and the mixture was stirred for 15 minutes under a nitrogen atmosphere at a liquid temperature of 70 ° C. while maintaining the rotation speed of a high-speed stirrer at 12,000 rpm. The hydrophilic monomer composition was granulated. After that, the suspension was changed to a propeller-type stirring blade and maintained at 70 ° C. for 10 hours while stirring at 50 rpm to obtain a suspension.

Thereafter, the suspension was cooled, and then dilute hydrochloric acid was added to remove the dispersion stabilizer. Further, after washing with water was repeated several times, the polymer particles were dried.
7).

The toner particles (17) had a SF-1 value of 1
27, the value of SF-2 is 106, (SF-2) / (SF-
The value of 1) was 0.83, the weight average diameter was 6.2 μm, and the peak molecular weight was 2,000,000.

1.0 g of the toner particles (17) was precisely weighed and charged in a cylindrical filter paper, and tetrahydrofuran (THF) 200
Soxhlet extraction was performed for 20 hours in
The THF-insoluble matter was calculated by vacuum drying at 12 ° C. for 12 hours and measuring the weight of the residue, and it was 40% by weight based on the polymer particles.

100 parts by weight of the toner particles (17) and 2 parts by weight of hydrophobic silica fine powder (BET: 200 m ² / g) were dry-mixed with a Henschel mixer to obtain the toner (17).
After that, 6 parts by weight of the toner (17) and 94 parts by weight of a resin-coated magnetic ferrite carrier (average diameter: 50 μm) were mixed to prepare a two-component developer (17) for magnetic brush development.

In the molecular weight distribution of the THF-soluble portion of the toner (17) by GPC, a component having a molecular weight of 1,000 or less was fractionated by GPC, and the fraction was analyzed by ¹ H-NMR and ¹³ C-NM.
Analysis by R and IR revealed that the content of the component having a repeating unit of the polycarbonate resin in the structure contained in the component having a molecular weight of 1,000 or less was 0.5% by weight based on the toner. Was.

[0278] The 1,1-
Bis (4-hydroxyphenyl) cyclohexane polycarbonate is purified by repeating reprecipitation using dichloromethane and isopropanol so that low molecular weight components and impurities are reduced.

Table 8 shows the analysis results and the evaluation results of the toner particles (17) and the toner (17).

Example 17 The above-mentioned Example was repeated except that 1 part by weight of an unsaturated polyester (polyester obtained by condensing propoxylated bisphenol A and fumaric acid, peak molecular weight 10,000) was further added to the polymerizable monomer composition. In the same manner as in Example 16, a toner particle (18), a toner (18), and a developer (18) were prepared. Table 8 shows the analysis results and the evaluation results of the toner particles (18) and the toner (18).

Example 18 Instead of using 1,1-bis (4-hydroxyphenyl) cyclohexane polycarbonate as a polycarbonate resin, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane (having a peak molecular weight of 20,000,
Mw26000, Mn6500), and toner particles (19), toner (19) and developer (19) were prepared in the same manner as in Example 16 above.

The 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane polycarbonate used in the production of Toner (19) is repeatedly reprecipitated using dichloromethane and isopropanol to reduce low molecular weight components and impurities. It was purified as described above.

Table 1 shows the analysis results and the evaluation results of the toner particles (19) and the toner (19).

Example 19 Instead of using 1,1-bis (4-hydroxyphenyl) cyclohexane polycarbonate as a polycarbonate resin, 2,2-bis (3-methyl-4-hydroxyphenyl) propane (peak molecular weight 8,000, Mw
7800, Mn 2500).
6, the toner particles (20) and the toner (20)
And a developer (20).

[0285] The 2,2-
Bis (3-methyl-4-hydroxyphenyl) propane polycarbonate is purified by repeating reprecipitation using dichloromethane and isopropanol so that low molecular weight and impurities are reduced.

Table 8 shows the analysis results and the evaluation results of the toner particles (20) and the toner (20).

