JP2002196532A - Dry toner, method for producing the same and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dry toner giving a high resolution and high definition image, having satisfactory stability of a charged state, improved fixability and anti-offsetting property and capable of stably providing high quality images over a long period of time. SOLUTION: The dry toner has toner particles containing at least a bonding resin, a colorant and a wax component and an external additive. The bonding resin contains a component derived from at least one monomer selected from the group comprising butadiene, isoprene and chloroprene. When the specific surface area of the toner by the BET method when the toner is allowed to stand in an environment at 23 deg.C ambient temperature and 65% relative humidity for 72 hr is represented by A (m2/g) and the specific surface area of the toner by the BET method when the toner is allowed to stand in an environment at 50 deg.C ambient temperature and 3% relative humidity for 72 hr is represented by B (m2/g), A and B satisfy a specified relation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art As an electrophotographic technique, US Pat.
Numerous methods are known as described in Japanese Patent Publication No. 297,691, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748. Generally, an electrostatic latent image is formed on a photoreceptor by various means using a photoconductive substance, and then the electrostatic latent image is developed using a dry toner (hereinafter, also referred to as "toner"). After the transfer of the toner image to a transfer material such as paper or a film, the toner image is fixed by heating, pressure, heat and pressure, or solvent vapor to obtain a toner image.

As a method for visualizing an electrostatic latent image, a cascade developing method, a magnetic brush developing method, a pressure developing method and the like are known. Further, a method is also used in which a magnetic toner is used and a rotating sleeve having a magnetic pole disposed at the center is used to fly between the photosensitive member and the sleeve by an electric field.

The one-component developing system does not require carrier particles such as glass beads and iron powder as in the two-component developing system, so that the developing device itself can be reduced in size and weight. Further, in the two-component developing method, since it is necessary to keep the toner concentration in the carrier constant, a device for detecting the toner concentration and supplying a necessary amount of toner is required. Therefore, the developing device also becomes large and heavy here. Since such a device is not required in the one-component developing system, it can be generally made relatively small and light.

[0005] In recent years, LED and LBP printers have become the mainstream in the printer market, and the direction of technology has been increased to higher resolution, ie, 300,600 dpi to 1200,2400 dpi.
Accordingly, a higher definition has been required for the developing system. In addition, the functions of the copying machine have been advanced, and the digital copying machine is moving toward digitalization.
This direction is mainly a method of forming an electrostatic latent image with a laser, and therefore is also a direction of high resolution, and a high-resolution and high-definition developing method is required similarly to a printer.

In order to achieve high resolution and high definition, it is required to reduce the particle size of the toner. However, when the particle size of the toner is reduced, the chargeability of the toner particles increases, and in order to achieve the above object, control of the toner particle becomes important.

For example, in Japanese Patent Application Laid-Open No. 4-276762, the average particle size produced by a polymerization method is 3 to 8 μm.
A toner in which specific carbon black is adhered to the surface of m toner particles has been proposed. In the case where an image is output using a toner in which a material for controlling chargeability is disposed on the surface of a particle as described above, carbon black adhered to the surface of the particle may fall off when the number of sheets passed exceeds approximately 5,000. As a result, the chargeability of the toner greatly changes, and the charge stability becomes insufficient.

[0008] Proposals for imparting charge stability from the viewpoint of materials include, for example, JP-A-6-242631. However, when image evaluation was actually performed by the method described in the publication, there was still room for improvement in resolution.

In order to make the chargeability of the toner uniform, there is a method of increasing the regulating force on the toner by a regulating member or the like. If the regulating force on the toner is increased, the toner is likely to deteriorate due to friction, and the image quality tends to decrease as the number of output images increases.

Therefore, it is necessary to increase the strength of the toner. In general, the problem is solved by increasing the glass transition temperature of the binder resin of the toner or by introducing a crosslinking component into the binder resin to increase the elastic modulus in the temperature range below the glass transition temperature of the toner. However, as a result, it is necessary to increase the fixing temperature at the time of image formation, or in the case of fixing with a heat roller, to set the pressure applied by the roller to be high, and to reduce the necessary heat energy. Accordingly, problems such as an increase in power consumption and an increase in the frequency of roller contamination and winding offset occur.

On the other hand, in order to lower the fixing temperature, there are methods of lowering the glass transition temperature and reducing the amount of the cross-linking component. However, such a method has the above-mentioned adverse effects and furthermore, the blocking during storage of the toner. To reduce the
Not preferred.

Although various methods and apparatuses have been developed for a process for fixing a toner image to a sheet such as paper or film, the most common method at present is a fixed heat generating heater via a heat roller or a heat-resistant film. It is a compression heating method.

In the pressure heating method using a heating roller, a toner image is formed by passing the surface of a heat roller having releasability to the toner and the toner image surface of the sheet under pressure while passing the sheet under fixing. The fixing is performed.
In this method, since the surface of the heat roller and the toner image on the sheet to be fixed come into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image onto the sheet to be fixed is extremely good, and the fixing can be performed quickly. Can be.

However, in such a fixing method, since the surface of the heating roller and the toner image come into contact with each other under pressure and in a molten state, a part of the toner image adheres to and transfers to the surface of the fixing roller, and the next toner image is transferred. This is re-transferred to the fixing sheet, and the so-called offset phenomenon, which stains the sheet to be fixed, is likely to occur.
Since such an offset phenomenon is greatly affected by the fixing speed and the fixing temperature, generally, when the fixing speed is low,
If the surface temperature of the heating roller is set relatively low and the fixing speed is high, the surface temperature of the heating roller is set relatively high so that the amount of heat applied to the toner from the heating roller to fix the toner is always constant. It has been attempted to suppress the offset phenomenon by adjusting the amount.

Since the toner on the sheet to be fixed forms several toner layers, particularly in a system in which the fixing speed is high and the surface temperature of the heating roller is high, the toner layer in contact with the heating roller is covered with the toner layer. If the surface temperature of the heating roller is high because the temperature difference between the lowermost toner layer and the lowermost toner layer that is in contact with the fixing sheet is large, the toner in the uppermost layer is likely to cause an offset phenomenon (high-temperature offset), When the temperature is low, the toner in the lowermost layer is not sufficiently melted, so that a phenomenon in which the toner is not fixed on the sheet to be fixed (low-temperature offset) is likely to occur.

As a method for solving this problem, when the fixing speed is high, a method of increasing the pressure at the time of fixing and anchoring the toner to the sheet to be fixed is usually used. According to this method, the temperature of the heating roller can be reduced to some extent, and the high-temperature offset phenomenon of the uppermost toner layer can be prevented. However, since the shearing force applied to the toner becomes extremely large, the sheet to be fixed is wound around the fixing roller, and a winding offset occurs, or the separation claw for separating the sheet to be fixed from the fixing roller is fixed. Easy to appear in images. Further, since the pressure is high, the image quality of the fixed image tends to be deteriorated such as the line image is crushed or the toner is scattered at the time of fixing.

In high-speed fixing, generally, a toner having a lower melt viscosity than that in low-speed fixing is used, the surface temperature of the heating roller is lowered, and the fixing pressure is lowered, thereby preventing high-temperature offset and winding offset. The toner image is fixed. However, when such a toner having a low melt viscosity is used for low-speed fixing, an offset phenomenon is likely to occur at a high temperature.

By reducing the particle size of the toner, the resolving power and sharpness of an image are increased, while the fixability of a halftone portion formed with the toner having a small particle size is reduced. This phenomenon is particularly remarkable in high-speed fixing. This is because the amount of applied toner in the halftone portion is small, and the toner transferred to the concave portion of the fixing sheet has a small amount of heat given from the heating roller,
Further, the fixing pressure becomes worse because the pressure on the concave portion is suppressed by the convex portion of the sheet to be fixed. The toner transferred to the convex portion of the sheet to be fixed in the halftone portion is
Since the thickness of the toner layer is small, the shearing force applied to each toner particle is larger than that of a solid black portion having a large thickness of the toner layer.

Further, in order to cope with recent downsizing of the apparatus, high printing speed, and networking, the anti-offset area of the toner is widened to a low temperature side so that the fixing device can be simplified easily, and the toner can be fixed easily. Reducing the temperature to make the fixing process faster is an effective method.

Further, in order to prevent the offset phenomenon, the surface of the heating roller is processed with a material having excellent releasability such as a fluorine-based resin, or a means is applied by applying a releasing agent such as silicone oil to the surface of the heating roller. Is also possible. However, the method of applying silicone oil or the like is not preferable because not only the size of the fixing device is increased and the cost is increased, but also the device becomes complicated, which easily causes trouble.

Further, Japanese Patent Publication No. 57-493, Japanese Patent Application Laid-Open No. 50-44836 and Japanese Patent Application Laid-Open No. 57-37353 disclose a method for improving the offset phenomenon by making the resin asymmetric or crosslinked. Although described, the improvement relating to the fixing temperature has not been sufficiently made.

Generally, since the minimum fixing temperature is between the low-temperature offset and the high-temperature offset, the usable temperature range is between the minimum fixing temperature and the high-temperature offset. By increasing the temperature, the usable fixing temperature can be lowered and the usable temperature range can be widened, so that energy saving, high-speed fixing, and prevention of paper curl can be achieved. For this reason, a toner having good fixability and anti-offset property is always desired.

For this purpose, JP-A-9-265209 discloses a low molecular weight vinyl polymer component having a weight average molecular weight of 3 × 10 ³ to 1 × 10 ⁴ and a weight average molecular weight of 3 × 10 3
^An antioxidant is added to 100 parts by weight of a vinyl polymer mainly composed of a high molecular weight vinyl polymer component of ⁵ to 1 × 10 ⁶ .
It has been proposed that a toner resin composition containing 0.5 to 1 part as a main component is melted and kneaded, then cooled and finely pulverized so that a fixing temperature range can be widened by a toner obtained. However, in this method, the fixing region is merely shifted to the low temperature side, and the offset on the high temperature side is likely to be deteriorated.

On the other hand, Japanese Patent Application Laid-Open No. 8-262799 discloses a high molecular weight styrene-acrylic resin having a molecular weight peak in a region of 500,000 or more in molecular weight distribution measured by gel permeation chromatography, and a molecular weight of 50,000. A toner is proposed from a styrene-acrylic resin having a peak in a region of 500,000 to 500,000, a styrene-acrylic resin having a crosslinked structure, and a polyester resin binder resin having a molecular weight peak in a region having a molecular weight of 50,000 or less. Support for high-speed fixing is still insufficient.

Further, there has been proposed a technique for improving low-temperature fixability by using a capsule toner composed of a core material and an outer shell provided so as to cover the surface of the core material. Among them, it is reported that when a low melting point wax or the like which is easily plastically deformed is used as a core material, fixing can be performed only by pressure (US Pat. No. 3,269,626; Japanese Patent Publication No. 46-15876; JP-B-44-9880, JP-A-48-75032, JP-A-48-75
No. 033). However, the fixing strength is inferior, and it is used only for limited applications. When a liquid core material is used, if the strength of the shell material is low, fixing can be performed only by pressure, but it may crack in the developing unit and stain the inside of the machine. Large pressure is required to destroy the particles, resulting in an image with too high gloss, and it is difficult to adjust the strength of the shell material.

Therefore, when used alone as a core material for heat and pressure fixing, blocking occurs at a high temperature, but a resin having a low glass transition point which improves the fixing strength is used, and blocking resistance and the like are imparted as an outer shell. For this purpose, a capsule toner for fixing a heat roller having a high melting point resin wall formed by interfacial polymerization has been devised (JP-A-61-5).
No. 6352). However, since the wall material has a high melting point and is tougher and harder to break, the performance of the core material has not been fully exploited.

In Japanese Patent Application Laid-Open No. 8-286416, an unsaturated polyester resin or a styrene-acryl resin is coated by adsorbing and polymerizing a mixture of a polymerizable monomer and particles obtained by suspension polymerization. Techniques are disclosed. According to this technique, it is possible to obtain a toner which is very excellent in durability and more improved in fixability than the above-mentioned toner, but there is still room for improvement in low-temperature fixability.

Further, a capsule toner for fixing with a heat roller in which the fixing strength of the core material is improved by the same concept has been proposed (JP-A-58-205162, JP-A-58-20).
No. 5163, JP-A-63-128357, JP-A-63-128358, JP-A-63-1283.
No. 59, JP-A-63-128360, JP-A-63-128361, JP-A-63-128362
No.). However, since the manufacturing method is a spray-drying method, a load is imposed on the manufacturing equipment, and the performance of the core material cannot be fully exploited because the shell material is not devised.

Further, the capsule toner proposed in JP-A-63-281168 has a description that the material is a thermotropic liquid crystal polyester.
No. 4358, the capsule toner has been described as a crystalline polyester, but because none of the polyester is amorphous, the resin melts sharply, but the amount of energy required for melting is large, Further, since the core material has a high glass transition temperature, the fixability is poor.

As described above, encapsulated toners using various materials and manufacturing methods have been proposed. However, all of them have sufficient low-temperature fixing properties, anti-offset properties, anti-blocking properties, and stress resistance in a developing device. It has not been satisfied, and no quantitative value has been shown so far, particularly with respect to the physical properties of the capsule toner satisfying these properties.

On the other hand, in the capsule toner proposed in Japanese Patent Application Laid-Open No. 7-301947, the degree of deformation of the toner when a load is applied within a certain load range in a micro-compression tester, and the change in the cohesion before and after heating and leaving. Stipulates,
This alone does not take into account toner deterioration during the development process, and is not actually satisfactory.

As materials, thermoplastic elastomer and 200
There has been proposed a toner having a specified storage elastic modulus at ℃ (Japanese Patent Application Laid-Open No. 7-271096), but its effect is focused on improvement of offset resistance and prevention of wrapping around a heat roller. It is still insufficient.

A toner using a polyene compound such as butadiene or isoprene, which is a general-purpose material, has been proposed in JP-A-7-271096. It is only to prevent winding.

For the above reasons, in the fixing process, although a toner having a wide fixing temperature range and excellent in anti-offset property is desired, those points are sufficiently satisfied, and high resolution and high resolution are achieved. In fact, no toner satisfies the definition and the charging stability.

In the method for producing the toner, after the step of suspension-polymerizing the polymerizable monomer composition in the presence of an oil-soluble polymerization initiator until the polymerization conversion falls within the range of 30 to 97%,
A method of further polymerizing by adding a water-soluble polymerization initiator,
It is disclosed in JP-A-11-160909. However, in this method, a macromonomer is used, and the reactivity is lower than that of a normal monomer, and is insufficient for obtaining a toner having excellent durability.

On the other hand, if the transfer residual toner remains on the photoconductor when the toner image formed on the photoconductor in the development process is transferred to the transfer material in the transfer process, it is cleaned in the cleaning process and stored in a waste toner container. It needs to be stored.
For this cleaning step, conventionally, blade cleaning, fur brush cleaning, roller cleaning and the like have been used. In either method, the toner remaining after transfer is mechanically scraped off or dammed and collected in a waste toner container. Therefore, there is a problem caused by such a member being pressed against the surface of the photoconductor. For example, when a toner having a large amount of transfer residue is used, it is necessary to strongly press the member, and the life of the photosensitive member is shortened because the photosensitive member is worn.

From the viewpoint of the apparatus, the provision of such a cleaning apparatus inevitably increases the size of the apparatus, which has been a bottleneck when aiming for a more compact apparatus. Furthermore, from the viewpoint of ecology, a system that does not use waste toner is desired in terms of effective use of toner.

Here, Japanese Patent Application Laid-Open Nos. Sho 59-133573, Sho 62-203182, and Sho 63-1 disclose cleaner related technologies.
No. 33179, JP-A-64-20587, JP-A-2-302772, JP-A-5-2289, JP-A-5-53482, JP-A-5-6138
There is a publication No. 3 and the like, but there is no mention of a desirable toner configuration.

In the developing / cleaning configuration essentially having no cleaning device, the surface of the photoreceptor is rubbed with toner and a toner carrier, the toner in the non-image area is collected by the toner carrier, and the image area is In such a case, it is necessary to provide a configuration for developing. At the time of this rubbing, if the oppositely charged toner such as the transfer residual toner or the fogging toner can be easily reversed, electrical recovery becomes easy. One way to achieve this is to add a polar component to the toner.

That is, a toner containing many polar components utilizes the general phenomenon that the charging speed is high. However, as described above, a toner such as polyethylene or polypropylene is used to improve the offset property of the toner. When a release agent having almost no toner is added, the charging speed of the toner decreases, and the smooth recovery of the toner on the photoconductor in the developing process is hindered. As a result, a print image that is originally an image-free area stained with a toner in an image form, that is, a so-called ghost image is obtained.

As described above, in the developing / cleaning structure, a technique for achieving both the fixing property of the toner and the image characteristics is desired. Furthermore, the technology to collect toner in the development process
This can be said to be very important even in a system in which the pressing of the member is weakened in order to extend the life of the photoconductor.

[0042]

SUMMARY OF THE INVENTION An object of the present invention is to provide a dry toner which has solved the above-mentioned problems.

An object of the present invention is to provide a dry toner having excellent charge stability.

An object of the present invention is to provide a dry toner capable of obtaining a high-resolution and high-definition image and having excellent fixability and offset resistance.

An object of the present invention is to provide a toner capable of stably obtaining a high-quality image for a long period of time.

Another object of the present invention is to provide a dry toner which is highly applicable to an electrophotographic process which does not adversely affect a photoreceptor, a toner carrier, an intermediate transfer member, etc., a method for producing the above toner, and the above toner. To provide an image forming method using the same.

Further, an object of the present invention is to provide a contactless type image forming process using a cleaner-less structure or an intermediate transfer member while maintaining the fixing property and the resolution.
An object of the present invention is to provide an electrophotographic image forming method capable of improving transferability, suppressing generation of a ghost by improving toner recovery, and further improving durability.