Example 20 Toner particles (21) and toner (2) were prepared in the same manner as in Example 11 except that resin (1) was changed to resin (2).
1) and a developer (21) were prepared. Toner particles (2
Table 8 shows the analysis results and the evaluation results of 1) and the toner (21).
Shown in

Example 21 Toner particles (22) and toner particles were prepared in the same manner as in Example 16 except that a compound of a monoazo dye and iron was used instead of the salicylic acid-based iron complex used in Example 16. (2
2) and a developer (22) were prepared. Toner particles (2
Table 8 shows the analysis results and the evaluation results of 2) and the toner (22).
Shown in

Comparative Example 7 Comparative toner particles (23), comparative toner (23) and comparative developer (23) were prepared in the same manner as in Example 12 except that no polycarbonate resin was used. Table 8 shows the analysis results and the evaluation results of the comparative toner particles (23) and the comparative toner (23).

Comparative Example 8 Comparative toner particles (24), comparative toner (24) and comparative developer (24) were prepared in the same manner as in Example 16 except that no polycarbonate resin was used. Table 8 shows the analysis results and the evaluation results of the toner particles (24) and the comparative toner (24).

Comparative Example 9 Bisphenol A-biphenol-diethylene glycol copolymerized polycarbonate (peak molecular weight: 1200
0, Mw: 13000, Mn: 4100, Tg: 50
℃) 100 parts by weight ・ Carbon black (BET specific surface area = 85 m ² / g)
10 parts by weight ・ Negative charge control agent (salicylic acid-based iron complex) 2 parts by weight ・ Low end molecular weight polyethylene having a maximum endothermic peak of 107 ° C. 5
Parts by weight

The above materials were uniformly mixed and melted, and then pulverized. Thereafter, in the same manner as in Example 1, comparative toner particles (25), comparative toner (25), and comparative developer (25) were prepared.

The bisphenol A-biphenol-diethylene glycol copolymerized polycarbonate used in the production of the comparative toner (25) was not purified by reprecipitation.

Table 8 shows the analysis results and evaluation results of the comparative toner particles (25) and the comparative toner (25).

[0295]

[Table 8]

The above Examples 12 to 22 and Comparative Examples 7 to 9
(13) to developer (13) having toners (13) to (22) and comparative toners (23) to (25) respectively manufactured by
Using the same image forming apparatus as used in Examples 1 to 8 and Comparative Examples 1 to 4 using (22) and comparative developers (23) to (25), only the printout test method is changed as follows. Except for this, various evaluations were performed in the same manner.

The printout test was conducted at room temperature and normal humidity (25
After leaving the developer for one week in an environment of (° C., 60% RH), the developer (1) is printed at a printout speed of 8 sheets (A4 size) / min.
3) to (22) and the comparative developers (23) to (25) are successively replenished in a single color continuous mode (that is, a mode in which toner consumption is promoted without stopping the developing device). After performing a printout test on the sheet, the developer was allowed to stand for one week in a high-temperature and high-humidity (30 ° C., 80% RH) environment.
A printout test was performed on a single sheet. Then, the obtained printout image was evaluated for items described below. Tables 9 and 10 show the evaluation results.

[0298]

[Table 9]

[0299]

[Table 10]

Embodiment 22 and Comparative Example 10 The developing device of the image forming apparatus shown in FIG. 3 was replaced with the developing device shown in FIG. 4, and the moving speed of the toner carrier surface was 3 times smaller than the moving speed of the electrostatic latent image carrier surface. And the toner (13) manufactured in Example 11 and the comparative toner (23) manufactured in Comparative Example 7 were sequentially replenished in a single color intermittent mode (ie, one sheet). The evaluation was performed in the same manner as in the above-described embodiment using a mode in which the developing unit was stopped for 10 seconds each time printing was performed, and the deterioration of the toner was promoted by the preliminary operation of the developing device at the time of restart.

The surface roughness Ra of the toner carrier used here was
The toner regulating blade used was one in which urethane rubber was adhered to a phosphor bronze base plate and the contact surface with the toner carrier was coated with nylon. Tables 11 and 12 summarize the evaluation results.

[0302]

[Table 11]

[0303]

[Table 12]

Example 23 and Comparative Example 11 In this example, a commercially available laser beam printer LBP-
The reuse mechanism was attached to EX (manufactured by Canon Inc.), modified, and used again. That is, in FIG. 5, after the untransferred toner on the photosensitive drum 40 is scraped off by the elastic blade 42 of the cleaner 41 which is in contact with the photosensitive drum, the toner is sent into the cleaner by the cleaner roller, and the cleaner screw 43 is further moved. Thereafter, the toner is returned to the developing device 46 via the hopper 45 by the supply pipe 44 provided with the conveying screw, and a system utilizing the collected toner is attached again. As the primary charging roller 47, the conductive carbon coated with the nylon resin is dispersed. the rubber roller (diameter 12 mm, contact pressure 50 g / cm) using a dark portion potential V _D = -700 V, the light potential V _L = -200 V was formed by laser exposure (600 dpi) to the electrostatic latent image bearing member. A developing sleeve 48 having a surface roughness Ra of 1.1 coated with a resin in which carbon black is dispersed as a toner carrier is set to be 1.1 times the moving speed of the photosensitive drum surface. The gap between the photosensitive drum and the developing sleeve (between SD) was 270 μm, and a urethane rubber blade was used as a toner regulating member in contact with the developing sleeve. An AC bias component was superimposed on a DC bias component as a developing bias.

The fixing device shown in FIGS. 6 and 7 is used as the heating fixing device H. The surface temperature of the heating element 31d of the heating element 31 is 170 ° C., and the heating element 21 is a sponge having a silicone rubber foam as a lower layer. The total pressure between the pressure rollers 33 is 8k
g, the nip between the pressure roller and the film is 6 mm, and the fixing film 32 has a low-resistance release layer in which a conductive substance is dispersed in PTEF (high molecular weight type) on the contact surface with the transfer material. A 60 μm heat-resistant polyimide film was used.

Under the above set conditions, room temperature and normal humidity (25 ° C., 6
0% RH), after leaving the developer for one week, 4 sheets (A4
At the printout speed of (size) / min, the toner (18) manufactured in Example 16 and the comparative toner (24) manufactured in Comparative Example 8 are sequentially replenished while intermittent mode (that is, one sheet is printed out). The printout test is performed for 1000 sheets in a mode in which the developing unit is stopped for 10 seconds each time, and the deterioration of the toner is promoted by the preliminary operation at the time of restart.
Next, after leaving the developer in a high-temperature and high-humidity (30 ° C., 80% RH) environment for one week, a printout test of 1,000 sheets was performed in the same manner as described above. Then, the obtained printout image was evaluated for items described below.

The matching between the simultaneously used image forming apparatus and the developer was also evaluated after the completion of the printout test.

The above evaluation results are summarized in Tables 13 and 14.

[0309]

[Table 13]

[0310]

[Table 14]

Example 24 The toner (17) manufactured in Example 16 was manufactured in the same manner as in Example 23 except that the toner reuse mechanism in FIG. 5 was removed.
Mode (ie, a mode that promotes toner consumption without stopping the developing unit) while sequentially replenishing toner.
A printout test was performed.

The obtained printout image was evaluated for the items described below, and also for matching with the used image forming apparatus. As a result, all items were good.

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

[Evaluation of Printout Image] <1> Image Density Printout of 1,000 sheets was performed on ordinary plain paper for copying machines (75 g / m ² ) at normal temperature and normal humidity, and the image density of the 1000th printout image was obtained. Was evaluated. The image density was measured using a “Macbeth reflection densitometer” (manufactured by Macbeth) with respect to the printout image of the white background portion where the original density was 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> Change in Image Density Printout was performed on ordinary plain paper for copying machines (75 g / m ² ) at normal temperature and normal humidity, and then at 1000 ° C. for high-temperature and high-humidity. The image density of the 1000th image was measured, and the image density change was calculated from the following equation. The image density was measured using a “Macbeth reflection densitometer” (manufactured by Macbeth) with respect to the printout image of the white background portion where the original density was 0.00. Image density change = density of normal temperature and normal humidity−density of the 5000th sheet A: less than 0.05 B: 0.05 or more, less than 0.10 C: 0.10 or more, less than 0.15 D: 0.15 or more

<3> Image fog 1000 prints were made on ordinary plain paper for copying machines (75 g / m ² ) at normal temperature and normal humidity, and 1000 prints were measured with a “Reflectometer” (manufactured by Tokyo Denshoku Co., Ltd.). The fog density (%) was calculated from the difference between the whiteness of the white background portion of the printout image of the eyes 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