[0048]

SUMMARY OF THE INVENTION The present invention provides a dry toner comprising at least a toner particle containing a binder resin, a colorant and a wax component, and an external additive,

(1) The binder resin contains a component derived from at least one monomer selected from the group consisting of butadiene, isoprene and chloroprene,
(2) The main glass transition temperature (Tg) of the toner measured by a differential scanning calorimeter (DSC) is 40 to 70.
(3) The specific surface area according to the BET method when left in an environment of the ambient temperature of 23 ° C. and a relative humidity of 65% for 72 hours is A (m ² / g), the ambient temperature of the toner is 50 ° C. When the specific surface area by the BET method when left in an environment of a relative humidity of 3% for 72 hours is B (m ² / g), A and B satisfy the following formula: 0.8 ≦ A ≦ 4.0 0.80 ≦ (B / A) ≦ 1.05 (4) The circle equivalent number of the toner in the circle equivalent diameter-circularity scattergram based on the number of toners measured by the toner flow type particle image measuring apparatus. Average diameter D1 is 2
10 μm, and the average circularity of the toner is 0.950
0.995, the circularity standard deviation is less than 0.040, and (5) tetrahydrofuran (TH
F) In the molecular weight distribution measured by gel permeation chromatography (GPC), the soluble component has a main peak molecular weight in the range of 2 × 10 ³ to 1 × 10 ⁵ and a THF insoluble component of 5 to 60% by mass. The present invention relates to a dry toner.

Further, the present invention provides a diene monomer component-containing resin containing a component derived from at least one monomer selected from the group consisting of butadiene, isoprene and chloroprene, a polymerizable vinyl monomer, and a colorant. , A polymerizable monomer composition containing a wax and a polymerization initiator, dispersed in an aqueous medium, granulated, and polymerized in the aqueous medium to produce toner particles, wherein the polymerization initiator Is a radical polymerization initiator, and relates to a method for producing a dry toner, wherein a radical polymerization initiator is newly added when the conversion of the polymerization reaction is in the range of 10 to 95% by mass.

Further, according to the present invention, there is provided a charging step of applying a voltage to a charging member to charge an electrostatic latent image carrier, and an electrostatic step of forming an electrostatic latent image on the charged electrostatic latent image carrier. A latent image forming step, and a developing step of adhering the toner carried on the toner carrier to the electrostatic latent image formed on the electrostatic latent image carrier to form a toner image on the electrostatic latent image carrier Process, a transfer step of electrostatically transferring the toner image formed on the electrostatic latent image carrier to a transfer material with or without an intermediate transfer body, and a toner image electrostatically transferred to the transfer material Fixing step of fixing the image forming method,

The toner is a dry toner having toner particles containing at least a binder resin, a colorant and a wax component, and an external additive. (1) The binder resin is a group consisting of butadiene, isoprene and chloroprene. And (2) a main glass transition temperature (Tg) of the toner measured by a differential scanning calorimeter (DSC) of 40 to 40.
(3) an ambient temperature of the toner of 23 ° C.
BET when left in an environment with a relative humidity of 65% for 72 hours
The specific surface area of law A (m ² / g), ambient temperature 50 ° C. of the toner, when the BET specific surface area when left for 72 hours in a relative humidity of 3% Environmental and B (m ² / g) A and B satisfy the following formula: 0.8 ≦ A ≦ 4.0 0.80 ≦ (B / A) ≦ 1.05 (4) The toner is measured by a flow type particle image measuring apparatus. In a circle equivalent diameter-circularity scattergram based on the number of toners, the circle equivalent number average diameter D1 of the toner is 2 to 2.
10 μm, and the average circularity of the toner is 0.950
0.995, the circularity standard deviation is less than 0.040, and (5) tetrahydrofuran (TH
F) In the molecular weight distribution measured by gel permeation chromatography (GPC), the soluble component has a main peak molecular weight in the range of 2 × 10 ³ to 1 × 10 ⁵ and a THF insoluble component of 5 to 60% by mass. And an image forming method.

[0053]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

<1> Dry Toner of the Present Invention The dry toner of the present invention (hereinafter referred to as “toner”) has toner particles containing at least a binder resin, a colorant and a wax component, and inorganic fine powder.

The binder resin in the toner of the present invention contains a component derived from at least one monomer selected from butadiene, isoprene and chloroprene (hereinafter also referred to as “diene monomer”). .

None of the above diene monomers has an oxygen atom. Therefore, since there is no site for adsorbing moisture in the air, electric charge leakage hardly occurs in the toner. Therefore, the influence of humidity on the charge amount is reduced, and as a result, the chargeability of the toner is stabilized. Furthermore, since one molecule has two double bonds capable of undergoing radical polymerization, it is easy to form a three-dimensional structure, which may be caused by, for example, a viscosity increasing effect or formation of a network structure. Therefore, without being significantly affected by the manufacturing method, to improve the existing state of the material (half) dissolved and dispersed in the toner particles such as pigments and charge control agents, to stabilize the chargeability, Is considered to be able to improve the color of the toner. When a monomer such as styrene or hydrogenated vinylcyclohexane is used, the former effect due to the absence of an oxygen atom can be obtained, but the latter effect due to having two double bonds in one molecule. Is difficult to obtain due to the characteristics of the monomer. Furthermore, in the case of monomers such as divinylbenzene, when both double bonds in one molecule react, the structure is cross-linked by a rigid benzene ring, and the flexibility between the cross-linking points of the polymer is lost. Adverse effects on the surface or increase brittleness. For the reasons described above, a diene monomer is used as an essential component in the present invention.

In addition, butadiene, chloroprene and isoprene have boiling points of -4.4 ° C, 59.4 ° C, 3
At 4.1 ° C., both are highly volatile at normal pressure. Therefore, when a diene monomer is directly introduced into a toner produced by a suspension polymerization method described below, the diene monomer volatilizes during polymerization. Therefore, it is preferable to carry out suspension polymerization under pressure or to prepare a resin in advance by another means and add it. The latter is more preferable for quantitatively introducing into the toner.

The resin containing a diene monomer is preferably a solution polymerization under pressure, an emulsion polymerization, a soap-free polymerization, or the like.

As the resin containing a diene monomer used in the suspension polymerization, a resin polymerized with a polymerization initiator having a carboxyl group, a sulfate group or the like is preferably used. The reason is that the diene monomer-containing resin is easily localized near the surface of the toner particles obtained by including a polar group in the polymer, and the effect of improving durability can be obtained by taking a three-dimensional structure. That's why.

In the present invention, the total content of components derived from butadiene, isoprene and chloroprene contained in the binder resin is preferably 0.1 to 20% by mass based on the toner.

In order to prevent low-temperature and high-temperature offsets, the toner is mixed with a high molecular weight resin or a crosslinked resin having a peak molecular weight exceeding 5 × 10 ⁵ in the molecular weight distribution measured by GPC of the THF-soluble portion of the toner. , Toner THF
In general, the viscoelasticity of a toner is designed by using a low molecular weight resin having a peak molecular weight of about 1 × 10 ^{3 to} 5 × 10 ⁴ in a molecular weight distribution measured by GPC of a soluble component as a binder resin. However, if the content of the diene monomer in the binder resin exceeds 20% by mass, it may be difficult to produce a toner having such a design, which may cause a problem. Therefore, the content of the diene monomer preferably does not exceed 20% by mass of the toner, and more preferably ranges from 0.1 to 10% by mass. The content of the diene monomer in the binder resin is 0.1% by mass.
If it is less than 3, the stabilization of charging, which is an effect of the present invention, cannot be sufficiently achieved, and a high-resolution and high-definition image may not be obtained.

The measurement of the content of the diene monomer contained in the toner of the present invention is not particularly limited, but is carried out by a combination of a pyrolysis gas chromatograph and a mass spectrum or by a combination of elemental analysis and other measuring methods. I can do it. It is also possible to estimate the amount of the diene monomer component by quantifying the amount of the diene monomer contained in the THF-soluble component in the toner by ¹ H-NMR, ¹³ C-NMR, or the like.

In the present invention, the monomer constituting the binder resin is, as described above, a monomer selected from the group consisting of butadiene, chloroprene, and isoprene.
(Hereinafter, also referred to as `` diene monomer '') is not particularly limited as long as it contains as an essential component, other monomers constituting the binder resin, for example, styrene, o (m-, p -)
Styrene monomers such as -methylstyrene, m (p-)-ethylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate , (Meth) acrylic acid-n-
Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid-2 -Ethylhexyl, adamantyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, isobornyl (meth) acrylate, dimethylaminoethyl (meth) acrylate (Meth) acrylate monomers such as diethylaminoethyl (meth) acrylate; maleic ester monomers such as dimethyl maleate and diethyl maleate; vinyl ether monomers such as ethyl vinyl ether and cyclohexyl vinyl ether Monomer; (meth) acrylic acid, maleic acid,
Fumaric acid, maleic anhydride, cyclohexene, (meth)
Monomers such as acrylonitrile and acrylamide are preferably used. These may be used alone or in combination of two or more.

Among them, styrene monomers such as styrene and styrene derivatives are preferred when copolymerized with a diene monomer because of excellent charge stability of the toner. As the binder resin in the present invention, a copolymer of the above styrene monomer and a diene monomer, particularly a copolymer of butadiene, is preferable.

The resin containing a diene monomer as an essential component used as a binder resin in the present invention (hereinafter referred to as “diene monomer component-containing resin”) is used to improve the charge stability of the toner. In addition, it may be modified with epoxy, maleic anhydride, maleic acid (half) ester, and / or a methacrylic acid derivative.

Further, as the binder resin in the present invention,
Of the above-mentioned diene monomer component-containing resin with polystyrene, styrene- (meth) acrylic copolymer, general polyester, polyurethane, epoxy resin, polyolefin, polyamide, polysulfone, polycyanoaryl ether, polyarylene sulfide It is also possible to use a block copolymer or a graft-modified copolymer obtained by grafting an alkyl (meth) acrylate, (meth) acrylic acid, maleic acid or a styrene monomer onto a resin containing a diene monomer component.

In the present invention, other resins can be used in combination with the resin containing the diene monomer component. Other resins used in combination with the diene monomer component-containing resin include commonly used styrene-acrylic resins,
Various resins such as a polyester resin and an epoxy resin are exemplified.

These resins can be obtained by polymerizing the following monomers. Specific monomers include styrene-based monomers such as styrene, o (m-, p-)-methylstyrene, m (p-)-ethylstyrene; methyl (meth) acrylate, (meth) acrylic Ethyl acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate,
N-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) ) Acrylic acid-2
-Ethylhexyl, adamantyl (meth) acrylate,
(Meta) such as dodecyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate ) Acrylic ester monomers; maleic ester monomers such as dimethyl maleate and diethyl maleate; vinyl ether monomers such as ethyl vinyl ether and cyclohexyl vinyl ether; (meth) acrylic acid, maleic acid, Examples include monomers such as fumaric acid, maleic anhydride, butadiene, isoprene, cyclohexene, (meth) acrylonitrile, and acrylamide. These may be used alone or in combination of two or more.

In the present invention, the resin used in combination with the diene monomer component-containing resin is preferably contained in the binder resin in an amount of 50 to 99.9% by mass, and more preferably 80 to 99.9% by mass.
-99.9% by mass, more preferably 85-99.5% by mass, particularly preferably 85-98% by mass. The type of the resin is preferably a styrene-acrylic resin.

The resin used in combination with the resin containing the diene monomer component may be used alone or with a theoretical glass transition temperature (Tg) of 4 or less.
The above monomers are appropriately mixed and used so as to show 0 to 75 ° C. In order to set the theoretical glass transition temperature (Tg) as described above, generally, the published Polymer Handbook, 2nd edition
III-139 to 192 (manufactured by John Wiley & Sons). Similarly, when other resins are used in combination, they may be used alone or in a theoretical glass transition temperature (Tg).
Are appropriately mixed and used so as to show a temperature of 40 to 75 ° C.

If the theoretical glass transition temperature is lower than 40 ° C., problems tend to occur in terms of storage stability and durability stability of the toner, while if it exceeds 75 ° C., the fixing point of the toner may increase. is there. 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, the color reproducibility is poor, and the
This is not preferable because the transparency of the HP image is reduced.

The toner of the present invention contains a colorant and a wax component in addition to the binder resin.

The toner of the present invention is used as a releasing agent such as a hydrocarbon compound, a higher fatty acid, a higher alcohol and a derivative thereof in the toner for the purpose of improving the releasability at the time of hot roll fixing. It is preferable to mix a wax component. Specific examples of such wax components include paraffin wax and its derivatives, microcrystalline wax and its derivatives, Fischer-Tropsch wax and its derivatives, polyolefin wax and its derivatives, carnauba wax and its derivatives, alcohol, fatty acid, and acid amide. , Esters, ketones, hydrogenated castor oil and derivatives thereof, vegetable waxes, animal waxes, mineral waxes, petrolactam, and derivatives include oxides, block copolymers with vinyl monomers and graft-modified products. included.

These wax components may be used alone or in combination of two or more.

[0075] These wax components were found to have a viscosity of 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 130 degree region. By having the maximum endothermic peak in the above temperature range, it greatly contributes to low-temperature fixing, and also effectively exhibits releasability. If the maximum endothermic peak is less than 40 ° C., the self-cohesive force of the wax component becomes weak, resulting in poor high-temperature offset resistance and excessively high gloss.

On the other hand, if the above-mentioned maximum endothermic peak exceeds 130 ° C., the fixing temperature becomes high and it becomes difficult to appropriately smooth the surface of the fixed image. It is not preferable from the point of view. 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 measurement was performed at a heating rate of 10 ° C./min. In the present invention, the addition amount of these wax components is not particularly limited, but is preferably 0.5 to 30% by mass based on the toner.

As the colorant used in the toner of the present invention, conventionally known inorganic and organic dyes / pigments can be used, and include the following yellow colorants, magenta colorants and cyan colorants. .

Further, carbon black, aniline black, acetylene black, magnetic substance,
A baked pigment or a mixture of a yellow colorant / magenta colorant / cyan colorant shown below and toned to black may be used.

When carbon black is used in the toner of the present invention, the primary particle size is preferably 25 to 80 nm. Regarding the particle size of carbon black, 25 nm
If it is smaller, sufficient dispersion may not be obtained due to the fine primary particle size, and it may be difficult to make full use of it. 80
If it is larger than nm, only a low-density image can be obtained due to insufficient coloring power as a toner even if dispersed well.
Alternatively, inconveniences such as an increase in toner consumption may occur. Furthermore, as for the particle size of the carbon black, the particle size is more preferably 35 to 70 nm,
The charge polarity and charge amount of the transfer residual toner by the charging member can be more reliably and uniformly controlled, which is more advantageous in terms of the stability of the charge amount of the toner and the toner coloring power.

Further, the toner of the present invention uses a magnetic substance as a black colorant, and can be used as a magnetic toner. Magnetic materials that can be used in this case include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; and metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, and antimony. , Beryllium, bismuth, cadmium, calcium, manganese, selenium, alloys with metals such as 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 for a polymerization method 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 preferably have an average particle size of 2 μm or less, more preferably 0.1 to 0.5 μm.
m. The amount of the magnetic substance contained in the toner particles is 20 to 200 parts by mass per 100 parts by mass of the binder resin.
It is part by mass, particularly preferably 40 to 150 parts by mass. In addition, the magnetic characteristics when 796 kA / m (10 kOe) is applied show a coercive force (Hc) of 1580 to 23700 A / m.
(20-300 Oersted), saturation magnetization (σs) 50
~ ²⁰⁰ Am ² / kg (emu / g), residual magnetization (σ
r) A magnetic material of ^{2 to 20} Am ² / kg (emu / g) is preferred.

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, 62, 74, 83, 9
3, 94, 95, 109, 110, 111, 128, 129, 147, 168, 180
Is 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, 26, 48: 2, 48:
3, 48: 4, 57: 1, 81: 1, 144, 146, 166, 169, 177, 18
4, 185, 202, 206, 220, 221, 254 are particularly preferred.

As the cyan coloring agent, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds and basic dye lake compounds can be used. Specifically, CI Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 6
2, 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 colorant to be added is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

When a magnetic material is used as the black colorant, it is preferable to use 40 to 150 parts by mass with respect to 100 parts by mass of the binder resin, unlike other colorants.

The toner of the present invention may contain a charge control agent, and any known charge control agent can be used. In particular, the charge speed is high and a constant charge amount is stably maintained. Preferred charge control agents are preferred. Further, when the toner particles are produced by a direct polymerization method, a charge control agent having a low polymerization inhibitory property and having substantially no solubilized substance in an aqueous dispersion medium is particularly preferable. Specific compounds include salicylic acid as a negative charge control agent, naphthoic acid, a metal compound of an aromatic carboxylic acid such as dicarboxylic acid, a polymer compound having a sulfonic acid or carboxylic acid group in a side chain, a boron compound, Urea compounds, silicon compounds,
Calix arene. Examples of the positive charge control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in a side chain, a guanidine compound, and an imidazole compound. The charge control agent is preferably used in an amount of 0.5 to 10 parts by mass based on 100 parts by mass of the binder resin.

In the present invention, the addition of a charge control agent is not essential. When a two-component developing method is used, triboelectric charging with a carrier is used, and when a non-magnetic one-component blade coating developing method is used, Also, frictional charging with the blade member can be positively used.

If a charge control agent is used in the toner of the present invention, the compounds represented by the following formula (I) are more preferable.

Formula (I)

[Outside 2]

[Wherein X ₁ and X ₂ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a halogen atom, and X ₁ and X ₂ may be the same or different; And m ′ represent an integer of 1 to 3, and R ₁ and R ₃
Is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms,
18 alkenyl group, a sulfonamide group, a mesyl group, a sulfonyl group, a hydroxyl group, an alkoxy group having 1 to 18 carbon atoms, an acetylamino group, benzoylamino group, a halogen atom or -COOR _5, R ₁ and R ₃ N and n ′ may be the same or different, n and n ′ represent an integer of 1 to 3, R ₂ and R ₄ represent a hydrogen atom or a nitro group, R ₅ represents an alkyl group or an aryl group, A ⁺ represents a hydrogen ion, a sodium ion, a potassium ion or an ammonium ion. ]

As the lower alkyl group for X ₁ and X ₂ ,
1-10 carbon atoms such as methyl group, ethyl group and propyl group
Alkyl group. Examples of the lower alkoxy group for X1 and X2 include a C1-C10 alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group.

Examples of the halogen atom for X ₁ , X ₂ , R ₁ and R ₃ include fluorine, bromine, chlorine and iodine.

Preferred examples of X ₁ and X ₂ include a hydrogen atom and a nitro group.

Examples of the alkyl group having 1 to 18 carbon atoms for R ₁ and R ₃ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group.

Examples of the alkenyl group having 1 to 18 carbon atoms for R ₁ and R ₃ include a vinyl group, an allyl group, a propenyl group and a butenyl group.

Examples of the alkoxy group having 1 to 18 carbon atoms for R ₁ and R ₃ include a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

R ₁ and R ₃ may be a group represented by —COOR ₅ , wherein R ₅ is a methyl group, an ethyl group, a propyl group, a phenyl group, or a naphthyl group.

Among them, preferred R ₁ and R ₃ include chlorine.

Preferred R ₂ and R ₄ include hydrogen.

Preferred specific examples of the charge control agent include compounds represented by the following general formulas (II) and (III).

[0104]

[Outside 3]

[0105]

[Outside 4]

The charge control agent is preferably used in an amount of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the binder resin.

In the toner of the present invention, an external additive is mixed with the toner particles in order to improve charge stability, developability, fluidity and durability.

The external additives used in the present invention include inorganic fine powders. Specifically, silica fine powder,
Titanium oxide and alumina fine powder are exemplified, and silica fine powder is particularly preferably used. The specific surface area by nitrogen adsorption measured by BET method. Among the 30 m ² / g or more, particularly in the range of 50 to 400 m ² / g give good results. Inorganic fine powder 0.0 to 100 parts by mass of toner particles
It is good to use 1 to 8 parts by mass, preferably 0.1 to 5 parts by mass. The specific surface area of the inorganic fine powder can be calculated by the BET method by a method described later, similarly to the specific surface area of the toner.

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

Other external additives contained in the toner of the present invention include lubricants such as Teflon (registered trademark), zinc stearate, and polyvinylidene fluoride (in particular, polyvinylidene fluoride is preferable); cerium oxide, silicon carbide, Abrasive such as strontium titanate (preferably strontium titanate); anti-caking agent; conductivity-imparting agent such as carbon black, zinc oxide, antimony oxide and tin oxide; And the like.

In the present invention, in the case of a toner manufactured by adding inorganic fine powder or other external additives to toner particles, and stirring and mixing the toner particles, various physical properties of the toner particles, which will be described later, are measured as follows. It can be performed using the toner particles after removing these inorganic fine particles and other external additives. The method of removing these inorganic fine particles and other external additives from the surface of the toner particles is not particularly limited. For example, the method can be carried out by washing the toner with water as follows.

First, 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, relatively large inorganic fine particles and other external additives are released from the toner particles,
The toner particles and the inorganic fine particles and other external additives are separately dispersed in water. Next, the toner particles are isolated from the mixed dispersion. As an isolation method, for example, a filtration operation is performed using a filter paper having an appropriate aperture to separate toner particles on the filter paper and an aqueous solution containing inorganic fine particles and other external additives in the filtrate. it can. Further, as another isolation method, a method of isolating toner particles by wet classification of the mixed dispersion can be employed.

The toner of the present invention has a main glass transition temperature (Tg) of 40 to 70 ° C. in a DSC curve measured by a differential scanning calorimeter. In the present invention, when a plurality of resins having different glass transition temperatures are used, a plurality of glass transition temperatures may be observed in DSC. In that case, the larger endotherm is defined as the main glass transition temperature.

When the main glass transition temperature is less than 40 ° C.,
If the blocking resistance of the toner decreases, the fluidity in the developing device decreases, and the toner easily fuses on the toner carrier or the electrostatic latent image carrier, which is not preferable. 7
When the temperature exceeds 0 ° C., the melt viscosity of the toner given a certain amount of heat becomes high, and as a result, the fixing temperature becomes high.
That is, in order to increase the required amount of heat or fix the image with the same amount of heat, for example, the pressure applied to the transfer material must be increased, which is not preferable. More preferred glass transition temperature of the toner of the present invention is 42 to 68 ° C,
Particularly, it is 45 to 65 ° C.

The DSC curve of the toner according to the present invention can be measured by a highly accurate internal heating input compensation type differential scanning calorimeter based on the measurement principle. For example, DSC-7 manufactured by PerkinElmer can be used. For the measurement method, see "ASTM D34
18-8 ”. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the heat quantity correction uses the heat of fusion of indium. An aluminum pan is used as a measurement sample, an empty pan is set as a control, and the measurement can be performed at a heating rate of 10 ° C./min.

The glass transition temperature (Tg) can be specifically measured by the following method.

After the sample was once heated and cooled,
The glass transition temperature (Tg) is defined as the intersection between the baseline before the endothermic peak and the middle line after the endothermic peak from the DSC curve at the time of the second temperature rise, and the rising curve (see FIG. 8).

The toner has a glass transition temperature (Tg) of 40 to 40 in a DSC curve measured by a differential scanning calorimeter.
In order to be observed at 70 ° C., specifically, it may be adjusted by changing the type and ratio of the polymerizable monomer.

The toner of the present invention has an ambient temperature of 23.
B when left for 72 hours in an environment at 65 ° C and a relative humidity of 65%
The specific surface area according to the ET method is A (m ² / g), and the specific surface area according to the BET method when the toner is left in an environment of an ambient temperature of 50 ° C. and a relative humidity of 3% for 72 hours is B (m ² / g). Sometimes 0.8 ≦ A ≦ 4.0 and 0.80 ≦ (B
/A)≦1.05. If A is less than 0.8, it may be difficult to control the fluidity of the toner, or it may be difficult to obtain a high-resolution image. If it exceeds 4.0, the chargeability of the toner may be reduced. Due to the large variation or poor matching with the toner carrier or the electrostatic latent image carrier, it may be difficult to obtain a high quality image. Further, the range of 1.0 ≦ A ≦ 3.0 is more preferable. The value of (B / A) is 0.85 ≦ (B / A) ≦ 1.
05, and more preferably 0.90 ≦ (B /
A) The range of ≦ 1.05 is preferred, and particularly, 0.92 ≦
(B / A) ≦ 1.03, most preferably 0.92 ≦ (B
/A)≦1.00.

The fact that (B / A) decreases means that the external additive such as silica existing on the toner surface is
It indicates that it is buried when left in an environment of 0 ° C. and a relative humidity of 3% for 72 hours. If this value is less than 0.80, a high-quality image tends not to be stably obtained.
When (B / A) exceeds 1.05, it means that the toner particles themselves are largely deformed, and a high-quality image may not be stably obtained.

The specific surface area according to the BET method in the present invention means, for example, that a nitrogen gas is adsorbed on a sample surface using a specific surface area measuring device, Autosorb 1 (manufactured by Yuasa Ionics), and the specific surface area is determined using a BET multipoint method. Is calculated.

A method for producing a toner satisfying the above-mentioned specification relating to the BET specific surface area is not particularly limited. For example, a resin particle containing a diene monomer is produced by a pulverization method or a polymerization method, and the resin particles are produced in the vicinity of the surface. This can be achieved by reacting unreacted double bonds of the existing diene monomer.

The toner particles thus obtained have a three-dimensional structure without significantly impairing the flexibility of the surface of the particles, thereby increasing the strength. Therefore, even when the toner is left in a high-temperature and high-humidity environment, the external additive is less likely to be buried in the toner particles, and deformation of the toner particles themselves is suppressed. Further, since a network structure is formed by the diene monomer on the surface of the toner, the toner is less affected by moisture in the air, and the charging is further stabilized.

The method for producing the toner of the present invention will be described in detail later.

The toner of the present invention must have the following shape in order to improve transferability and developability in a well-balanced manner. That is, the circle-equivalent number average diameter in the number-based particle size frequency distribution of the toner is 2 to 10 μm, the average circularity in the circularity frequency distribution is 0.950 to 0.995,
It is preferably from 0.960 to 0.995, more preferably from 0.970 to 0.995, and has a circularity standard deviation of 0.1.
By precisely controlling the particle shape of the toner so as to be less than 040, preferably less than 0.035, transferability and developability can be improved in a well-balanced manner.

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

However, by controlling the circularity standard deviation of the circularity frequency distribution as described above, the toner of the present invention has good stability against environmental fluctuations in developing property and transferability, and furthermore has good durability. Becomes The reason is that when a thin layer of toner is formed on the toner carrier in the developing step, a sufficient amount of toner coating can be maintained even if the regulating force of the toner layer thickness regulating member is made stronger than usual. It is considered that the charge amount of the toner on the toner carrier can be made higher than usual without damaging the toner carrier.

The average circularity in the circularity frequency distribution is set to 0.
950 to 0.995, more preferably 0.970 to 0.90.
By setting it to 995, the transferability of toner having a small particle diameter, which has been regarded as difficult in the past, can be greatly improved, and the developing ability for a low-potential latent image can be significantly improved. It is particularly effective when developing a digital minute spot latent image. When the average circularity is less than 0.950, not only the transferability but also the developability may be reduced. On the other hand, when the average circularity exceeds 0.995, the surface of the toner is significantly deteriorated, and there is a tendency that problems such as durability occur.

In the case of a spherical toner having an average circularity of 0.950 to 0.995, the particles usually come into contact with each other at points, so that the pressure at the contact point is increased, and the external toner existing on the surface of the toner particles is increased. Additives are easily embedded in the toner. However, since the toner of the present invention has a network structure formed by diene monomers on the surface of the toner particles, the surface strength is high and the embedding of the external additive is suppressed. For this reason, even when used for a long period of time, the initial excellent characteristics are maintained. This tendency indicates that the average circularity is 0.970 to 0.995.
This is particularly noticeable in the toner having

In the case where the intermediate transfer method is performed in the transfer step in order to cope with various types of transfer materials, the transfer step is performed substantially twice. This is an inviting problem. In digital full-color copiers and printers, color image
(Blue) filter, G (green) filter, R
(Red) After color separation using a filter, a dot latent image of 20 to 70 μm is formed on the photoreceptor, and Y (yellow)
Toner, M (magenta) toner, C (cyan) toner,
It is necessary to reproduce a multicolor image faithful to a document by utilizing the subtractive color mixing action using each color toner of B (black) toner. At this time, since a large amount of each color toner of Y toner, M toner, C toner, and B toner is put on the photoreceptor or the intermediate transfer member corresponding to the color information of the original or the CRT, Color toners are required to have extremely high transferability. In order to satisfy such a higher level requirement, the above-mentioned average circularity of the toner is 0.950 to 0.950.
0.995, preferably 0.970 to 0.995, and the circularity standard deviation is less than 0.040, preferably 0.1 to 0.99.
It is preferably less than 035.

In the toner of the present invention, the number of toners having a circularity of less than 0.950 is 15% by number or less in the number-based circle equivalent diameter-circularity scattergram measured by the flow type particle image measuring apparatus. Is preferred. When the toner having a circularity of less than 0.950 exceeds 15% by number, untransferred toner tends to increase, which is not preferable.

In the present invention, the circularity is used as a simple method for quantitatively expressing the shape of a particle. In the present invention, a flow type particle image analyzer FP manufactured by Toa Medical Electronics Co., Ltd.
The particle shape is measured using IA-1000, and the circularity is determined by the following equation. Further, as shown by the following equation, the value obtained by dividing the total sum of the measured circularities of all the particles by the total number of particles is defined as the average circularity.

[0133]

[Outside 5]

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

[0135] The measuring device "FPIA-1000" used in the present invention calculates the circularity of each particle, and then calculates the circularity.
In calculating the average circularity and the circularity standard deviation, the circularity was determined to be 0.400 to 1.0 depending on the circularity obtained.
00 is divided into 61 divided ranges at intervals of 0.010, such as 0.400 or more and less than 0.410, 0.410 or more and less than 0.420 ... 0.990 or more and less than 1.000, and 1.000. A calculation method of calculating an average circularity and a circularity standard deviation using the center value and frequency of a point is used.

Each value of the average circularity and the standard deviation of the circularity calculated by this calculation method, and each value of the average circularity and the standard deviation of the circularity calculated by the above-mentioned calculation formula directly using the circularity of each particle. Is very small and practically negligible, and in the present invention, each of the above-described methods is used for data handling reasons such as shortening the calculation time and simplifying the calculation formula. Utilizing the concept of a calculation formula that directly uses the circularity of particles, such a calculation method partially modified is used.

The degree of circularity in the present invention is an index indicating the degree of irregularity of particles, and is 1. if the particles are perfectly spherical.
000, and the degree of circularity becomes smaller as the surface shape becomes more complicated.

The equivalent circle diameter is

[0139]

[Outside 6]

The circle-equivalent number average diameter (D1) represents the average value of the circle-equivalent diameter of the toner on a number basis, and the particle diameter (central value) at the dividing point i of the particle size distribution. To d
If i and the frequency are fi, they are expressed by the following equation.

[0141]

[Outside 7]

The dividing points of the particle size distribution in the present invention are as shown in the following table.

[0143]

[Table 1]

As a specific measuring method, for example, 10 m of ion-exchanged water in which an impure solid substance or the like has been removed in a container is used.
1 is prepared, and a surfactant, preferably an alkyl benzene sulfonate, is added as a dispersant therein, and then 0.02 g of a measurement sample is further added to uniformly disperse. As a means for dispersing, using a UH-50 ultrasonic dispersing machine (manufactured by SMT Corporation) with a titanium alloy chip having a diameter of 5 mm attached as a vibrator, using a dispersion treatment for 5 minutes to obtain a dispersion for measurement. . At this time, the temperature of the dispersion is 40 ° C.
It cools suitably so that it may not become above.

As a specific method of measuring the circularity and the equivalent circle diameter, about 5 mg of a toner is dispersed in 10 ml of water in which about 0.1 mg of a nonionic surfactant is dissolved to prepare a dispersion, and an ultrasonic wave ( (20 kHz, 50 W) was applied to the dispersion for 5 minutes, and the concentration of the dispersion was set to 5,000 to 20,000 / μl.
The circularity distribution of particles having an equivalent circle diameter of at least m and less than 159.21 μm is measured.

The outline of the measurement is described in the catalog of FPIA-1000 (June 1995 edition) issued by Toa Medical Electronics Co., Ltd., the operation manual of the measuring apparatus and Japanese Patent Application Laid-Open No. 8-136.
No. 439, which is as follows.

The sample dispersion liquid is passed through a flow path (spread along the flow direction) of a flat and flat transparent flow cell (about 200 μm thick). The strobe and the CCD camera are mounted on the flow cell so as to be positioned on opposite sides of the flow cell so as to form an optical path that intersects with the thickness of the flow cell. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a range parallel to the flow cell 2
Photographed as a two-dimensional image. The diameter of a circle having the same area is calculated as the equivalent circle diameter from the area of the two-dimensional image of each particle. The circularity of each particle is calculated from the projected area of the two-dimensional image of each particle and the perimeter of the projected image using the above-described circularity calculation formula. In the present invention, 0.6
Particles having a circle equivalent diameter of 0 μm or more and less than 159.21 μm are measured.

In order to make the shape of the toner as described above, specifically, in the case of the polymerization method toner, the polymerization method and the polymerization temperature may be adjusted, and in the case of the pulverized toner, the pulverization conditions may be adjusted.

The tetrahydrofuran (THF) soluble component of the dry toner of the present invention has a main peak molecular weight in the range of 2 × 10 ³ to 1 × 10 ^{5 in} the molecular weight distribution measured by gel permeation chromatography (GPC). And the THF-insoluble content is 5 to 60% by mass.

In the present invention, the molecular weight of the binder resin in the toner is a value determined as the molecular weight in terms of polystyrene from the molecular weight distribution by GPC. In the toner of the present invention, the molecular weight distribution measured by GPC of the THF-soluble component has a main peak molecular weight in the range of 2 × 10 ³ to 1 × 10 ⁵ , preferably 5 × 10 ^{3 to} 5 × 10 ⁴ range. When the main peak molecular weight is lower than 2 × 10 ³ , the charging characteristics may be adversely affected, and when stored at a high temperature, the resin component containing the diene monomer migrates to the toner surface, and the blocking resistance May have adverse effects. If the main peak molecular weight exceeds 1 × 10 ⁵ , the melt viscosity becomes too high, causing a problem in fixability,
The flexibility of the resin component containing the diene monomer cannot be effectively exhibited, and a low-temperature offset occurs.

In the present invention, the THF-soluble component of the toner is a toner component that is soluble in THF. Specifically, a binder resin is a main component, and a wax component and the like are also included.
The THF-soluble component of the toner can be obtained as follows.

After the toner sample is placed in THF and left for several hours, it is shaken sufficiently, mixed well with THF (until the sample is no longer united), and left still for 12 hours or more. At this time, the time of being left in THF is set to be 24 hours or more. Thereafter, a sample processing filter (pore size 0.2 μm, for example, Myshoridisk H-25-
5: available from Tosoh Corporation, and ExciloDisk 25CR: available from Germanic Science Japan) to obtain a THF-soluble component. The concentration of the obtained solution is adjusted so that the binder resin component has a concentration of 0.5 to 5.
It is adjusted to be 0 mg / ml and used as a GPC sample.

In the present invention, the molecular weight distribution of the THF soluble portion of the toner by GPC can be measured under the following conditions.

That is, the column was stabilized in a heat chamber at 40 ° C., and THF (tetrahydrofuran) as a solvent was passed through the column at this temperature at a flow rate of 1 ml per minute, and the THF-soluble toner sample solution (the THF (Soluble matter) is injected and measured. In measuring the molecular weight of the toner sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number.

As standard polystyrene samples for preparing a calibration curve, for example, TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, manufactured by Tosoh Corporation
F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500
The calibration curve can be prepared by using the standard polystyrene sample of at least about 10 points.

As the detector, a detector in which an RI (refractive index) detector and a UV (ultraviolet) detector are arranged in series is used. As the column, it is better to combine a plurality of commercially available polystyrene gel columns, and in the present invention, for example,
Shodex GPC KF-801, 802, 803, 804, 8 manufactured by Showa Denko
05, 806, 807, 800P. As the apparatus, a high-speed GPC HPLC8120 GPC manufactured by Tosoh Corporation can be used.

In the present invention, the THF-insoluble content is 5 to 5.
It must be 60% by weight. Preferably, 5-55
% By mass. When the THF-insoluble content is 5% by mass or more, it is considered that the three-dimensional formation in the vicinity of the toner surface by the diene monomer is favorably performed. 5 THF insolubles
When the amount is less than 3% by mass, the three-dimensional formation near the toner surface is insufficient, so that the durability at a high temperature becomes inferior, and the charge stability of the toner is maintained for a long time. It becomes difficult. On the other hand, if the THF-insoluble content exceeds 60% by mass, the features derived from the flexibility possessed by the binder resin containing the diene monomer are less likely to be exhibited, so that offset tends to occur during fixing.