<4> Hollow-out of Image At room temperature and normal humidity, the hollowness of the character of the “surprise” character pattern shown in FIG. 8A (the state of FIG. 8B was visually evaluated. A: Almost occurred No: B: Minor voids are observed C: Slight voids are seen D: Remarkable voids are seen

[Evaluation of Matching of Image Forming Apparatus] <1> Evaluation of Matching with Developing Sleeve After completion of the printout test, the state of fixation of residual toner on the surface of the developing sleeve was visually evaluated. A: Not generated. B: Almost no occurrence. C: There is some sticking. D: Many sticks.

<2> Matching with Photosensitive Drum After completion of the printout test, the occurrence of scratches on the surface of the photosensitive drum and adhesion of residual toner were visually evaluated. A: Not generated. B: Slight scratching is observed. C: There are sticking and scratches. D: Many sticks.

<3> Matching with Intermediate Transfer Body After the completion of the printout test, the surface of the intermediate transfer body was scratched and the state of fixation of residual toner was visually evaluated. A: Not generated. B: Residual toner is observed on the surface. C: There are sticking and scratches. D: Many sticks.

<4> Matching with Fixing Device After the completion of the printout test, the surface of the fixing film and the state of fixation of the residual toner were visually evaluated. A: Not generated. B: Slight sticking is observed. C: There are sticking and scratches. D: Many sticks.

[0322]

As described above, according to the present invention,
By specifying the binder component in the toner composition, a toner having good durability and transfer efficiency can be obtained. Further, the toner particles can be transferred with high efficiency without fusing the toner particles to the contact charging member, the photosensitive drum, and the intermediate transfer member, and the matching with the image forming apparatus is also suitable.

[Brief description of the drawings]

FIG. 1 is a schematic view of a tomographic plane of a toner according to the present invention.

FIG. 2 is a schematic explanatory view of an image forming apparatus suitable for the present invention.

FIG. 3 is an enlarged cross-sectional view of a main part of a developing device for a two-component developer used in an embodiment of the present invention.

FIG. 4 is an enlarged cross-sectional view of a main part of a developing device for a one-component developer used in an embodiment of the present invention.

FIG. 5 is a schematic diagram illustrating an image forming apparatus that reuses untransferred toner.

FIG. 6 is an exploded perspective view of a main part of the fixing device used in the embodiment of the present invention.

FIG. 7 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. 8 is a schematic diagram showing a state where a character image is hollow;

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Photoconductor (electrostatic latent image carrier) 2 Charging roller 3 Exposure 4 4-color developing device (4-1, 4-2, 4-3, 4-4) 5 Intermediate transfer body 6 Transfer material 7 Transfer roller 11 Development Agent carrier 13 Photoreceptor drum 30 Stay 31 Heater 31a Heater substrate 31b Heater 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 Exit guide (separation guide)

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G03G 15/20 101 G03G 9/08 325 331 333 365 384 15/08 507L (72) Inventor Masanori Ito 3 Shimomaruko 3 Ota-ku, Tokyo Inside No. 30-2 Canon Inc. (72) Inventor Yasawa Ayaki 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Keiji Kawamoto 3-30 Shimomaruko, Ota-ku, Tokyo Within No.2 Canon Inc. (72) Inventor Motoki Hisagi Within Canon Inc. 3- 30-2 Shimomaruko, Ota-ku, Tokyo

Claims (55)

[Claims] 1. A toner containing at least a binder resin, a colorant and a wax, wherein the binder resin is 0.1 to 50.0% by weight of a polycarbonate resin and a polycarbonate resin based on the weight of the binder resin. 50.0 to 99.9% by weight of resin other than resin
The toner has a structure in which a repeating unit of a polycarbonate resin contained in a component having a molecular weight of 1,000 or less is contained in a structure in a molecular weight distribution by gel permeation chromatography (GPC) of a tetrahydrofuran (THF) -soluble component. Component based on the weight of the toner.
A toner characterized by containing 5.0% by weight or less. 2. The toner according to claim 1, wherein the toner is tetrahydrofuran (TH).
F) In the molecular weight distribution by gel permeation chromatography (GPC) of the soluble portion,
2. The composition according to claim 1, wherein a component having a repeating unit of a polycarbonate-based resin contained in the following components in the structure is 10.0% by weight or less based on the weight of the toner. 3. Toner. 3. The toner according to claim 1, wherein the toner is tetrahydrofuran (TH).
F) In the molecular weight distribution by gel permeation chromatography (GPC) of the soluble portion,
2. The composition according to claim 1, wherein a component having a repeating unit of a polycarbonate resin contained in the following components in the structure is contained in an amount of 5.0% by weight or less based on the weight of the toner. Toner. 4. The polycarbonate resin has a peak molecular weight in a molecular weight range of 1,000 to 500,000 in a molecular weight distribution by gel permeation chromatography (GPC) of a tetrahydrofuran (THF) soluble portion. 4. The toner according to any one of 1 to 3, above. 5. The polycarbonate resin has a peak molecular weight in a molecular weight region of 2,000 to 100,000 in a molecular weight distribution by gel permeation chromatography (GPC) of a tetrahydrofuran (THF) -soluble portion. 4. The toner according to any one of 1 to 3, above. 6. The resin other than the polycarbonate resin contains at least one resin selected from the group consisting of a styrene-acrylic resin, a polyester resin and an epoxy resin. 5. The toner according to any one of 5. 7. The toner has a shape factor SF-1 of 100 to 160 and a shape factor SF-2 of 1 by an image analyzer.
The toner according to any one of claims 1 to 6, wherein the toner has a particle diameter of 00 to 140. 8. The toner has a shape factor SF-1 of 100 to 140 and a shape factor SF-2 of 1 by an image analyzer.
The toner according to any one of claims 1 to 6, wherein the toner has a number of 00 to 120. 9. The toner according to claim 1, wherein the ratio of the shape factor SF-1 to the shape factor SF-2 (SF-2 / SF) is determined by an image analyzer.
The toner according to any one of claims 1 to 8, wherein -1) is 1.0 or less. 10. The toner according to claim 1, wherein the toner has a weight average particle size of 2 μm to 10 μm.
The toner according to any one of the above. 11. The toner according to claim 1, wherein the toner has a weight average particle size of 4 μm to 8 μm. 12. The toner has a coefficient of variation (A) of 35% or less based on a number distribution calculated from the following equation: variation coefficient (A) = [S / D ₁ ] × 100. The toner according to any one of claims 1 to 11, wherein 13. The toner according to claim 1, wherein the toner contains the wax in an amount of 0.1 to 50% by weight based on the weight of the toner. 14. The toner according to claim 1, wherein the toner contains the wax in an amount of 0.5 to 30% by weight based on the weight of the toner. 15. The wax according to claim 1, wherein the wax has a maximum endothermic peak upon temperature rise in a temperature range of 40 to 130 ° C. in a DSC curve by a differential scanning calorimeter. The toner according to any one of the above. 16. The wax according to claim 1, wherein the wax has a maximum endothermic peak at a temperature rise of 50 to 100 ° C. in a DSC curve by a differential scanning calorimeter. The toner according to any one of the above. 17. The toner according to claim 1, wherein the polycarbonate resin is present on the surface of the toner particles. 18. The toner according to claim 1, wherein the polycarbonate resin is present on the surface of the toner particles, and the wax is dispersed inside the toner particles. The toner according to any one of the above. 19. The toner according to claim 17, wherein the polycarbonate resin is continuously present on the surface of the toner particles. 20. The toner according to claim 17, wherein the polycarbonate resin is present discontinuously on the surface of the toner particles. 21. The toner, comprising: a polymerizable monomer, a colorant,