In the present invention, the diene monomer is used to prepare TH.
The F-insoluble content can be controlled relatively easily. That is, if the content of the diene monomer in the toner is increased, the THF-insoluble content can be increased.

However, the THF-insoluble content of the toner of the present invention is as follows:
When toner is manufactured by a pulverization method, not just by the amount of diene monomer, it is added to react the amount of diene monomer contained and unreacted double bonds near the toner particle surface. It depends on the amount of polymerization initiator to be used. In this case, the effect of the diene monomer amount tends to be large. Further, when a toner is produced by suspension polymerization, the amount of a diene monomer, the amount of a polymerization initiator used in a polymerization reaction or a reaction treatment, the polymerization temperature, the temperature in a reaction treatment, and the like are affected. When the amount of the polymerization initiator used is changed, the peak molecular weight of the THF-soluble component is greatly affected. Therefore, when the THF-insoluble component is adjusted in the present invention, the peak molecular weight of the THF-soluble component is adjusted. Must also be considered.

In addition, the same effect can be obtained by adding a monomer having two or more polymerizable double bonds.

Examples of such a monomer include o (m-, p-)-divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate,
Triethylene glycol (meth) acrylate, o (m-, p
-)-Divinylcyclohexane, trimethylolethanetri (meth) acrylate, trimethylolpropanetri (meth) acrylate, and pentaerythritol tetra (meth) acrylate can be exemplified. These monomers may be used alone or in combination of two or more.

In the present invention, the THF-insoluble content of the toner means the mass ratio of the binder resin component insoluble in THF of the binder resin composition in the toner particles. This is a measure of the degree of crosslinking of the resin composition. However, even if the THF-insoluble content is 0% by mass, it does not necessarily mean that crosslinking has not occurred. In the present invention, the THF-insoluble matter is defined by a value measured as follows.

That is, when the toner is a non-magnetic toner, the content of the pigment and the like are measured in advance by a known method when the toner is a magnetic toner. Next, a fixed amount of 0.5 to 1.0 g of the toner is weighed (W
₁ g), placed in cylindrical thick paper (No. 86R, manufactured by Toyo Denshi Paper), and subjected to a Soxhlet extractor.
After extracting with a solvent for 20 hours and evaporating the soluble component extracted with the solvent, vacuum drying is performed at 100 ° C. for several hours, and the amount of the THF-soluble resin component is weighed (W ₂ g).
When the mass of the THF-soluble component among the pigments and the magnetic material contained in the above-mentioned toner constant amount is W ₃ g, and the mass of the THF-insoluble component is W ₄ g, the following formula is obtained. The THF-insoluble content in the resin composition can be calculated.

[0164]

[Outside 8]

<2> Method for Producing Dry Toner of the Present Invention Various methods can be used for producing the toner of the present invention, but it is preferable that a part or the whole be produced by a polymerization method. A part of the toner is manufactured by a polymerization method after it is obtained by polymerizing only a binder resin by applying solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, block copolymerization, grafting, or the like. A method in which toner particles are obtained by a pulverization method, a melt spraying method, or the like, and the whole toner is manufactured by a polymerization method. And a method for simultaneously producing a binder resin and a toner.

When the toner of the present invention is produced by a pulverization method, the resin containing a diene monomer component, a wax component, a coloring agent (a magnetic substance may be used), a resin used together if necessary, a charge control agent And other additives are sufficiently mixed with a mixer such as a hen shell mixer or a ball mill, and then melt-kneaded using a heat kneader such as a pressure kneader or an extruder. Alternatively, the particles are made to collide with a target under a jet stream and pulverized 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 by a classification process. Further, the toner of the present invention can be obtained by sufficiently mixing the classified powder with an external additive such as silica fine particles using a mixer such as a Henschel mixer. As the production method of the present invention, for example, a polymerization initiator and a diene monomer component-containing resin present on the toner surface are reacted with a spheroidized toner particle with a polymerizable monomer added as necessary. This can increase the strength near the toner particle surface.

The diene monomer component-containing resin constituting the binder resin contained in the toner of the present invention may be contained in the toner in any shape and state, and other resins constituting the binder resin may be used. And may be in a phase separated state. When the toner is manufactured by the pulverization method, it is not necessary that the resin containing the diene monomer component is melted together with the other resin in the melt-kneading step, and the resin is dispersed in the melted other resin. Is also good. In such a case, the resin containing the diene monomer component in the toner is in a state of being dispersed in another resin used in combination. When a resin containing a diene monomer component and another resin are previously uniformly dissolved and mixed using a solvent such as xylene, the resin containing a diene monomer component is finely dispersed in the other resin, or in some cases, is compatibilized. Is done. Without performing such a homogenizing operation, knead the powder of the diene monomer component-containing resin and another resin, and,
When the kneading is performed at a temperature lower than the melting temperature of the diene monomer component-containing resin, the diene monomer component-containing resin is dispersed in the toner in the form of a powder, so that 1 μm or less, preferably 0.5 μm It is preferable to use a diene monomer component-containing resin finely pulverized below.

As another method for producing a toner, the classified powder obtained in the classifying step is mixed with a fluidizing agent or separately with a finely divided resin containing a diene monomer component, and thoroughly mixed. There is also a method in which a resin containing a diene monomer component is fixed to the resin. In this case, the resin in the classified powder may or may not contain the resin containing a diene monomer component. Further, after fixing, the toner particles may be subjected to smoothing and spheroidizing treatment. Further, the polymerization initiator, and the polymerizable monomer added as necessary, are adsorbed on the toner particles after fixing or after the sphering treatment, and are reacted with the diene monomer component-containing resin present on the surface. This can increase the strength near the toner particle surface.

Further, a composition comprising a monomer component having a diene monomer component-containing resin and a polymerization initiator is adsorbed on toner particles serving as cores having no resin containing a diene monomer component, and It is also possible to obtain a special effect.

As another method, Japanese Patent Publication No. 56-139
Similarly to the method described in JP-A-45-45, a melt spray method of using a disk or a multi-fluid nozzle to atomize a molten mixture containing a diene monomer component-containing resin constituting a binder resin into air to obtain a spherical toner is known. No. In addition, polymer particles containing no diene monomer are produced by a polymerization method, and then a resin containing a particulate diene monomer component is attached to the surface of the polymer particles, and if necessary, the particles are smoothed. And a method of performing a sphering treatment.

In each case, the binder resin was prepared by solution polymerization,
It is obtained by performing polymerization by applying bulk polymerization, suspension polymerization, emulsion polymerization, block copolymerization, grafting and the like.

In the case where the whole toner of the present invention is produced by a polymerization method, a resin containing a diene monomer component is dissolved in a monomer composition, which is disclosed in JP-B-36-10231 and JP-A-Sho 59-59.
No. 6,184,842, a method for producing a toner directly by using a suspension polymerization method, a method in which an aqueous organic solvent that is soluble in a monomer and insoluble in a polymer obtained is directly used. The toner of the present invention can be obtained by a dispersion polymerization method for producing a toner 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. Further, a method of providing a surface layer with a diene monomer component-containing resin and a monomer (composition) of another resin on a core particle having no diene monomer component-containing resin, or In the toner particles having a diene monomer component-containing resin, a polymerization initiator, preferably a diene monomer component-containing resin present on the surface with a highly hydrophilic polymerization initiator remains in the toner particles, or if necessary. Preferably, a step for increasing the strength near the surface of the toner particles by reacting with the added monomer component is preferably used. At that time, it is also preferable to add the diene monomer component-containing resin and the polymerizable monomer together.

Further, under pressure, a polymerizable monomer composition containing a resin containing a diene monomer component, another polymerizable vinyl monomer, a wax, and a colorant is subjected to suspension polymerization, emulsion polymerization, or the like. The toner of the present invention can be obtained by dispersion polymerization.

Among the toner production methods described above, the melt spraying method tends to broaden the particle size distribution of the obtained toner, and the dispersion polymerization method shows that the obtained toner shows an extremely sharp particle size distribution. The range of choice is narrow, and the use of an organic solvent tends to complicate and complicate the manufacturing apparatus from the viewpoint of treatment of waste solvent and flammability of the solvent. Also, the emulsion polymerization method has an advantage that the particle size of the toner is relatively uniform, but generally the particle size of the generated particles is very fine, and it is difficult to use the toner as it is,
Further, the terminal of the used water-soluble polymerization initiator and the emulsifier may be present on the surface of the toner particles, and may lower the environmental characteristics of the toner.

On the other hand, a method for producing the toner particles by smoothing and spheroidizing the toner particles obtained by the pulverizing method,
Alternatively, the suspension polymerization method makes it easy to keep the circularity and circularity standard deviation of the toner within a desired range,
Although this is a preferred method, in the present invention, production by a suspension polymerization method is the most preferred production method.

In the method for producing the toner of the present invention by the suspension polymerization method, it is particularly easy to control the shape of the toner particles, and the diene monomer component-containing resin is used as a raw material for the binder resin. Since it is sufficient to dissolve in the body composition, there are many types of resins that can be used, and this is a particularly preferable production method.

In the present invention, as described above, various production methods can be used, but it is important that the resin is pulverized in the case of the pulverization method, and that the polymerization conversion rate described later is used in the case of the polymerization method. That is, the unreacted double bond of the component contained in the toner particles, particularly the double bond of the component derived from the diene monomer, is reacted to form a cross-link on the surface of the toner particle.

In the present invention, the following production method is particularly preferred.

A resin containing a diene monomer component, a colorant, a wax, a radical polymerization initiator, and other additives as necessary are added to the polymerizable vinyl monomer, and the mixture is treated with a homogenizer, an ultrasonic disperser or the like. And dissolving or dispersing it uniformly to prepare a polymerizable monomer composition. The polymerizable monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer using an ordinary stirrer, homomixer, or homogenizer. Preferably, the granulation is performed by adjusting the stirring speed and the stirring time so that the droplets of the polymerizable monomer composition have a desired size of the toner particles. Thereafter, by the action of the dispersion stabilizer, while stirring to such an extent that the particle state is maintained and the sedimentation of the particles is prevented, the polymerizable vinyl monomer is polymerized in an aqueous medium to generate toner particles. . When the conversion of the polymerization reaction is in the range of 10 to 95% by mass, a method of adding a radical polymerization initiator newly to increase the strength near the surface of the toner particles is preferably exemplified.

In the present invention, examples of the polymerization initiator include 2,2′-azobis- (2,4-dimethylvaleronitrile),
2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyri Azo-based polymerization initiators such as lonitrile and diazo-based polymerization initiators; peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide Radical polymerization initiators such as product polymerization initiators are preferably used. The amount of the polymerization initiator used varies depending on the desired degree of polymerization, but is generally used in an amount of 0.5 to 20% by mass based on the polymerizable monomer. The type of polymerization initiator is
Depending on the polymerization method, it is used in one or a combination of two or more selected from the above-mentioned polymerization initiators with reference to the 10-hour half-life temperature.

The polymerization initiator newly added when the conversion of the polymerization reaction is in the range of 10 to 95% by mass includes:
Although the oil-soluble polymerization initiator as described above may be used, the following water-soluble radical polymerization initiator can also be used.

Examples of the water-soluble radical polymerization initiator include polymerization initiators such as sodium persulfate, potassium persulfate, and ammonium persulfate. One or a combination of two or more of these can be used. is there. A water-soluble radical polymerization initiator is preferred because it can be easily added at the time of production and can be added in an aqueous solution. Further, a polymerization initiator having high water solubility or high hydrophilicity is preferably used from this point, because it efficiently acts on the diene monomer-containing resin present on the surface of the toner particles.

Conversely, since the oil-soluble radical polymerization initiator can be added by emulsifying or dispersing in water, it is possible to expand the options of the polymerization initiator and control the reactivity. Is preferred.

The amount of the radical polymerization initiator used when newly added varies depending on the desired degree of polymerization, but is preferably used in the range of 0.5 to 10% by mass based on the polymerizable monomer. .

Examples of the aqueous medium include water and a mixed solvent of water / alcohol. Water is preferably used. In the suspension polymerization method, usually, the polymerizable monomer composition 100
It is preferable to use 100 to 5000 parts by mass of water as a dispersion medium with respect to parts by mass.

In the method for producing a toner of the present invention, when the conversion of the polymerization reaction is in the range of 10 to 95% by mass,
It is preferable to newly add a radical polymerization initiator. However, if a radical polymerization initiator is newly added before reaching 10% by mass, the conversion of the polymerization reaction is extremely low, so that the polymerizability in a state where the particle shape is not stable is obtained. Since the amount of the polymerization initiator with respect to the monomer increases, the peak molecular weight of the obtained binder resin component may be too low, which is not preferable. More preferably, the timing of newly adding the radical polymerization initiator is such that the conversion is 20 to 95% by mass, particularly 25 to 90% by mass.
It is in the range of mass%.

The conversion of the polymerization reaction can be calculated, for example, as follows.

Using a gas chromatograph, the amount of unreacted polymerizable monomer remaining in the system was determined from a previously prepared calibration curve, which was defined as an unconverted rate (%).
The value subtracted from 00 is determined as the conversion. In particular,
It can be measured by the internal standard method under the following conditions.

(Conversion rate:%) = 100- (unconverted rate determined from a calibration curve based on the amount of unreacted polymerizable monomer) Sample: A vial containing 5 μl of a sample (polymerization reaction solution) and 1 μl of dimethylformamide And use a sealed one. Measurement device: HP6890 (made by HP) Carrier gas: Industrial pure helium split (split ratio 100: 1), linear velocity 35 cm / sec Column: HP-INNOWax inner diameter 0.2 mm, length 50 m, film thickness 0.4 μm Temperature rise: 40 After holding at 2 ° C. for 2 minutes, the temperature is raised to 200 ° C. at a rate of 20 ° C. per minute. Inlet temperature: 120 ℃ Detector: FLD 220 ℃

In the present invention according to the production method, the three-dimensional network is formed by reacting the polymerizable double bond of the binder resin containing the diene monomer component-containing resin in the vicinity of the particle surface, thereby improving the strength of the toner particles. The present invention provides an efficient method for improving the polymerization efficiency. When the polymerization conversion exceeds 95% by mass at the time when a radical polymerization initiator is newly added, the remaining polymerizable monomer is extremely low. Since the polymerization initiator is newly added in a state where the particles are almost solidified, the molecular motion in the particles is extremely restricted, and the polymerizability of the binder resin including the resin containing the diene monomer component is extremely low. It is not preferable because the double bond tends to be unable to react well. On the other hand, when the polymerization conversion rate has not reached 10% by mass at the time when the radical polymerization initiator is newly added, conversely, since free molecular movement is possible, the polymerization initiator is newly added. However, no reaction occurs as if a three-dimensional network is formed on the particle surface.

In the present invention, when the 10-hour half-life temperature of the newly added radical polymerization initiator is T1 (° C.) and the reaction system temperature at the time of addition is T2 (° C.), 5 ≦ (T2-
It is preferable to satisfy the relationship of T1) ≦ 30. Satisfying this relationship is preferable because the radical polymerization initiator efficiently participates in the reaction.

When the toner is produced by suspension polymerization, the dispersion stabilizer used may be an inorganic compound such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, or water. Calcium oxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate,
Examples include barium sulfate, bentonite, silica, and alumina. As organic compounds, polyvinyl alcohol,
Examples include gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, hydroxyethylcellulose, sodium salts of carboxymethylcellulose, polyacrylic acid and its salts, and starch. It is preferable to use 0.2 to 20 parts by mass of these dispersion stabilizers with respect to 100 parts by mass of the polymerizable monomer composition.

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 above 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 obtained by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high-speed stirring.

To finely disperse these dispersion stabilizers,
0.001 to 0.1 parts by mass of a surfactant may be used in combination. This is to promote the intended action of the dispersion stabilizer, for example, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, lauric acid Anionic surfactants such as sodium, potassium stearate, potassium oleate, nonionic surfactants such as ethylene oxide and / or propylene oxide adducts of alkyl phenols, cationic surfactants of alkyl onium salt type, betaine type And amino acid type amphoteric surfactants.

The polymerization reaction time is preferably 2 to 24 hours. If the time is less than 2 hours, the desired conversion rate of the polymerizable monomer is not attained, the unreacted polymerizable monomer is large, and the removal step becomes complicated. If the time exceeds 24 hours, the reaction time is too long and the productivity is too long. Is preferably 2 to 24 hours.

The polymerization temperature is 40 ° C. or higher, generally 5 ° C.
What is necessary is just to set to the temperature of 0-90 degreeC. The temperature may be raised in the latter half of the polymerization reaction, and furthermore, in order to remove unreacted polymerizable monomers and by-products in the latter half of the reaction, or after completion of the reaction, a part of the aqueous medium is distilled off from the reaction system. May be. After the reaction,
After the generated toner particles are washed, they are collected by filtration and dried.

In the method of producing a toner according to the present invention, a known crosslinking agent, chain transfer agent, polymerization inhibitor and the like may be further added to control the degree of polymerization.

In the case of producing a toner by a polymerization method, the particle size distribution and the particle size of the toner particles are controlled by the type or amount of the dispersion stabilizer, mechanical device conditions (for example, the peripheral speed of the rotor, the number of passes, The shape can be adjusted by controlling the solid content concentration in an aqueous medium or the like.

<3> Image Forming Method of the Present Invention The image forming method of the present invention comprises a charging step of applying a voltage to a charging member to charge an electrostatic latent image carrier; An electrostatic latent image forming step of forming an electrostatic latent image;
A developing step of attaching the toner of the present invention carried on the toner carrier to the electrostatic latent image formed on the electrostatic latent image carrier to form a toner image on the electrostatic latent image carrier; An image forming method includes a transfer step of transferring a toner image formed on an electrostatic latent image carrier to a transfer material; and a fixing step of fixing the toner image transferred to the transfer material.

Next, some embodiments of the image forming method of the present invention will be specifically described with reference to the drawings, but the present invention is not limited thereto.

FIG. 5 shows an image forming apparatus performed by a one-component developing method.

In the image forming method of the present invention, as shown in FIG.
The “photosensitive drum” may rotate in the opposite direction, or rotate in the same direction (in FIG. 5, the toner carrier 202 rotates in the direction opposite to the arrow C, and the photosensitive drum 209).
May rotate in the direction of arrow D).

[0203] The moving speed of the surface of the toner carrier in the developing area is 1.0 to 1.0 with respect to the moving speed of the surface of the electrostatic latent image carrier.
It is preferable to set the speed so as to be 5 to 3.0 times. By setting the moving speed to be 1.05 to 3.0 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. Becomes

[0204] In the developing step, when the electrostatic latent image on the electrostatic latent image carrier and the toner thinly coated on the toner carrier are developed while being in contact with each other (hereinafter, abbreviated as "contact development"). In particular, if the peripheral speed of the toner carrier is less than 1.05 times the peripheral speed of the electrostatic latent image carrier, the stirring effect of the toner on the electrostatic latent image carrier becomes insufficient, Good image quality cannot be expected. Further, when developing an image that requires a large amount of toner over a wide area, such as a solid black image, the amount of toner supplied to the electrostatic latent image is insufficient and the image density is reduced. The higher the peripheral speed ratio, the greater the amount of toner supplied to the development site. In addition, since toner is frequently attached to and detached from the latent image, unnecessary portions (non-image portions) of the toner are collected and added to the necessary portions (image portions). Images can be obtained. Further, as the image forming method of the present invention, it is also possible to apply a developing and cleaning step described below. In the developing and cleaning step, when there is a transfer residual toner closely adhered to the electrostatic latent image carrier, Since it is important to adjust the chargeability of the transfer residual toner by the peripheral speed difference between the surface of the electrostatic latent image carrier and the toner adhered portion and then recover the toner by electric field cleaning, the higher the peripheral speed ratio, the higher the peripheral speed ratio. It is convenient for collecting the transfer residual toner. However, if the peripheral speed ratio exceeds 3.0, on the other hand, in addition to the various problems caused by the excessive charging of the toner as described above (image density reduction due to excessive toner charge-up, etc.), mechanical Deterioration of the toner due to stress and adhesion of the toner to the toner carrier may occur or be promoted, which is not preferable.

As the electrostatic latent image carrier in the present invention,
A photosensitive drum or a photosensitive belt having a photoconductive insulating material layer such as a-Se, CdS, ZnO ₂ , OPC, and a-Si is preferably used.

An OPC photosensitive member (photosensitive drum or photosensitive belt) having an organic photosensitive layer containing a binder resin such as a polycarbonate resin, a polyester resin, and an acrylic resin also has good transferability and cleaning properties, and poor cleaning. This is preferable because toner fusion to the photoconductor and filming of the external additive hardly occur.

In the present invention, when the developing step is a non-contact developing method, the surface roughness Ra (μm)
Is preferably from 0.2 to 1.5. Surface roughness R
By setting a to 1.5 or less, the toner carrying capacity of the toner carrier is suppressed, the toner layer on the toner carrier is made thinner, and the number of times of contact between the toner carrier and the toner increases. Since the chargeability of the toner is also improved, the image quality is synergistically improved.

Further, when the developing step is a contact developing method, the surface shape of the toner carrier is changed to the surface roughness Ra.
(Μm) is preferably set to 0.2 to 3.0, since both high image quality and high durability can be achieved. The surface roughness Ra correlates with the toner carrying ability and the toner charging ability. When the surface roughness Ra of the toner carrier exceeds 3.0, not only is it difficult to reduce the thickness of the toner layer on the toner carrier, but also the chargeability of the toner may not be improved. No improvement in image quality can be expected. By setting the ratio to 3.0 or less, the toner carrying ability on the surface of the toner carrier is suppressed, 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. Since the chargeability of the toner is also improved, the image quality is synergistically improved. On the other hand, when the surface roughness Ra is smaller than 0.2, it may be difficult to control the amount of toner coating.

The surface roughness Ra of the toner carrier can be set in the above range, for example, by changing the polishing state of the surface layer of the toner carrier. That is, if the surface of the toner carrier is polished roughly, the surface roughness can be increased, and if the surface is polished finely, the surface roughness can be reduced. In the present invention, the surface roughness Ra of the toner carrier is determined by the JIS surface roughness “JIS B 0601”.
Surface roughness measuring device (Surfcoder SE-30)
H, manufactured by Kosaka Laboratory Co., Ltd.). 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, the direction of the vertical magnification is the Y axis, and the roughness curve is When y = f (x), the value obtained by the following equation is expressed in micrometers (μm).

[0210]

[Outside 9]

As the toner carrier having the above-mentioned properties, a so-called elastic roller having an elastic layer on its surface is preferably used.

As the configuration of the elastic roller, a core metal is used.
The outer periphery is covered with an elastic layer, and as the material of the elastic layer, silicone rubber or Teflon rubber is preferably used.

The hardness of the elastic layer used is preferably 20 to 65 degrees in Asker C hardness.

Further, the resistance of the toner carrier is a volume.
10 in resistance^Two-10⁹A range of about Ω · cm is preferable. Stillness
When there is a pinhole etc. on the surface of the latent image carrier,
10 ^TwoIf it is lower than Ωcm, overcurrent may flow,
10 on the contrary⁹If it is higher than Ωcm,
Toner charge-up is likely to occur, resulting in low image density.
Easy to invite below. Keep the volume resistance of the elastic layer in the above range
In some cases, elastic materials such as carbon black and iron oxide
It can be adjusted by blending and dispersing the electric conductivity imparting agent.

The amount of toner on the toner carrier is regulated by a regulating member. As the toner regulating member, a regulating member arranged at a fixed distance from the toner carrier, or a contact with the toner carrier. A regulating member made of an elastic body is exemplified.

The amount of toner on the toner carrier is preferably 0.1 to 1.5 mg / cm ² , and 0.2 to 0.9 mg / cm ^2.
/ Cm ² is more preferred. If it is less than 0.1 mg / cm ^2, it is difficult to obtain a sufficient image density,
^If it exceeds 2, it becomes difficult to uniformly tribocharge the individual toner particles, which causes fogging.

In the present invention, as the regulating member disposed at a fixed distance from the toner carrier, a metal blade,
A doctor blade, which is a ferromagnetic metal blade such as a magnetic blade, or a rigid roller or sleeve made of metal, resin, ceramic, or the like may be used, and a magnet generating means may be provided inside thereof.

The regulating member made of an elastic body which is brought into contact with and opposed to the toner carrier is not particularly limited as long as the toner is applied by pressure to make the layer thinner. An elastic body such as a roller may be used, but a blade made of an elastic body is preferable.

[0219] The contact with the toner carrier in opposition means that
For example, the base portion on the upper side of the elastic blade is fixed to the toner container, and the variable portion is bent in the forward or reverse direction of the toner carrier against the elasticity of the blade,
This means that the inner surface of the blade (the outer surface in the case of the opposite direction) is brought into contact with the surface of the toner carrier with an appropriate elastic pressure. According to such an apparatus, a stable and dense toner layer is formed on the toner carrier with little influence from environmental fluctuation. Although the reason is not always clear, since the elastic body forcibly rubs against the toner carrier surface, the toner is always charged in the same state regardless of a change in behavior due to an environmental change of the toner. It is presumed.

FIG. 5 shows a developing blade 201 as a regulating member for regulating the thickness of the toner layer. The developing blade 201 is in contact with the toner carrier 202 via the toner layer. The contact pressure at this time is preferably in the range of 5 to 50 g / cm.

[0220] If the amount is less than 5 g / cm, it becomes difficult to control the amount of toner coating, and it may also be difficult to uniformly apply triboelectric charging to the toner, which causes fogging. On the other hand, if it is larger than 50 g / cm, the toner particles may be subjected to an excessive load, so that the deformation of the particles and the fusion of the toner to the developing blade or the toner carrier are apt to occur, which is not preferable.

For the elastic regulating member, it is preferable to select a material of a triboelectric series suitable for charging the toner to a desired polarity, and a rubber elastic material such as silicone rubber, urethane rubber, NBR, or polyethylene terephthalate. It can be used by selecting from a synthetic resin elastic body, a metal elastic body such as stainless steel, steel, and phosphor bronze. Further, a composite thereof may be used.

When durability is required for the elastic regulating member and the toner carrier, it is preferable that the elastic member is bonded to the sleeve contact portion of the metal elastic member with resin or rubber or is coated. .

Further, an organic substance or an inorganic substance may be added to the elastic regulating member, may be melted and mixed, or may be dispersed. For example, metal oxides, metal powders, ceramics, carbon allotropes, whiskers, inorganic fibers, dyes, pigments,
By adding a surfactant, the chargeability of the toner can be controlled. In particular, when the elastic body is a molded body such as rubber or resin, fine particles of metal oxide such as silica, alumina, titania, tin oxide, zirconia, and zinc oxide, carbon black, a charge control agent generally used for toner Is also preferable.

For the purpose of loosening the toner, a developing blade as a regulating member for regulating the amount of toner on the toner carrier, a supply roller as a supplying member for supplying toner to the toner carrier, and a DC electric field are applied to the brush member. It is also preferable to apply an alternating electric field. By the action of the loosening function, the uniform thin layer coating property and uniform charging property on the toner carrier are further improved, and the supply and stripping of the toner at the supply portion is more smoothly performed, so that a high quality image having a sufficient image density is obtained. Can be obtained.

In the developing step in the present invention, the electrostatic latent image carrier and the toner carrier have a certain distance, and the development can be performed by forming an alternating electric field between the two. Specific examples of the developing method include a jumping developing method. "Fixed interval" above
Means that the thickness is set to be equal to or greater than the thickness of the toner layer on the toner carrier. An alternating electric field can be formed between the electrostatic latent image carrier and the toner carrier by, for example, applying an AC bias between the two.

As the developing step in the contact developing method described above, for example, development can be performed using a developing means having a developing device 31 as shown in FIG. In particular,
While a DC or AC bias is applied to the toner carrier 37 by the power source 36, the toner 34 supplied from the application roller 32 and having the toner layer thickness regulated by the developing blade 33 as a regulating member is in contact with the photosensitive drum 35. In the state,
Development takes place. It is preferable to use an elastic roller as the toner carrier. When using an alternating electric field, a triangular wave, rectangular wave, sine wave, or duty ratio (Duty
Ratio) or a waveform in which the alternation is periodically turned off can be selected and used. However, in the present invention, a DC electric field having a small voltage load on the photosensitive drum is preferably used, and Is set to an appropriate value between the dark portion potential (potential immediately after the charging process) on the photosensitive drum and the bright portion potential (potential of the exposed portion after the exposure process).

As the condition of the developing step in the image forming method of the present invention, it is preferable to use the reversal developing method in any of the jumping developing method and the contact developing method. Further, the use of a developing and cleaning step (also referred to as a “cleanerless process”) in which the transfer residual toner remaining on the electrostatic latent image carrier in the transfer step is collected by the toner carrier during the developing step is also used in an apparatus. This is preferable because the size can be significantly reduced.

That is, in the case of reversal development, this developing and cleaning step includes an electric field for recovering toner from the dark portion potential of the electrostatic latent image carrier to the toner carrier by the developing bias, and an electrostatic latent image carrying process from the toner carrier. This is done by the action of an electric field that causes the toner to adhere to the light potential of the body.

A DC or AC bias is applied to the transfer residual toner not only at the time of development but also after the transfer step and before the development step, so as to collect the residual toner on the electrostatic latent image carrier. May be controlled. At this time, the DC bias is located between the light portion potential and the dark portion potential.

In the case of the contact developing method described above, in the developing and cleaning step, an electric field acting between the photosensitive member, which is an electrostatic latent image carrier, and the elastic roller facing the photosensitive member surface via the toner is used. Since the transfer residual toner is cleaned, the surface of the elastic roller or the vicinity of the surface has a potential, and it is necessary to have an electric field in a narrow gap between the surface of the photoconductor and the surface of the toner carrier. For this reason, it is necessary to maintain the electric field while preventing the conduction with the surface of the photoconductor by controlling the resistance of the elastic rubber of the elastic roller to the medium resistance region, or to provide a thin insulating layer on the surface layer of the conductive roller. Further, it is also possible to adopt a configuration in which a conductive layer is provided on a conductive roller on a conductive roller on which the side facing the photoreceptor surface is covered with an insulating material, or on a side not facing the photoreceptor with an insulating sleeve. It is also possible to employ a configuration in which a rigid roller is used as the toner carrier and the photosensitive member is a flexible member such as a belt. The resistance of the roller as a toner carrying member is preferably in the range of 10 ² ~10 ⁹ Ω · cm.

Referring to FIG. 5, a description will be given of a method of forming an image in a single color when a developing and cleaning step is used in the image forming method of the present invention.

In FIG. 5, the developing device 200
04, and a photoconductor 20 which is an electrostatic latent image carrier
9 and the toner carrier 202 which rotates in the direction of arrow C in contact with
A developing blade 201 serving as a regulating member for controlling the amount of toner and for providing charging;
An application roller 203 that rotates in the direction of arrow B in order to attach the toner to the toner carrier 02 and apply a charge to the toner by friction with the toner carrier 202 is provided. A developing bias power supply 217 is connected to the toner carrier 202. Application roller 2
03 is also connected to a bias power supply 218. When negatively chargeable toner is used, the bias power supply 218 is connected to a negative side of the developing bias.
When a positively chargeable toner is used, the voltage is set on the positive side of the developing bias.

The transfer device 206 is connected to a transfer bias power supply 216 having a polarity opposite to that of the photosensitive member 209. Here, the length of the contact portion between the photoconductor 209 and the toner carrier 202 in the rotation direction, that is, the so-called development contact width is 0.2 to 0.2.
8.0 mm is preferred. When the thickness is less than 0.2 mm, a sufficient image density cannot be obtained due to an insufficient development amount, and the recovery of the transfer residual toner may be insufficient. If it exceeds 8.0 mm, the toner supply amount becomes excessive, fog is likely to occur, and the wear of the photoconductor may be adversely affected.

A charging roller 210 as a primary charging member
Performs direct charging in contact with the photoconductor 209. A bias power supply 215 is connected to the primary charging member 210 so as to uniformly charge the surface of the photoconductor 209. The primary charging member 210 used here is a charging roller having a basic configuration including a central core 210b and a conductive elastic layer 210a formed on the outer periphery thereof. The charging roller 210 is connected to the photosensitive member 2
09 is pressed against the surface of the photoconductor 09 with a pressing force, and is rotated by the rotation of the photoconductor 209 (the charging roller 210 rotates in the direction of arrow A).

Preferred process conditions when a charging roller is used include a contact pressure of the roller of 5 to 500 g / cm.
As the applied bias, a DC bias or a DC bias with an AC bias superimposed is used.
Although not particularly limited, in the present invention, an applied bias of only a DC bias is preferably used, and a bias value in this case is used in an absolute value range of 0.2 to 5.0 kV.

In the image forming apparatus of the present invention, various charging methods can be used.
A contact charging method of charging the electrostatic latent image carrier by bringing the charging member into contact with the electrostatic latent image carrier is preferably used. In the case of using the contact charging method, if a large amount of transfer residual toner is present, it adheres to the charging member, and as a result, charging failure is caused, and charging unevenness may occur on an image. That is, when charging is performed by the contact charging method, it is necessary to suppress the transfer residual toner amount to be smaller than when charging is performed by corona discharge or the like that does not contact the electrostatic latent image carrier. For these reasons, in the contact charging method, it is preferable to use the toner of the present invention in which the average circularity and the circularity standard deviation are strictly defined.

Other charging members in the contact charging method include a method using a charging blade and a method using a conductive brush. The charging in these contact charging methods is
Compared with non-contact corona charging, a high voltage is not required and generation of ozone can be suppressed, which is preferable.
The material of the charging roller and the charging blade as the contact charging means is preferably a conductive rubber, and a release coating may be provided on the surface thereof. Nylon resin, PVDF (polyvinylidene fluoride), PVDC
(Polyvinylidene chloride) is applicable.

Following the primary charging step, an electrostatic latent image corresponding to the information signal is formed on the photosensitive member 209 by exposure 211 from the light emitting element, and the electrostatic latent image is Develop to form a toner image. Further, the image forming method of the present invention can perform suitable development when a digital latent image is developed. Next, the toner image is transferred onto the transfer material 205 by the transfer device 206. As described above, in the image forming method of the present invention, it is preferable that the photosensitive member 209 and the transfer device 206 are in contact with each other via the transfer material 205.

Further, the transfer toner 212 on the transfer material 205
Passes through a fixing device having a heating roller 208 as a heating element and a pressure roller 207 as a pressure member, and is fixed on a transfer material to obtain a permanent image.

The fixing step is not particularly limited, but in the present invention, a fixing step using a heat fixing device is preferable. Further, the fixing step between the above-mentioned heating roller and a pressure roller opposed to and pressed against the heating roller is preferable. And fixing by heating and pressing is more preferable.

As the heating roller, a roller having a built-in heating element such as a halogen heater therein may be used, and the pressure roller may be formed of an elastic member.

In addition to the above-described heat roller system having a heat roller and a pressure roller as the basic structure, the method of heating and fixing with a heater via a film may be used as the heating and pressing means. Can be used because it shows good matching. As specifically shown in FIG. 3 and FIG. 4, the film end regulating flange 25 supports the left and right ends of the fixing film 22. A stay 20 is arranged in a cylindrical fixing film 22, and is integrally provided with a power supply connector 26 and a power cutoff member 27, and is equipped with a heating element 21 to constitute a fixing heating unit.
The film end regulating flange 25 applies a pressing force to the stay 20 by contracting the coil spring 24 between the coil spring 24 and a spring receiving member (not shown). As a result, a fixing nip portion having a predetermined width is formed between the lower surface of the fixing film 22 and the upper surface of the pressure roller 23. The heating element 21 includes a heater substrate 21a, a heating element 21b, a surface protection layer 21c, and a temperature detecting element 21d. The pressure roller 23 is a sponge pressure roller having a foam such as silicone rubber in a lower layer. As the fixing film 22, it is preferable to use a heat-resistant film on the contact surface with the transfer material. As the heat-resistant film, specifically, a film having a low-resistance release layer in which a conductive substance is dispersed in a resin such as PTFE can be used.

For example, the surface temperature of the temperature measuring element 21d of the heating element 21 is set to 180 ° C., and the heating element 21 and a sponge pressure roller 2 having a silicone rubber foam as a lower layer are used.
3 is 6 kg, and the nip between the pressure roller 23 and the fixing film 22 is 8 mm. The fixing film 22 has a low-resistance release layer in which a conductive material is dispersed in PTFE (high molecular weight type) on a contact surface with the transfer material.
A heat-resistant polyimide film of 0 μm can be used.

On the other hand, the transfer residual toner 213 remaining on the photoconductor 209 without being transferred is transferred to the photoconductor 209 and the charging roller 2.
10 and again reaches the developing contact portion, and is collected in the developing device 200 via the toner carrier 202 by the developing and cleaning process. The transfer residual toner on the photoreceptor after the transfer is collected in the developing and cleaning step, and the collected toner is collected in the developing device and used again for development.

The image forming method of the present invention may be a full-color image forming method using an intermediate transfer system, and the above-described contact developing system can be suitably used.

FIG. 2 shows an example of a color image forming apparatus (copier or laser beam printer) using an intermediate transfer belt as an intermediate transfer member. The toner used in the image forming method of the present invention is the above-described toner of the present invention. Other than using the intermediate transfer belt, another image forming method using the same image forming apparatus as described above can be used.

A photosensitive drum 101, which is a drum-shaped electrophotographic photosensitive member serving as a first electrostatic latent image carrier, is driven to rotate at a predetermined peripheral speed (process speed) in the X direction indicated by an arrow. During the rotation of the photosensitive drum 101, the primary charger 102
, And is uniformly charged to a predetermined polarity potential, and then subjected to exposure 103 by image exposure means (not shown). In this way, an electrostatic latent image corresponding to the first color component image (for example, a yellow color component image) of the target color image is formed.

Next, the electrostatic latent image is developed into a yellow component image of the first color by a first developing device (yellow developing device 141). At this time, the second to fourth developing devices, namely, the magenta developing device 142, the cyan developing device 143, and the black developing device 144 are not operating and do not act on the photosensitive drum 101. The color yellow component image is not affected by the second to fourth developing units.

The intermediate transfer belt 120 is driven to rotate at the same peripheral speed as the photosensitive drum 101 in the direction of arrow W.

[0251] The first
The primary transfer bias applied to the intermediate transfer belt 120 from the bias power source 129 via the primary transfer roller 162 while the yellow component image of the color passes through the contact portion between the photosensitive drum 101 and the intermediate transfer belt 120 Is transferred onto the outer peripheral surface of the intermediate transfer belt 120 (primary transfer).

After the transfer of the first color yellow toner image corresponding to the intermediate transfer belt 120, the surface of the photosensitive drum 101 is cleaned by the cleaning device 113.

Hereinafter, similarly, the magenta toner image of the second color,
A cyan toner image of the third color and a black toner image of the fourth color are formed, sequentially transferred and superimposed on the intermediate transfer belt 120, and a composite color toner image corresponding to a target color image is formed.

The secondary transfer roller 163 corresponds to the secondary transfer opposing roller 164 and is supported in parallel with the intermediate transfer belt 1.
It is arranged on the lower surface of the unit 20 so as to be separated therefrom.

The primary transfer bias for transferring the toner image from the photosensitive drum 101 to the intermediate transfer belt 120 is applied from a bias power supply 129 with a polarity opposite to that of the toner.
The applied voltage is, for example, in the range of +100 V to +2 kV.

From the photosensitive drum 101 to the intermediate transfer belt 12
When the first to third color toner images are primarily transferred to 0,
It is also possible to separate the secondary transfer roller 163 from the intermediate transfer belt 120. When the transfer residual toner charging member 152 is provided as shown in FIG. 2B, this is also separated from the intermediate transfer belt 120. A voltage is applied to the transfer residual toner charging member from a bias power supply 126.

The paper feed roller 111 passes through the guide 110.
The transfer material P, which is the second image carrier, is fed to the contact portion between the intermediate transfer belt 120 and the secondary transfer roller 163 at a predetermined timing. When the secondary transfer bias is applied to the secondary transfer roller 163 by the bias power supply 128, the full-color image transferred on the intermediate transfer belt 120 is secondarily transferred to the transfer material P. The transfer material P on which the toner image has been transferred is introduced into the fixing device 115 and is fixed by heating.

After the image transfer to the transfer material P is completed, the transfer residual toner cleaning device 150 is brought into contact with the intermediate transfer belt 120, and the surface of the intermediate transfer belt 120 is cleaned.

As an intermediate transfer member, an intermediate transfer drum can be used in place of the intermediate transfer belt. An example is described below.

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

As the medium resistance elastic layer, silicone rubber, Teflon rubber, chloroprene rubber, urethane rubber,
Elastic materials such as EPDM (terpolymer of ethylene-propylene-diene) include carbon black, zinc oxide,
A solid or foamed layer whose electrical resistance (volume resistance) is adjusted to a medium resistance of about 10 ⁵ to 10 ¹¹ Ω · cm by mixing and dispersing a conductivity imparting agent such as tin oxide and silicon carbide is preferably used. Can be

The intermediate transfer drum is provided in contact with the lower surface of the electrostatic latent image carrier while being supported in parallel with the electrostatic latent image carrier, and has the same circumference as the electrostatic latent image carrier. It rotates in the same or opposite direction as the electrostatic latent image carrier at a speed.

A transfer device is provided in parallel with the intermediate transfer drum and in contact with the lower surface of the intermediate transfer drum. The transfer device is, for example, a transfer roller or a transfer belt, and has the same peripheral speed as the intermediate transfer drum. To rotate in the same direction at the contact portion.

The transfer device is disposed so as to be in direct contact with the intermediate transfer drum. In the case of a transfer roller, the transfer roller basically has a core metal at the center and a conductive elastic layer forming the outer periphery thereof.

A general material can be used for the intermediate transfer drum and the transfer roller. By setting the volume specific resistance of the elastic layer of the intermediate transfer drum to be smaller, the voltage applied to the transfer roller can be reduced, a good toner image can be formed on the transfer material, and the transfer material can be wound around the intermediate transfer drum. Can be prevented. In particular, it is particularly preferable that the volume resistance of the elastic layer of the intermediate transfer drum is at least 10 times the volume resistance of the elastic layer of the transfer roller.

For example, the conductive elastic layer of the transfer roller may have a volume resistivity of 10 ⁶ to 10 ¹⁰ Ω · such as polyurethane or ethylene-propylene-diene terpolymer (EPDM) in which a conductive material such as carbon is dispersed. It is made of an elastic material of about cm. A bias is applied to the core of the transfer roller from a low voltage power supply, and the bias condition is preferably 0.2 to 10 kV in absolute value.

In the above description, an image forming method by a one-component developing method having a developing and cleaning step, or an image forming method of an intermediate transfer system using an image forming apparatus having an intermediate transfer belt and an intermediate transfer drum has been described. The toner of the present invention can be suitably used in image forming methods other than those described above.

[0268]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

All parts in the following formulations are parts by mass.

<1> Production of Diene Monomer Component-Containing Resins Diene monomer component-containing resins 1 to 10 were produced as follows.

<Production of Resin 1 Containing Diene Monomer Component> In a reaction vessel capable of reducing pressure, 80 parts by mass of styrene, 1 part by mass of 2,2′-azobisisobutyronitrile and 500 parts by mass of benzene were added. Then, 20 parts by mass of 1,3-butadiene was charged by distillation through a liquefaction meter, and then degassed under reduced pressure until bubbles of dissolved air disappeared, and sealed under vacuum. This was polymerized while shaking in a thermostat at 60 ° C. After the completion of the polymerization, the sealed tube was opened, and the content was poured into methanol for reprecipitation. The supernatant was decanted, and the precipitate was washed with methanol.
(1.5 mmHg) under reduced pressure for 24 hours to obtain a styrene-butadiene copolymer (diene monomer component-containing resin 1). The composition ratio of this polymer was determined as follows.
As a result, the mass ratio of styrene / butadiene is 80/2.
It was 0. Table 2 shows the mixing ratio of the raw materials, and Table 3 shows the characteristic values.

The measurement of the content of the component derived from the diene monomer was performed using ¹ H-NMR as follows.

The polymer 50 to 10 which has been sufficiently washed and dried
0 mg was weighed and dissolved in 1.0 ml of a deuterated solvent containing 1% by volume of tetramethylsilane for 24 hours, and if necessary, an insoluble content was removed with a membrane filter.
FT-NMR device J
It measured using NM-EX400 (made by JEOL Ltd.).

[0274]

[Table 2] ──────────────────────────────────── Resin name Diene monomer Other single monomer Body ──────────────────────────────────── Type Prepared amount Type Prepared amount (parts by mass) (parts by mass ──────────────────────────────────── ──────────────────────────────────── Diene monomer component containing resin 1 Phthadiene 20 Styrene 80 Diene Resin containing monomer component 2 Phthadiene 25 4-Chlorostyrene 75 Resin containing diene monomer component 3 Isophthalene 12 Styrene 88 Resin containing diene monomer component 4 Chloroprene 30 Styrene 70 Resin containing diene monomer component 5 Phthadiene 15 Styrene 85 ────────────────────────────────────

[0275]

[Table 3] ──────────────────────────────────── Resin name Composition of obtained resin By GPC Molecular weight distribution ──────────────────────────────────── Derived from diene monomer and other monomer Component derived Component Mn Mw す る Diene monomer component-containing resin 1 20 80 19000 48000 Resin containing diene monomer component 2 23 77 7000 49000 Resin containing diene monomer component 3 13 87 12000 58000 Resin containing diene monomer component 4 28 72 9000 32000 Resin containing diene monomer component 5 15 85 17000 180000 ──────────────────────────────────── <Production of resin 2 containing diene monomer component > Table 2 shows the types and amounts of the monomers used. A diene monomer component-containing resin 2 was obtained in the same manner as in the production of the diene monomer component-containing resin 1, except that the resin was changed as shown in (1). Table 3 shows the characteristic values.

<Production of Resin 3 Containing Diene Monomer Component> In a pressure-resistant bottle equipped with a septum cap, 126 parts by mass of water were added.
3.3 parts by mass of disproportionated potassium rosinate, 0.07 parts by mass of sodium salt of naphthalenesulfonic acid-formalin condensate, 0.07 parts by mass of tetraethylenepentamine, 50 parts by mass of styrene, 0.17 part of tertiary dodecyl mercaptan Parts by mass, and then using a liquefaction meter to measure isoprene 9
A part by mass was charged, and 2 parts by mass of isoprene was vaporized to expel internal air and plugged. The mixture was attached to a rotary polymerization phase rotating plate at 5 ° C. and stirred for 30 minutes, and then a solution of 0.1 parts by mass of cumene hydroperoxide and 3.5 parts by mass of styrene was injected using a syringe to initiate polymerization. After 72 hours, 3.5 parts by mass of a 10% aqueous solution of sodium dimethyldithiocarbamate was injected to terminate the polymerization, and unreacted monomers were expelled by blowing steam. After adding phenyl-6-naphthylamine corresponding to 2% of the copolymer, a 25% saline solution and then 1% sulfuric acid were poured to coagulate the copolymer, washed with water, and dried to obtain a resin containing a diene monomer component. 3 was obtained. Table 3 shows the characteristic values.

<Production of Diene Monomer Component-Containing Resin 4> A diene monomer component-containing resin 4 was prepared in the same manner as in the preparation of the diene monomer component-containing resin 3, except that the type and amount of the monomers used were changed as shown in Table 2. A monomer component-containing resin 4 was obtained. Table 3 shows the characteristic values.

<Production of Diene Monomer Component-Containing Resin 5> 85 parts by mass of styrene, 15 parts by mass of butadiene, 5 parts by mass of sodium fatty acid, and 200 parts by mass of ion-exchanged water were mixed.
The reactor was placed in an autoclave as a polymerization vessel. Subsequently, 3.5 parts by mass of n-dodecyl mercaptan and potassium persulfate 0.1 part by mass.
2 parts by mass were added and emulsion polymerization was carried out at 50 ° C. for 15 hours to obtain a diene monomer component-containing resin 5. Table 3 shows the characteristic values.

<Production of Resin 6 Containing Diene Monomer Component>
In a 0 l autoclave, 114 parts by mass of benzyl sodium, 368 parts by mass of toluene and 9900 parts by mass of n-hexane were charged under a nitrogen stream, and the mixture was heated to 30 ° C. The polymerization was stopped by adding 200 parts by mass of methanol. Next, 1000 parts by mass of clay was added and stirred vigorously, followed by filtration to obtain a transparent polymer solution containing no alkali. Next, unreacted butadiene, toluene, n-
Hexane was distilled off to synthesize a diene monomer component-containing resin 6 having a number average molecular weight of 1900. Table 4 shows the characteristic values.

[0280]

[Table 4] ───────────────────────────── Resin name Molecular weight distribution by GPC Number average molecular weight (Mn) ───── ──────────────────────── Resin containing diene monomer component 6 1900 Resin containing diene monomer component 7 2000 Resin containing diene monomer component 8 9000 Diene monomer component-containing resin 9 10000 Diene monomer component-containing resin 10 11000 ───────────────────────────── <diene Production of monomer component-containing resin 7> 1000 parts by mass of diene monomer component-containing resin 6 and 150 parts of maleic anhydride
2 parts by mass of xylene, 300 parts by mass of xylene, and 2 parts by mass of Antigen 3C (trade name of Sumitomo Chemical Co., Ltd.) were charged into a 2 l autoclave and reacted at 190 ° C. for 8 hours under a nitrogen stream. Next, unreacted maleic anhydride and xylene were distilled off under reduced pressure to synthesize a maleated polybutadiene having a number average molecular weight of 2,000 (resin 7 containing a diene monomer component).

The structure of the acid group in the maleated polybutadiene (A) ′ is mostly represented by the following formula (IV).

[0282]

[Outside 10]

Also included are those having a structure of the following formula (V) which is partially hydrolyzed with water contained in air or a solvent.

[0284]

[Outside 11]

Table 4 shows the characteristic values of the resin 7 containing the diene monomer component.

<Production of Diene Monomer Component-Containing Resin 8> In the production example of the diene monomer component-containing resin 6, except that the butadiene used as a raw material was changed to 6500 parts by mass of isoprene, The diene monomer component-containing resin 8 was obtained in the same manner as in the production of Table 4 shows the characteristic values.

<Production of Resin 9 Containing Diene Monomer Component> In a 2 liter reactor equipped with a condenser, a peracetic acid charging port, and a N ₂ introduction pipe, the solid content of the resin 8 containing the diene monomer component was 46.3%. Of ethyl acetate solution was charged. Next, 0.2 parts by mass of sodium 2-ethylhexyltripolyphosphate was dissolved in 280 parts by mass of peracetic acid (30%, ethyl acetate solution). Thereafter, while maintaining the reaction temperature at 50 ° C., the peracetic acid solution was added dropwise over about 4 hours. Thereafter, the temperature was kept at 50 ° C. for further 6 hours.

Next, 680 parts by mass of purified water was added, and 30
After stirring for minutes, the mixture was allowed to stand at 50 ° C. After 30 minutes, the separated aqueous phase was gradually withdrawn. Next, 300 parts by mass of ethyl acetate was added, 800 parts by mass of purified water was further added, and the mixture was stirred for 30 minutes. Then, the mixture was allowed to stand at 50 ° C. for 30 minutes to extract an aqueous phase. Further, 700 parts by mass of purified water was added, and the mixture was stirred at 50 ° C. for 30 minutes. Next, the mixture was allowed to stand at 50 ° C. for 30 minutes, and the aqueous phase was extracted to obtain 650 parts by mass of an ethyl acetate solution having a solid content of 30.1%.

Subsequently, the obtained upper layer solution was placed in a thin film evaporator at 50 ° C. and 2700 to 6700 Pa (20 to 50 mmH).
g) and 300 ml / h, and diene monomer component-containing resin 9 having the desired epoxy group was added to 18
0 parts by mass were obtained. Table 4 shows the characteristic values.

<Production of Resin 10 Containing Diene Monomer Component>
Condenser, jacketed 2l with a N ₂ inlet tube
In the reactor, 11 of the synthesized diene monomer component-containing resin 7 was added.
150 parts by mass of glycidyl methacrylate was added to 50 parts by mass, and the mixture was heated to 60 ° C. in a reaction vessel and reacted for 12 hours to obtain 1,300 parts by mass of a resin 10 containing a diene monomer component. Table 4 shows the characteristic values.

<2> Production of Resin Used in Conjunction with Diene Monomer-Containing Resin Resins 1 and 2 were produced as follows.

<Production of Resin 1> 200 parts by mass of xylene was placed in a glass separable flask equipped with a thermometer, a stainless steel stirrer, a falling condenser, and a nitrogen inlet tube, and the temperature was raised to the reflux temperature. To this, 80 parts by mass of styrene, 20 parts by mass of n-butyl acrylate and di-te
After dropping a mixture of 2.3 parts by mass of rt-butyl peroxide, the solution polymerization was completed in 7 hours under reflux of xylene to obtain a low molecular weight resin solution.

On the other hand, 65 parts by weight of styrene, 25 parts by weight of butyl acrylate, 10 parts by weight of monobutyl maleate, 0.2 parts by weight of polyvinyl alcohol, 200 parts by weight of deaerated water, and 0.5 parts by weight of benzoyl peroxide were mixed and suspended. Dispersed. The above suspension and dispersion solution is heated to 85 ° C. under a nitrogen atmosphere.
For 24 hours to complete the polymerization to obtain a high molecular weight resin.

30 parts by mass of the high-molecular-weight resin is put into a low-molecular-weight resin solution containing 70 parts by mass of the low-molecular-weight resin, completely dissolved in a solvent and mixed.
The solvent was distilled off to obtain Resin 1.

When the resin 1 was analyzed, the peak molecular weight on the low molecular weight side was 10,000, and the peak molecular weight on the high molecular weight side was 56.
10,000, the weight average molecular weight (Mw) was 300,000, and the number average molecular weight (Mn) was 550,000. The glass transition temperature was 55 ° C.

<Production of Resin 2> A low molecular weight resin solution was obtained in the same manner as in the production of Resin 1.

On the other hand, 75 parts by mass of styrene, 25 parts by mass of butyl acrylate, 0.2 parts by mass of polyvinyl alcohol, 200 parts by mass of degassed water, and 0.5 parts by mass of benzoyl peroxide 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 high molecular weight resin.

30 parts by mass of the high-molecular-weight resin is put into a low-molecular-weight resin solution containing 70 parts by mass of the low-molecular-weight resin, completely dissolved in a solvent and mixed.
The solvent was distilled off to obtain Resin 2.

When the resin 2 was analyzed, the peak molecular weight on the low molecular weight side was 12,000 and the peak molecular weight on the high molecular weight side was 5
80,000, the weight average molecular weight (Mw) was 300,000, and the number average molecular weight (Mn) was 550,000. The glass transition temperature was 55 ° C.

<3> Production of Toners Toners 1 to 12 of the present invention and comparative toners 1 to 6 as comparative toners were produced as follows.

<Production of Toner 1> 100 parts by mass of resin 1 10 parts by mass of resin 1 containing diene monomer component 10 parts by mass of carbon black (BET specific surface area = 90 m ² / g) Compound (II)) 2 parts by mass Low-molecular-weight polyethylene (maximum endothermic peak = 115 ° C.) 5 parts by mass The above materials are mixed by a blender, and melted and kneaded by a biaxial extruder heated to 160 ° C. After the cooled kneaded material was coarsely pulverized by a hammer mill, the coarsely pulverized material was finely pulverized by a jet mill.

Next, a surface modification treatment was carried out using a device for applying a mechanical impact by rotating a rotor, and the obtained particles were classified to obtain a classified powder 1. On the other hand, the high-speed stirring device T
650 parts by mass of ion-exchanged water and 0.1 part
500 parts by mass of an aqueous solution of mol / l-Na ₃ PO ₄
The rotation speed was adjusted to 12000 rpm, and the mixture was heated to 70 ° C. Here, 1.0 mol / l-CaCl ₂ aqueous solution 80
An aqueous dispersion medium containing fine parts of a poorly water-soluble dispersion stabilizer (calcium phosphate salt) was prepared. 127 parts by mass of the classified powder 1 was gradually added to an aqueous dispersion medium containing a dispersion stabilizer, heated to 60 ° C. and maintained at the same temperature,
0.7 parts by mass of t-butyl peroxy neodecanoate was added to sodium dodecylbenzenesulfonate 0.01%.
A dispersion liquid obtained by ultrasonically dispersing the mixture in parts by mass and 20 parts by mass of ion-exchanged water was added over 5 minutes, and then the mixture was kept at the same temperature for 5 hours to perform a reaction. After the completion of the reaction, the suspension was cooled, and then dilute hydrochloric acid was added to remove the dispersion stabilizer. Further, after repeating water washing several times, drying was performed, and the reaction-treated particles A
I got

Hydrophobic silica fine powder (BET) treated with 100 parts by mass of the reaction-treated particles A and silicone oil
1.2 parts by mass of specific surface area (240 m ^{2 /} g) were dry-mixed with a Henschel mixer to obtain Toner 1 of the present invention.

The average circularity of the toner 1 is 0.953, the standard deviation of the circularity is 0.039, and the circle-equivalent number average diameter D1 is 5.
3 μm, the peak molecular weight on the high molecular weight side was 580,000, and the peak molecular weight on the low molecular weight side was 11,000.

<Production of Toner 2> Toner 2 was obtained in the same manner as in the production of Toner 1 except that the kind and amount of the binder resin were changed. Table 5 shows the types and amounts of the materials used, and Table 8 shows the analysis results of the toner.

[0306]

[Table 5]

<Production of Toner 3> 650 parts by mass of ion-exchanged water and 0.1 mol / l were placed in a 2-liter four-necked flask equipped with a high-speed stirrer TK homomixer (manufactured by Tokushu Kika Kogyo KK).
-Charge 500 parts by mass of an aqueous solution of Na ₃ PO ₄ , and
It was adjusted to 2000 rpm and heated to 70 ° C. 80 parts by mass of a 1.0 mol / l-CaCl ₂ aqueous solution was added thereto to prepare an aqueous dispersion medium containing a minute water-insoluble dispersion stabilizer (calcium phosphate salt).

On the other hand, dispersoids include:-82 parts by mass of styrene-18 parts by mass of 2-ethylhexyl acrylate-10 parts by mass of carbon black (BET specific surface area = 90 m ² / g)-Resin containing diene monomer component 1 10 Parts by mass Wax (ester wax, maximum value of endothermic peak = 76 ° C) 7 parts by mass Negative charge control agent (compound (II)) 2 parts by mass The above mixture is used for 3 hours using an attritor (Mitsui Metals). After the dispersion, 3 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to prepare a polymerizable monomer composition.

Next, the polymerizable monomer composition was charged into the aqueous dispersion medium, and the mixture was heated under a nitrogen atmosphere at an internal temperature of 70 ° C. while maintaining the rotation speed of a high-speed stirrer at 12,000 rpm.
The mixture was stirred for 0 minute to granulate the polymerizable monomer composition. After that, when the stirrer was replaced with a propeller stirring blade and kept at the same temperature for 2 hours while stirring at 50 rpm, a solution in which 0.4 parts by mass of potassium persulfate was dissolved in 20 parts by mass of ion-exchanged water was taken over 5 minutes. After the addition, the mixture was kept at the same temperature for 8 hours to complete the polymerization. The conversion of the polymerization reaction when potassium persulfate was added was 43%.

After completion of the polymerization, 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, it was dried to obtain polymer particles 3. The polymer particles 3 had a mass average diameter of 6.8 μm.

100 parts by mass of the above polymer particles 3 and 1.5 parts by mass of hydrophobic silica fine powder (BET specific surface area 240 m ^{2 /} g) treated with silicone oil were dry-mixed with a Henschel mixer to obtain the toner of the present invention. It was set to 3.

The average circularity of the toner 3 is 0.989, the standard deviation of the circularity is 0.021, and the average number D1 of the circle-equivalent number is 5.
5 μm, the peak molecular weight was 26,000.

<Production of Toners 4 to 10> Toners 4 to 10 were obtained in the same manner as in the production of Toner 3, except that the type and amount of the binder resin and the reaction temperature during the reaction treatment were changed. Table 6 shows the types and amounts of the materials used, and Table 8 shows the analysis results of the toner.
Shown in

[0314]

[Table 6]

<Production of Toners 11 and 12> Table 6 was prepared by changing the type and amount of the binder resin and the reaction temperature during the reaction treatment.
Toner 3 was prepared by adding a dispersion obtained by ultrasonically dispersing the organic peroxide in the table at 0.01 parts by mass of sodium dodecylbenzenesulfonate and ion-exchanged water at the polymerization conversion rate shown in Table 5 over 5 minutes. In the same manner as in the production of
And 12 were obtained. Table 6 shows the types and amounts of the materials used, and Table 8 shows the analysis results of the toner.

<Production of Comparative Toner 1>
Comparative toner 1 was obtained in the same manner as in the production of toner 1, except that the amount of addition was changed. Table 5 shows the types and amounts of materials used.
Table 8 shows the analysis results of the toner.

<Production of Comparative Toner 2>
Comparative toner 2 was obtained in the same manner as in the production of toner 1, except that the amount of addition was changed and the reaction treatment with the initiator was not performed. Table 5 shows the types and amounts of the materials used, and Table 8 shows the analysis results of the toner.

<Production of Comparative Toners 3 to 6> Comparative toners 3 to 6 were obtained in the same manner as for toner 3 except that the type of binder resin and the amount added were changed. Table 7 shows the types and amounts of the materials used, and Table 8 shows the analysis results of the toner.

<Production of Comparative Toner 7> 650 parts by mass of ion-exchanged water and 0.1 mol in a 2 liter four-necked flask equipped with a high-speed stirrer TK homomixer (manufactured by Tokushu Kika Kogyo KK)
/ L-Na ₃ PO ₄ aqueous solution 500 parts by weight were charged, and adjust the rotation speed 12000 rpm, was allowed to warm to 70 ° C..
80 parts by mass of a 1.0 mol / l-CaCl ₂ aqueous solution was added thereto to prepare an aqueous dispersion medium containing a minute water-insoluble dispersion stabilizer (calcium phosphate salt).

[0320] On the other hand, the dispersoid as, ethylhexyl acrylate 18 parts by mass Carbon black to Styrene 82 parts by mass of 2-ethyl (BET specific surface area = 90m ² / g) 10 parts by mass Unsaturated polyester 10 parts by mass Wax ( Ester wax, maximum value of endothermic peak = 76 ° C) 7 parts by mass ・ Negative charge control agent (compound (II)) 2 parts by mass After dispersing the above mixture using an attritor (Mitsui Metals Co., Ltd.) for 3 hours, 3 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to prepare a polymerizable monomer composition.

Next, the polymerizable monomer composition was charged into the aqueous dispersion medium, and the mixture was maintained at 12,000 rpm under a nitrogen atmosphere at an internal temperature of 70 ° C. while maintaining the rotation speed of the high-speed stirrer at 12,000 rpm.
The mixture was stirred for 0 minute to granulate the polymerizable monomer composition. Thereafter, the stirrer was replaced with a propeller stirring blade, and at the same temperature maintained for 2 hours while stirring at 50 rpm, 8.2 parts by mass of styrene monomer, 1.8 parts by mass of n-butyl acrylate, 2.5 parts by mass of unsaturated polyester , A polymerizable monomer composition prepared by dissolving and dispersing 0.4 parts by mass of potassium persulfate in 40 parts by mass of ion-exchanged water is added over 60 minutes, and further maintained at the same temperature for 8 hours to complete the polymerization. did. At the time when the polymerizable monomer composition was added, the conversion of the polymerization reaction was 6
It was 0%.

After completion of the polymerization, 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, it was dried to obtain polymer particles 7. The comparative polymer particles 7 had a mass average diameter of 7.0 μm.

100 parts by mass of the above polymer particles 7 and 1.5 parts by mass of hydrophobic silica fine powder (BET specific surface area 240 m ^{2 /} g) treated with silicone oil were dry-mixed with a Henschel mixer to obtain a comparative toner 7. And

The average circularity of the comparative toner 7 was 0.97.
5. The standard deviation of the circularity is 0.031, and the number average diameter D is equivalent to a circle.
1 was 5.8 μm, and the peak molecular weight was 300000. Table 8 shows the analysis results of the toner.

[0325]

[Table 7]

[0326]

[Table 8]

<Example 1> Toners 1 to 12 of the present invention and comparative toners 1 to 7 obtained as described above were evaluated as follows.

First, the image forming apparatus used in this embodiment will be described. In this example, a commercially available laser beam printer LBP-PX (manufactured by Canon) was modified and used for non-magnetic one-component development. The image forming apparatus will be described with reference to FIG.

In this embodiment, the negative (negative) polarity on the photosensitive member
A reversal developing device for developing a latent image using a negative (negative) toner was used.

FIG. 1 is a schematic explanatory view of a cross section of a laser beam printer applied to the present invention. The OPC photosensitive drum 10 (diameter 24 mm) rotates in the direction of the arrow, and is uniformly charged by the charging roll 11 so that the dark portion potential (Vd) becomes −600 V. Next, the image portion is exposed by the exposure device 14 to form an electrostatic latent image having a bright portion potential (Vl) of -150V. The toner layer on the toner carrier 17 having the toner application roller 16 and the photosensitive drum 10 are set in contact with each other at an interval of 300 μm without contact, and an AC bias (f = 1800 Hz, Vpp = 1400 V) and a DC bias (Vdc = − 400 V) was applied to the toner carrier 17 by the bias applying means V, and the image portion was developed with the negative toner T to form a toner image on the photosensitive drum 10.

[0331] The obtained toner image is transferred onto a transfer material P by a transfer roll 19, and the toner remaining on the surface of the photosensitive drum 10 is cleaned by a cleaner 13. On the other hand, the transfer material P separated from the photosensitive drum 10 is heated and fixed by the heat fixing device H in order to fix the toner image on the transfer material P. Image formation is performed by repeating the above steps. At this time, as the heat fixing device H, the one shown in FIGS. 3 and 4 is used, the surface temperature of the temperature detecting element 21d of the heating body 21 is 190 ° C., and the total pressure between the heating body 21 and the pressure roller 23 is 6 kg. , Pressure roller 2
The nip between 3 and the fixing film 22 is 3 mm, and the fixing film 22 is a heat-resistant polyimide film having a thickness of 50 μm and having a low-resistance release layer in which a conductive material is dispersed in PTFE on a contact surface with the transfer material. did.

The surface roughness Ra (μm) of the toner carrier used here is 1.5, and the material of the toner layer thickness regulating blade is stainless steel.

In this embodiment, the image forming apparatus shown in FIG. 1 is used, and is controlled at normal temperature and normal humidity (25 ° C., 60% RH).
High temperature and high humidity (30 ° C, 80% RH) and low temperature and low humidity (15
The toners 1 to 12 of the present invention and the comparative toners 1 to 6 are printed in an intermittent mode (that is, every time one sheet is printed) at a printout speed of 28 sheets / min (A4 size) under an environment of 10 ° C. and 10% RH. Mode in which the developing unit is stopped for 10 seconds and the deterioration of the toner is promoted by the preliminary operation at the time of restarting.
A 00 printout test was performed. Then, the obtained printout image was evaluated for items described below.

<Evaluation of printout image>

(1) Image density 500 using ordinary paper for copying machines (75 g / m ² )
Evaluation was made based on the image density at the end of the zero-sheet printout test. The image density was measured by using a "Macbeth reflection densitometer" (manufactured by Macbeth Co., Ltd.) with respect to a printout image of a white background portion having a document density of 0.00. A: 1.40 or more B: 1.35 or more and less than 1.40 C: 1.00 or more and less than 1.35 D: less than 1.00

(2) Image fog "Reflectometer MODEL TC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.)
Was used to calculate the fog density (%) from the difference between the whiteness of the white portion of the printout image at the end of the printout test and the whiteness of the transfer paper, and the image fog was evaluated. A green filter was used as the filter. The smaller the number,
It means less fog. A: less than 1.5% B: 1.5% or more, less than 2.5% C: 2.5% or more, less than 4.0% D: 4.0% or more

(3) Uniformity of Halftone Image The image quality of the printout image at the end of the printout test was evaluated according to the following criteria. A: Very good. B: Good image, though slightly rough. C: A level that is rough but has no practical problem. D: Severe but rough.

(4) Fixability The fixability was evaluated by applying a load of 50 g / cm ² , rubbing the fixed image five times with soft thin paper, and reducing the image density before and after rubbing (%). A: less than 5% B: 5% or more and less than 10% C: 10% or more, less than 20% D: 20% or more

(5) Offset Resistance The offset resistance was evaluated by printing out a sample image having an image area ratio of about 5% and evaluating the degree of stain on the image after 5,000 sheets. A: Dirt is not generated. B: Slight dirt is seen. C: Some dirt is seen. D: Remarkable dirt is generated.

The results of these evaluations are shown in Table 9.

[0341]

[Table 9]

<Example 2> Toners 3 to 12 of the present invention and comparative toners 3 to 7 obtained in the above-described toner production examples.
Was evaluated as follows.

First, as an image forming apparatus, an apparatus having the same structure as the image forming apparatus shown in FIG. Specifically, it is as follows.

A 600 dpi laser beam printer (manufactured by Canon: LBP-860) was prepared, and the process speed was changed to 60 mm / s.

The cleaning rubber blade in this process cartridge was removed, the charging method of the apparatus was set to direct charging performed by bringing the rubber roller into contact with the electrostatic latent image carrier (photoconductor), and the applied voltage was set to a DC component (−1200 V). did. Next, the developing portion of the process cartridge was modified. Medium resistance rubber roller made of silicone rubber dispersed with carbon black instead of stainless steel sleeve (diameter 16 mm, hardness ASKER C 45 degrees, resistance 10 ⁵ Ω
cm) was used as a toner carrier and was in contact with the photoreceptor. The developing contact width at this time was set to about 3 mm. The peripheral speed of rotation of the toner carrier was the same in the contact portion with the photoconductor, and the toner carrier was driven to be 150% of the peripheral speed of the photoconductor.

The photoreceptor used here has a diameter of 30 m.
m, a 254 mm Al cylinder as the base,
On this, layers having the following structures were sequentially laminated by dip coating to prepare a photoreceptor. 1) Conductive coating layer: mainly composed of tin oxide and titanium oxide powders dispersed in a phenol resin (film thickness 1.5 μm)
m). 2) Subbing layer: mainly composed of modified nylon and copolymerized nylon (film thickness: 0.6 μm). 3) Charge generation layer: mainly composed of a butyral resin in which a titanyl phthalocyanine pigment having absorption in a long wavelength region is dispersed (film thickness: 0.6 μm). 4) Charge transport layer: Mainly a hole transporting triphenylamine compound dissolved in a polycarbonate resin (molecular weight 20,000 according to Ostwald viscosity method) at a mass ratio of 8:10 (film thickness: 20 μm).

As means for applying toner to the toner carrier, an application roller made of urethane foam rubber was provided in the developing device, and was brought into contact with the toner carrier. A voltage of about -550 V is applied to the application roller. Further, a stainless steel blade coated with a resin for controlling the coat layer of the toner on the toner carrier was attached such that the contact pressure with the toner carrier was about 20 g / cm. An outline is shown in FIG. Further, the applied voltage at the time of development is changed to a DC component (−450
V) only.

The image forming apparatus was modified and the process conditions were set as follows so as to be adapted to the modification of the process cartridge.

The modified device uniformly charges the electrostatic latent image carrier using a roller charger (only DC is applied). After charging, an image is exposed to a laser beam to form an electrostatic latent image by exposing the image portion to a visible image with toner, and then the toner image is transferred to a transfer material by a roller to which a voltage is applied.

Further, the photosensitive member charging potential is set to a dark portion potential of -6.
The voltage was set to 00V, and the bright portion potential was set to -150V. 75 g / m ² paper was used as the transfer material.

With the above image forming apparatus, the toners 3 to 12 of the present invention and the comparative toners 3 to 7 were used at a temperature of 15 ° C.
A durability test was performed under the conditions of 10% / humidity.

The durability was evaluated by printing a character at a print area ratio of 3% and evaluating as follows.

(1) Contamination of toner on charging roller: Judgment was made based on the number of sheets on which charging unevenness occurred due to contamination of the charging member on the halftone image. A: Not generated up to 3000 sheets B: Generated between 2700 and less than 3000 sheets C: Generated between 2000 and less than 2700 sheets D: Generated when less than 2000 sheets

(2) Fusion of Photoconductor and Sleeve of Toner: At the stage when white spots occurred on a solid black image, the surface of the photoconductor and the surface of the sleeve were observed to confirm the presence or absence of fusion. If no fusion was observed, the durability evaluation was continued. A: Not generated up to 3000 sheets B: Generated between 2700 and less than 3000 sheets C: Generated between 2,000 and less than 2700 sheets D: Generated when less than 2000 sheets Charging roller contamination, photoconductor fusion and sleeve fusion When no adhesion occurred, image printing was continued up to 3000 sheets. The greater the number of generated sheets, the better the durability of the toner.

(3) Transferability in the initial stage of durability: The transfer residual toner on the photoreceptor at the time of image development was taped off with a Mylar tape and stripped off. Evaluation was made by subtracting the Macbeth concentration. Therefore, the smaller the value, the better the transferability. A: less than 0.05 B: 0.05 to less than 0.10 C: 0.10 to less than 0.20 D: 0.20 or more

(4) As for the resolving power in the early stage of durability (at the time of 100 sheets), the electric field is easily closed by the latent image electric field, and it is difficult to reproduce FIG.
An image of an isolated dot pattern having a small diameter (X = 50 μm) as shown in (1) was printed out, and the dot reproducibility was evaluated. A: 2 or less defects / 100 B: 3 to 5 defects / 100 C: 6 to 10 defects / 100 D: 11 or more defects / 100 defects

(5) Offset property: durability 100 from the beginning
Stain generated on the back side of the image sample on each sheet was observed, and the number of generated sheets was counted. A: not generated B: generated 1-2 sheets / 100 C: generated 3-5 / 100 D: generated 6 or more / 100

(6) Measurement of fog: REFL manufactured by Tokyo Denshoku Co., Ltd.
Measured using ECTMETER MODEL TC-6DS. Using a green filter, the fog density (%) was calculated from the difference between the measured whiteness of the white portion of the printout image and the whiteness of the transfer paper, and the image fog was evaluated. The smaller the value, the less fog. 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 The evaluation results are shown in Table 10.

[0359]

[Table 10]

<Example 3> The toner 5 of the present invention and the comparative toner 6 obtained in the above toner production examples were evaluated as follows.

First, as the image forming apparatus, an apparatus having the same structure as the image forming apparatus shown in FIG. 2 of the above embodiment was used.

The details are as follows.

The moving speed of the toner carrier surface is set to be 150% of the moving speed of the electrostatic latent image carrier surface,
In a normal temperature and normal humidity (23 ° C., 65% RH) environment, the toners 5 and 6 ′ are transferred in a single color continuous mode at a printout speed of 20 sheets / minute (A4 size) (that is, without stopping the developing device). (A mode in which consumption of paper is promoted) and a printout test of 6000 sheets was performed at a print area ratio of 5%. Then, the obtained printout image was evaluated including the items described above and the state of contamination on the intermediate transfer belt.

(7) Intermediate transfer belt fusion, photoconductor fusion, and sleeve fusion of toner: The intermediate transfer belt, the surface of the photoconductor, and the surface of the sleeve were observed at the stage where slight white spots occurred on the solid black image. The presence or absence of fusion was checked. If no fusion was observed, the durability evaluation was continued. A: Not generated up to 6000 sheets B: Generated between 5500 sheets and less than 6000 sheets C: Generated between 5000 sheets and less than 5500 sheets D: Generated when less than 5000 sheets The results are shown in Table 11.

[0365]

[Table 11]

[0366]

As described above, the dry toner of the present invention is excellent in electrophotographic characteristics, gives a high-definition image, is excellent in charge stability, and has a toner carrier, an electrostatic latent image carrier, a fixing device, etc. The contamination on the intermediate transfer member is also small. Further, the method for producing a dry toner according to the present invention can efficiently produce a toner having the above-described excellent electrophotographic properties and little contamination of an image forming apparatus.

Further, by using a toner having an improved strength near the particle surface, in a contactless type image forming process using a cleaner-less structure or an intermediate transfer member, while maintaining the fixing property, the resolution, It is possible to improve the transferability, suppress the occurrence of ghost due to the improvement in toner recovery, and further improve the durability.

[Brief description of the drawings]

FIG. 1 shows a schematic configuration diagram of an example of an image forming apparatus to which an image forming method of the present invention can be applied.

FIG. 2 is a schematic configuration diagram of an image forming apparatus using an intermediate transfer belt for performing the image forming method of the present invention.

FIG. 3 is an exploded perspective view of a main part of the fixing device.

FIG. 4 is a cross-sectional view of a main part showing a film state when a fixing device applicable to the image forming method of the present invention is not driven.

FIG. 5 is a schematic configuration diagram of an image forming apparatus that forms an image by a one-component developing method.

FIG. 6 is a schematic configuration diagram of a developing device applicable to the image forming method of the present invention.

FIG. 7 shows a diagram of a small-diameter isolated dot pattern for checking the development characteristics of toner.

FIG. 8 shows a graph for measuring the glass transition temperature.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 15/08 507 G03G 9/08 325 15/20 101 346 21/10 384 15/08 507L 507B 507D 21 / 00 326 (72) Inventor Motoki Hisaki Within Canon Inc. 3- 30-2 Shimomaruko, Ota-ku, Tokyo (72) Inventor Tatehiko Chiba 3-30-2 Shimomaruko Shimomaruko, Ota-ku, Tokyo F Term (reference) 2H005 AA01 AA06 AA08 AA15 AB06 CA04 CA22 CA25 CB13 DA02 DA06 DA10 EA03 EA05 EA06 EA07 EA10 2H033 AA02 AA09 BA58 BE03 2H034 AA01 AA06 BA01 CA00 CB00 2H077 AA37 GA16 DB12 EA14

Claims (39)

[Claims] 1. A dry toner having an external additive and toner particles containing at least a binder resin, a colorant and a wax component, wherein (1) the binder resin is selected from the group consisting of butadiene, isoprene and chloroprene. Containing a component derived from at least one selected monomer,
(2) The main glass transition temperature (Tg) of the toner measured by a differential scanning calorimeter (DSC) is 40 to 70.
(3) The specific surface area according to the BET method when left in an environment of the ambient temperature of 23 ° C. and a relative humidity of 65% for 72 hours is A (m ² / g), the ambient temperature of the toner is 50 ° C. When the specific surface area by the BET method when left in an environment of a relative humidity of 3% for 72 hours is B (m ² / g), A and B satisfy the following formula: 0.8 ≦ A ≦ 4.0 0.80 ≦ (B / A) ≦ 1.05 (4) The circle equivalent number of the toner in the circle equivalent diameter-circularity scattergram based on the number of toners measured by the toner flow type particle image measuring apparatus. Average diameter D1 is 2
10 μm, and the average circularity of the toner is 0.950
0.995, the circularity standard deviation is less than 0.040, and (5) tetrahydrofuran (TH
F) In the molecular weight distribution measured by gel permeation chromatography (GPC), the soluble component has a main peak molecular weight in the range of 2 × 10 ³ to 1 × 10 ⁵ and a THF insoluble component of 5 to 60% by mass. A dry toner. 2. The dry method according to claim 1, wherein the total content of butadiene, isoprene and chloroprene contained in the binder resin is 0.1 to 20% by mass based on the toner. toner. 3. The dry method according to claim 1, wherein the total content of butadiene, isoprene and chloroprene contained in the binder resin is 0.1 to 10% by mass based on the toner. toner. 4. The dry toner according to claim 1, wherein the binder resin contains a copolymer of styrene and / or a styrene derivative and butadiene. 5. The dry toner according to claim 1, wherein the charge control agent is a charge control agent represented by the following general formula (I). [Outside 1] [Wherein X ₁ and X ₂ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a halogen atom,
X ₁ and X ₂ may be the same or different; m and m ′ each represent an integer of 1 to 3; R ₁ and R _{3 each} represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, 1-18 alkenyl group, sulfonamide group, mesyl group, sulfonyl group, hydroxyl group, alkoxy group having 1-18 carbon atoms,
Acetylamino group, benzoylamino group, a halogen atom or -COOR _5, R ₁ and R ₃ may be different even in the same, n and n 'represents an integer of 1 to 3, R ₂ and R ₄ represents a hydrogen atom or a nitro group,
R ₅ represents an alkyl group or an aryl group, and A ⁺ represents a hydrogen ion, a sodium ion, a potassium ion or an ammonium ion. ] 6. An average circularity of the toner is from 0.970 to 0.9.
The dry toner according to any one of claims 1 to 5, wherein the dry toner is 995. 7. The toner has an average circularity of 0.970 to 0.9.
The dry toner according to any one of claims 1 to 5, wherein the toner has a circularity standard deviation of less than 0.035. 8. In a scattergram of circle equivalent diameter-circularity scattergram based on the number of toners, the toner has a circularity of 0.95.
The dry toner according to any one of claims 1 to 7, wherein the number of toner particles less than 0 is 15% by number or less. 9. The dry toner according to claim 1, wherein the binder resin contains 50 to 99.9% by mass of a styrene-acrylic resin. 10. The dry toner according to claim 1, wherein the binder resin contains 80 to 99.9% by mass of a styrene-acrylic resin. 11. The dry toner according to claim 1, wherein the binder resin contains 85 to 98% by mass of a styrene-acrylic resin. 12. The dry toner according to claim 1, wherein the external additive is silica fine powder. 13. The silica fine powder having a BET specific surface area of 3
The dry toner according to claim 12, wherein the dry toner is 0 m ² / g or more. 14. The silica fine powder having a BET specific surface area of 5
The dry toner according to claim 12, wherein the dry toner is 0 to 400 m ² / g or more. 15. A specific surface area according to a BET method when left in an environment of a toner atmosphere temperature of 23 ° C. and a relative humidity of 65% for 72 hours is A (m ² / g).
B when left in an environment of 0 ° C. and a relative humidity of 3% for 72 hours
When the specific surface area by the ET method is B (m ² / g),
The dry toner according to any one of claims 1 to 14, wherein A and B satisfy the following formula: 0.8 ≦ A ≦ 4.0 0.90 ≦ (B / A) ≦ 1.05 16. The toner tetrahydrofuran (TH)
F) The soluble peak is characterized in that the main peak molecular weight is in the range of 5 × 10 ^{3 to} 5 × 10 ⁴ in the molecular weight distribution measured by gel permeation chromatography (GPC). The dry toner according to any one of the above. 17. The dry toner according to claim 1, wherein the toner has a THF-insoluble content of 5 to 55% by mass. 18. A diene monomer component-containing resin containing a component derived from at least one monomer selected from the group consisting of butadiene, isoprene and chloroprene, a polymerizable vinyl monomer, a colorant, a wax, and a polymer. A method for dispersing and granulating a polymerizable monomer composition containing an initiator in an aqueous medium, polymerizing in an aqueous medium, and producing toner particles, wherein the polymerization initiator initiates radical polymerization. A method for producing a dry toner, characterized in that the radical polymerization initiator (B) is newly added when the conversion of the polymerization reaction is in the range of 10 to 95% by mass, which is the agent (A). 19. The method according to claim 18, wherein the radical polymerization initiator (B) is water-soluble. 20. The dry toner according to claim 19, wherein the radical polymerization initiator (B) is a polymerization initiator selected from the group consisting of sodium persulfate, potassium persulfate and ammonium persulfate. Production method. 21. The method according to claim 18, wherein the radical polymerization initiator (B) is oil-soluble and is added by emulsifying or dispersing in water. 22. The radical polymerization initiator (B), which is a polymerization initiator selected from an azo polymerization initiator, a diazo polymerization initiator and a peroxide polymerization initiator. Item 23. The method for producing a dry toner according to Item 21. 23. A diene monomer component-containing resin containing a component derived from at least one monomer selected from the group consisting of butadiene, isoprene and chloroprene, a polymerizable vinyl monomer, a colorant, a wax, and a polymer. A method for dispersing and granulating a polymerizable monomer composition containing an initiator in an aqueous medium, polymerizing in an aqueous medium, and producing toner particles, wherein the polymerization initiator initiates radical polymerization. 18. The toner according to claim 1, wherein the radical polymerization initiator (B) is newly added when the conversion rate of the polymerization reaction is in the range of 10 to 95% by mass. A method for producing a dry toner, which is the toner according to any one of claims 1 to 3. 24. A charging step of applying a voltage to a charging member to charge an electrostatic latent image carrier, and an electrostatic latent image forming step of forming an electrostatic latent image on the charged electrostatic latent image carrier. Developing a toner image on the electrostatic latent image carrier by adhering the toner carried on the toner carrier to the electrostatic latent image formed on the electrostatic latent image carrier; A transfer step of electrostatically transferring the toner image formed on the electrostatic latent image carrier to a transfer material with or without an intermediate transfer body, and a fixing step of fixing the toner image electrostatically transferred to the transfer material Wherein the toner is a dry toner having at least a binder resin, toner particles containing a colorant and a wax component, and an external additive, wherein (1) the binder resin comprises: At least one unit selected from the group consisting of butadiene, isoprene and chloroprene (2) a main glass transition temperature (Tg) of the toner measured by a differential scanning calorimeter (DSC) of 40 to 70 ° C., and (3) a toner of the toner. Atmospheric temperature 23 ° C, relative humidity 6
The specific surface area by the BET method when left in an environment of 5% for 72 hours is A (m ² / g), and the ambient temperature of the toner is 50
BE when left for 72 hours in an environment of 3 ° C and 3% relative humidity
When the specific surface area by the T method is B (m ² / g), A
And B satisfy the following equation: 0.8 ≦ A ≦ 4.0 0.80 ≦ (B / A) ≦ 1.05 (4) The number of toners measured by the flow type particle image measuring apparatus for the toner In the reference circle equivalent diameter-circularity scattergram, the circle equivalent number average diameter D1 of the toner is 2 to 2.
10 μm, and the average circularity of the toner is 0.950
0.995, the circularity standard deviation is less than 0.040, and (5) tetrahydrofuran (TH
F) In the molecular weight distribution measured by gel permeation chromatography (GPC), the soluble component has a main peak molecular weight in the range of 2 × 10 ³ to 1 × 10 ⁵ and a THF insoluble component of 5 to 60% by mass. An image forming method, characterized in that: 25. In the developing step, the moving speed of the surface of the toner carrier in the developing area is 1.05 to 3.0 times the moving speed of the surface of the electrostatic latent image carrier. The image forming method according to claim 24, wherein: 26. The image forming method according to claim 24, wherein the thickness of the toner layer on the toner carrier is regulated by a regulating member, and the regulating member is a ferromagnetic metal blade. 27. The image forming method according to claim 26, wherein the ferromagnetic metal blades are arranged at regular intervals so as to face the toner carrier. 28. The image forming method according to claim 24, wherein the thickness of the toner layer on the toner carrier is regulated by a regulating member, and the regulating member is a blade made of an elastic body. 29. The blade according to claim 2, wherein the blade made of the elastic body is brought into contact with the toner carrier so as to face the toner carrier.
9. The image forming method according to 8. 30. In the developing step, an electrostatic latent image carrier and a toner carrier are arranged at a certain interval, and development is performed by forming an alternating electric field between the two. The image forming method according to any one of claims 24 to 29, characterized in that: 31. In the developing step, the development is performed while the electrostatic latent image formed on the electrostatic latent image carrier and the toner thinly coated on the toner carrier are brought into contact with each other. The image forming method according to any one of claims 24 to 29. 32. The method according to claim 24, wherein in the charging step, the charging member is brought into contact with the electrostatic latent image carrier to charge the electrostatic latent image carrier. Image forming method. 33. The image according to claim 24, wherein in the transfer step, the electrostatic latent image carrier is in contact with a transfer device via the transfer material. Forming method. 34. The image forming method according to claim 24, wherein the fixing step is a heat fixing step of heating and fixing the toner image on the transfer material. 35. The method according to claim 34, wherein the heating and fixing step is a step of heating and pressing and fixing the toner image to the transfer material by a heating member and a pressing member opposed to and pressed against the heating member. The image forming method as described in the above. 36. The image forming method according to claim 34, wherein a film is interposed between the transfer material and the heating element in the heat fixing step. 37. The method according to claim 24, further comprising a developing and cleaning step of recovering the transfer residual toner remaining on the electrostatic latent image carrier after the transfer step by the toner carrier in the developing step. The image forming method according to any one of the above. 38. After the transfer step, the transfer residual toner remaining on the electrostatic latent image carrier is cleaned and collected, and the collected toner is supplied to a developing unit to be used again for developing the electrostatic latent image. The image forming method according to any one of claims 24 to 36, further comprising a toner reuse mechanism to be provided. 39. A charging step of applying a voltage to a charging member to charge an electrostatic latent image carrier, and an electrostatic latent image forming step of forming an electrostatic latent image on the charged electrostatic latent image carrier. Developing a toner image on the electrostatic latent image carrier by adhering the toner carried on the toner carrier to the electrostatic latent image formed on the electrostatic latent image carrier; A transfer step of electrostatically transferring the toner image formed on the electrostatic latent image carrier to a transfer material with or without an intermediate transfer body, and a fixing step of fixing the toner image electrostatically transferred to the transfer material Wherein the toner is a dry toner having at least a binder resin, toner particles containing a colorant and a wax component, and an external additive, wherein (1) the binder resin comprises: At least one unit selected from the group consisting of butadiene, isoprene and chloroprene (2) a main glass transition temperature (Tg) of the toner measured by a differential scanning calorimeter (DSC) of 40 to 70 ° C., and (3) a toner of the toner. Atmospheric temperature 23 ° C, relative humidity 6
The specific surface area by the BET method when left in an environment of 5% for 72 hours is A (m ² / g), and the ambient temperature of the toner is 50
BE when left for 72 hours in an environment of 3 ° C and 3% relative humidity
When the specific surface area by the T method is B (m ² / g), A
And B satisfy the following formula: 0.8 ≦ A ≦ 4.0 0.80 ≦ (B / A) ≦ 1.05 (4) The number of toners measured by the flow type particle image measuring apparatus for the toner In the reference circle equivalent diameter-circularity scattergram, the circle equivalent number average diameter D1 of the toner is 2 to 2.
10 μm, and the average circularity of the toner is 0.950
0.995, the circularity standard deviation is less than 0.040, and (5) tetrahydrofuran (TH
F) In the molecular weight distribution measured by gel permeation chromatography (GPC), the soluble component has a main peak molecular weight in the range of 2 × 10 ³ to 1 × 10 ⁵ and a THF insoluble component of 5 to 60% by mass. An image forming method, wherein the toner is the toner according to any one of claims 2 to 17.