21. Polymerized toner particles produced by polymerizing a polymerizable monomer composition containing at least a wax and a polycarbonate-based resin in an aqueous medium, comprising polymerized toner particles. The toner described in the above. 22. A charging step of externally applying a voltage to a charging member to charge the electrostatic latent image carrier; a latent image forming step of forming an electrostatic latent image on the charged electrostatic latent image carrier; Developing the electrostatic latent image formed on the latent image carrier with toner to form a toner image; and developing the toner image formed on the electrostatic latent image carrier with or without an intermediate transfer member And a fixing step of heating and fixing the toner image transferred onto the recording material to the recording material, wherein the toner comprises at least a binder resin, a colorant, The binder resin contains 0.1 to 50.0% by weight of a polycarbonate resin and 50.0 to 99.9% by weight of a resin other than the polycarbonate resin, based on the weight of the binder resin.
The toner has a structure in which a repeating unit of a polycarbonate resin contained in a component having a molecular weight of 1,000 or less is contained in a structure in a molecular weight distribution by gel permeation chromatography (GPC) of a tetrahydrofuran (THF) -soluble component. Component based on the weight of the toner.
An image forming method characterized by containing 5.0% by weight or less. 23. The toner according to claim 1, wherein the toner is tetrahydrofuran (T
HF) In the molecular weight distribution by gel permeation chromatography (GPC) of the soluble component,
23. The toner according to claim 22, wherein a component having a repeating unit of a polycarbonate resin contained in the component of 0 or less in the structure is contained in an amount of 10.0% by weight or less based on the weight of the toner. The image forming method as described in the above. 24. The toner according to claim 1, wherein the toner is tetrahydrofuran (T
HF) In the molecular weight distribution by gel permeation chromatography (GPC) of the soluble component,
23. The toner according to claim 22, wherein a component having a repeating unit of a polycarbonate resin contained in the component of 0 or less in the structure is contained in an amount of 5.0% by weight or less based on the weight of the toner. The image forming method as described in the above. 25. The polycarbonate-based resin according to claim 1, wherein the molecular weight distribution of the tetrahydrofuran (THF) -soluble component by gel permeation chromatography (GPC) has a peak molecular weight in a molecular weight region of 1,000 to 500,000. 25. The image forming method according to any one of 22 to 24. 26. The polycarbonate resin according to claim 1, wherein the molecular weight distribution of the soluble portion of tetrahydrofuran (THF) by gel permeation chromatography (GPC) has a peak molecular weight in a molecular weight region of 2,000 to 100,000. 25. The image forming method according to any one of 22 to 24. 27. The resin according to claim 22, wherein the resin other than the polycarbonate resin contains at least one resin selected from the group consisting of a styrene-acrylic resin, a polyester resin and an epoxy resin. 26
The image forming method according to any one of the above. 28. The toner according to claim 2, wherein a shape factor SF-1 of the image analysis device is 100 to 160 and a shape factor SF-2 is 100 to 140.
28. The image forming method according to any one of 2 to 27. 29. The toner according to claim 2, wherein a shape factor SF-1 of the image analyzer is 100 to 140 and a shape factor SF-2 is 100 to 120.
28. The image forming method according to any one of 2 to 27. 30. The ratio of the shape factor SF-1 to the shape factor SF-2 (SF-2 / S
The image forming method according to any one of claims 22 to 29, wherein F-1) has a value of 1.0 or less. 31. The image forming method according to claim 22, wherein the toner has a weight average particle diameter of 2 μm to 10 μm. 32. The toner according to claim 22, wherein the toner has a weight average particle diameter of 4 μm to 8 μm.
0. The image forming method according to any one of 0. 33. The toner according to claim 33, wherein a coefficient of variation (A) based on a number distribution calculated from the following equation: variation coefficient (A) = [S / D ₁ ] × 100 is 35% or less. The image forming method according to any one of claims 22 to 32. 34. The image forming method according to claim 22, wherein the toner contains the wax in an amount of 0.1 to 50% by weight based on the weight of the toner. 35. The image forming method according to claim 22, wherein the toner contains the wax in an amount of 0.5 to 30% by weight based on the weight of the toner. 36. The wax according to claim 22, wherein the wax has a maximum endothermic peak upon heating in a temperature range of 40 to 130 ° C. in a DSC curve obtained by a differential scanning calorimeter. An image forming method according to any one of the above. 37. The wax according to any one of claims 22 to 35, wherein the wax has a maximum endothermic peak upon heating in a temperature range of 50 to 100 ° C. in a DSC curve obtained by a differential scanning calorimeter. An image forming method according to any one of the above. 38. The image forming method according to claim 22, wherein the polycarbonate resin is present on the surface of toner particles of the toner. 39. The toner according to claim 22, wherein the polycarbonate resin is present on the surface of the toner particles, and the wax is dispersed inside the toner particles. The image forming method according to any one of the above. 40. The image forming method according to claim 38, wherein the polycarbonate resin is continuously present on the surface of the toner particles. 41. The image forming method according to claim 38, wherein the polycarbonate resin is present discontinuously on the surface of the toner particles. 42. The toner, comprising: a polymerizable monomer, a colorant,
42. The toner according to claim 22, comprising polymerized toner particles produced by polymerizing a polymerizable monomer composition containing at least a wax and a polycarbonate resin in an aqueous medium. The image forming method as described in the above. 43. In the developing step, the toner is carried on a toner carrier and developed, and the moving speed of the surface of the toner carrier is controlled by the movement of the surface of the electrostatic latent image carrier. The speed is set to 1.05 to 3.0 times the speed, and the toner carrier has a surface roughness (Ra) of 1.5 μm or less.
The image forming method according to any one of claims 22 to 42, comprising: 44. In a developing step, the toner is carried on a toner carrier and developed. The toner carrier comprises a non-magnetic sleeve and a magnet contained inside the non-magnetic sleeve. 44. A toner layer is formed on the toner carrier by providing a ferromagnetic metal blade at a distance from the surface of the non-magnetic sleeve. Image forming method. 45. In the developing step, the toner is carried on the surface of the toner carrier and developed, and an elastic blade is brought into contact with the surface of the toner carrier to form the toner on the toner carrier. The image forming method according to any one of claims 22 to 43, wherein a toner layer is formed. 46. In the developing step, the toner is carried on a toner carrier and developed, and a gap is formed between the surface of the toner carrier and the surface of the electrostatic latent image carrier. The thickness of the toner layer carried on the toner carrier is smaller than the distance, and a developing bias having an AC bias is applied to the toner carrier during development. The image forming method according to any one of claims 22 to 42. 47. In the charging step, the charging member to which an external voltage is applied is brought into contact with the surface of the electrostatic latent image carrier to charge the electrostatic latent image carrier. Item 47. The image forming method according to any one of Items 22 to 46. 48. The fixing device according to claim 22, wherein in the fixing step, the fixing of the toner image to the recording material is achieved by using a heat fixing device in which the offset preventing agent is not supplied to the fixing member. The image forming method according to any one of the above. 49. In a fixing step, the toner image is formed on the recording material by using a heat fixing device having no cleaning member for cleaning the surface of the fixing member in contact with the surface of the fixing member. The image forming method according to any one of claims 22 to 47, wherein the fixing is achieved. 50. In the fixing step, the toner image transferred to the recording material is applied by using a heat fixing device that applies heat and pressure while the toner image transferred to the surface of the recording material is in contact with a film. The image forming method according to any one of claims 22 to 47, wherein image fixing is achieved. 51. In the developing step, the development of the electrostatic latent image is accomplished by a developing means having the toner, and the toner remaining on the surface of the electrostatic latent image carrier after the transfer is removed. Collecting and cleaning, supplying the collected toner to the developing unit, holding the collected toner in the developing unit, and achieving image formation using a toner reuse method used for developing the electrostatic latent image again. The image forming method according to any one of claims 22 to 50, wherein: 52. In the transfer step, the toner image formed on the electrostatic latent image carrier is transferred from the electrostatic latent image carrier to the recording material without passing through the intermediate transfer body. The image forming method according to any one of claims 22 to 51. 53. In the transfer step, a transfer member to which an external voltage is applied is brought into contact with the surface of the electrostatic latent image carrier via the recording material, and the toner image is transferred to the recording material. The image forming method according to claim 52, wherein the method is performed. 54. In the transfer step, a toner image formed on the electrostatic latent image carrier is primarily transferred to an intermediate transfer member, and the toner image primarily transferred to the intermediate transfer member is secondarily transferred to the recording material. The image is transferred.
2. The image forming method according to any one of 1. 55. In the transfer step, a transfer member to which a voltage is externally applied is brought into contact with the surface of the intermediate transfer body via the recording material, and the toner image is secondarily transferred to the recording material. 55. The image forming method according to claim 54, wherein: