JP2002365853A - Method for forming image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming images by which excellent low temperature fixing property and high temperature offset resistance are exhibited in from low to high-speed operations even in a fixing system with low pressure, high durability, stable high picture density and low fog can be obtained, excellent cleaning characteristics of a photoreceptor is obtained and long-term stable preferable image characteristics can be obtained. SOLUTION: The method for forming images to form fixed images on a recording material by heating and pressurizing to fix toner images on the recording material by a hating and pressurizing means, is characterized in that the toner contains at least a binder resin, a specified imidazolium salt and a coloring agent, the binder resin contains at least one kind of vinyl resin selected from a group composed of mixtures of vinyl resin having carboxyl groups and vinyl resin having glycidyl groups, vinyl resin having carboxyl groups and glycidyl groups, and vinyl resin having carboxyl groups and glycidyl groups reacting with each other, and a heating and pressurizing means by electromagnetic induction heating is used as the heating and pressurizing means.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a fixed image by heating and fixing a toner image used in a recording method such as an electrophotographic method, an electrostatic recording method, a magnetic recording method and a toner jet recording method. Image forming method

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
Many methods are known as described in Japanese Patent Application Laid-Open Publication No. Sho 43-24748 and the like. Generally, an electric latent image is formed on a photoreceptor by various means using a photoconductive substance. (Electrostatic latent image), then developing the latent image using toner, transferring a toner image to a transfer sheet (recording material) such as paper as necessary, and then heating, pressure, and heating and pressing. Alternatively, the toner is fixed by a solvent vapor or the like to obtain a copy, and the toner remaining on the photoreceptor without being transferred is cleaned by various methods, and the above steps are repeated.

In recent years, such a copying apparatus has become smaller, lighter, faster, more reliable, and on-demand, reflecting changing market needs such as network compatibility, compounding, and personalization. As a result, the performance required for toners is becoming more sophisticated.

As one example, there is a step of fixing a toner image on a recording material (transfer sheet) such as paper.

To date, various methods and apparatuses have been proposed and developed as a fixing method, but the most common method is a heating / pressing method using a fixed heating heater via a heat roller.

In this fixing method, the fixing roller is formed in a hollow shape, and a heating element is held on a central axis of the fixing roller by holding means. The heating element is formed of, for example, a tubular heating heater such as a halogen lamp, and generates heat when a predetermined voltage is applied. Since the halogen lamp is located at the center axis of the fixing roller, heat generated from the halogen lamp is uniformly radiated to the inner wall of the fixing roller, and the temperature distribution of the outer wall of the fixing roller becomes uniform in the circumferential direction. The outer wall of the fixing roller is heated until its temperature reaches a temperature suitable for fixing (for example, 150 to 210 ° C.). In this state, the fixing roller and the pressure roller rotate in the opposite directions while being pressed against each other, and sandwich the transfer sheet to which the toner has adhered. At a pressure contact portion between the fixing roller and the pressure roller (hereinafter also referred to as a nip portion), the toner on the transfer sheet is melted by the heat of the fixing roller, and is fixed to the transfer sheet by the pressure applied from both rollers.

However, in the above-described fixing device having a heating element composed of a halogen lamp or the like, the fixing roller is heated by using the radiant heat from the halogen lamp. It takes a relatively long time to reach a predetermined temperature suitable for fixing (hereinafter referred to as a warm-up time). in the meantime,
There is a problem that the user cannot use the copier or the printer and is forced to wait for a long time.

On the other hand, if a large amount of power is applied to the fixing roller in order to shorten the warm-up time and improve the operability of the user, the power consumption of the fixing device increases, which is contrary to energy saving. Had occurred. Therefore, in order to enhance the value of a product such as a copying machine or a printer, it is more and more important to achieve both energy saving (low power consumption) of the fixing device and improvement of user operability (on-demand printing). It has been emphasized.

[0009] As a fixing method to meet such a demand,
As disclosed in JP-A-59-33787, an induction heating type fixing device using high-frequency induction as a heating source has been proposed. In this induction heating fixing device, a coil is arranged concentrically inside a hollow fixing roller made of a metal conductor, and an induced eddy current is generated in the fixing roller by a high-frequency magnetic field generated by applying a high-frequency current to this coil. ,
The fixing roller itself generates Joule heat by the skin resistance of the fixing roller itself. According to the fixing device of the induction heating system, the electric-heat conversion efficiency is extremely improved, so that the warm-up time can be reduced.

Further, by combining the coil with a core (magnetic field blocking member) made of a magnetic material, a high-frequency magnetic field can be efficiently generated. In particular, when a core having a T-shaped cross section is used, the amount of heat required for the fixing device can be generated with low power due to the effective concentration of the high-frequency magnetic field and the effect of shielding the magnetic field from a portion other than the heat generating portion.

However, in the case of the above-described prior art, the following problems have occurred.

In the above-described induction heating type fixing device, it is necessary to reduce the heat capacity of the heat generating layer of the fixing roller as much as possible in order to take advantage of the feature that the warm-up time is reduced when the fixing device is started. If the thickness of the fixing roller is reduced as a means, it becomes difficult to set a high pressure at the fixing nip portion due to the rigidity of the fixing member,
The "pressing" fixing effect cannot be expected, and as a result, it is difficult to set the fixing fixing temperature low.

In addition, when fixing is performed continuously irrespective of the fixing method, heat is taken away by the sheet to be fixed, so that the temperature of the fixing roller temporarily drops immediately after the start of fixing.
At this time, in the induction heating type fixing device, since the heat capacity of the contents of the fixing roller is large, it takes much time to return to the set fixing temperature from the temperature drop due to the sheet passing, and it is easy to cause fixing defects. .

In the case of the induction heating system, heat transfer in the direction of the rotation axis of the fixing roller becomes slow. For example, when small-sized paper is continuously passed, fixing between the paper passing portion and the non-paper passing portion is performed. The difference in roller temperature is likely to increase. At this time, if the temperature is adjusted in the paper passing portion of the fixing roller, the temperature of the non-paper passing portion greatly exceeds the temperature suitable for fixing, so that toner is transferred to the surface of the fixing roller in the non-paper passing portion, so-called offset occurs, and recording is performed. Paper jam (hereinafter referred to as jam) due to the material (transfer sheet) being wound around the fixing roller is likely to occur.

The toner required for the induction heating type fixing device as described above has higher required performance than other types of toners, and further has a low-temperature fixing property and a low-temperature fixing property without impairing developability. Improvement in offset resistance is required.

Conventionally, various means have been proposed for the purpose of preventing toner from adhering to the surface of the fixing roller, that is, not causing offset, or improving the low-temperature fixing property. For example, the roller surface is formed of a material with excellent release properties from toner, such as silicone rubber or fluororesin,
Further, in order to prevent offset and prevent roller surface fatigue, the roller surface is coated with a thin film of a liquid having good releasability such as silicone oil. However, although this method is extremely effective in preventing toner offset, it requires a device for supplying an anti-offset liquid, which also complicates the fixing device and increases the size of the device. have.

Therefore, in order to realize an efficient fixing method while achieving good fixability of a toner-visible image to a recording material (transfer sheet), prevention of offset, and the like, the above-described fixing device must be used. Therefore, the characteristics of the toner are greatly affected.

In other words, particularly from the viewpoint of an offset prevention technology, an anti-offset method by supplying an anti-offset liquid is not preferable. Rather, it is strongly desired to develop a toner having a wide fixing temperature range and high anti-offset property. It is the current situation. Therefore, in order to increase the releasability of the toner itself, a method of adding a wax such as a low-molecular-weight polyethylene or a low-molecular-weight polypropylene, which sufficiently melts when heated, has also been performed. , And the charging characteristics become unstable, which tends to cause a decrease in developability during durability.
Therefore, various attempts have been made to improve the binder resin as other methods.

For example, a method of increasing the glass transition temperature (Tg) and the molecular weight of the binder resin in the toner in order to prevent offset, and improving the melt viscoelasticity of the toner is also known. However, when the offset phenomenon is improved by such a method, the developing property does not significantly affect but the fixing property becomes insufficient, and the fixing property at a low temperature required for high-speed development and energy saving, that is, There is a problem that the low-temperature fixability is poor.

In order to improve the low-temperature fixability of the toner, it is necessary to reduce the viscosity of the toner at the time of melting to increase the contact area with the fixing member. For this purpose, the Tg and the molecular weight of the binder resin used are reduced. Is required.

In other words, since low-temperature fixability and offset resistance have one side contradictory, it is very difficult to develop a toner that satisfies these functions simultaneously.

In order to solve this problem, for example, Japanese Patent Publication No. 51-23354 discloses a toner comprising a suitably crosslinked vinyl polymer by adding a crosslinking agent and a molecular weight modifier. Many blended toners based on a combination of Tg, molecular weight, and gel content have been proposed.

A toner containing such a crosslinked vinyl polymer or gel component exhibits an excellent effect in offset resistance. However, when the crosslinked vinyl polymer is used as a raw material for the toner in containing these components, the internal friction in the polymer becomes extremely large in the melt-kneading step in the production of the toner, and a large shear force is applied. It takes unity. For this reason, in many cases, the molecular chains are cut, resulting in a decrease in the melt viscosity and adversely affecting the offset resistance.

To solve this problem, Japanese Patent Laid-Open No.
Nos. 5-90509, 57-178249, 57-
JP-A-178250 and JP-A-60-4946 disclose that a resin having a carboxylic acid and a metal compound are used as a raw material of a toner, and are heated and reacted at the time of melt-kneading to form a crosslinked polymer and to be contained in the toner. .

Further, it has been disclosed in Japanese Patent Application Laid-Open No. Sho 61 (1994) that a binder having a vinyl resin monomer and a more specific monoester compound as essential constitutional units is reacted with a polyvalent metal compound to crosslink via a metal. No. 110155 and 61-
It is disclosed in Japanese Patent Publication No. 110156.

Also, Japanese Patent Application Laid-Open Nos. 63-214760 and 6
Nos. 3-217362, 63-217363, 63
In Japanese Patent No. 217364, it has a molecular weight distribution divided into two groups of a low molecular weight and a high molecular weight, and a carboxylic acid group contained on the low molecular weight side reacts with a polyvalent metal ion to crosslink (obtained by solution polymerization). A dispersion of a metal compound is added to the solution, and the mixture is heated and reacted).

In addition, JP-A-2-168264, JP-A-2-168264.
Nos. 235069, 5-173363, 5-173
In JP-A-366 and JP-A-5-241371, a toner for a toner in which the molecular weight, the mixing ratio, the acid value and the ratio of the low molecular weight component and the high molecular weight component in the binder resin are controlled to improve the fixing property and the anti-offset property, etc. Binder compositions and toners have been proposed.

In Japanese Patent Application Laid-Open No. 62-9256,
A binder composition for a toner in which two kinds of vinyl resins having different molecular weights and resin acid values are blended is disclosed.

Also, Japanese Patent Application Laid-Open Nos. 3-63661 and 3-6
Nos. 3662, 3-63663 and 3-11855
No. 2 discloses that a carboxyl group-containing vinyl copolymer and a glycidyl group-containing vinyl copolymer are reacted with a metal compound to cause crosslinking.

Further, JP-A-62-194260, JP-A-6-11890, JP-A-6-222612, and 7-2.
Nos. 0654, 9-185182, 9-24429
No. 5, No. 9-319410, No. 10-87837 and No. 10-90943, a resin composition composed of a carboxyl group-containing resin using a glycidyl group-containing resin as a cross-linking agent has a molecular weight distribution and gel. There have been proposed toner binder compositions and toners in which the content, the acid value, the epoxy value, and the like are controlled to improve the fixing property and the offset resistance.

Although these proposals described above have advantages and disadvantages in terms of improving the offset resistance, it is true that excellent effects can be obtained. But,
These introduce an acid group into the binder resin, and thus give the toner a negative charge, though there are some differences. As a result, there is no problem in application to a negatively chargeable toner, but when applied to a positively chargeable toner, the charge characteristics of the toner at the start-up and endurance, or in a high or low humidity environment are significantly impaired, and the image density is low. This leads to a decrease in developing characteristics such as fogging and fogging. In addition, the toner cannot be stably maintained at an appropriate charge amount, causing an increase in toner cohesiveness. For example, in a cleaning process, problems such as fusing, poor cleaning, clogging of waste toner conveyance, and leakage spots on the photoconductor are caused. However, when applied to an induction heating fixing device, the electrostatic attraction between the toner that forms the unfixed toner image before fixing and the transfer paper becomes insufficient, so that the fixing scatters and the fixing Pulling may occur, and these tend to occur more remarkably as the process speed during fixing is higher, and satisfactory results have not been obtained.

Although these proposals have the effect of greatly improving the balance between the fixing property, the anti-offset property and the anti-blocking property, they are still insufficient in a light pressure fixing system such as an induction heating fixing system. Performance has not been obtained. Further, the developing properties and mechanical strength of the toner are insufficient, and there is still room for improvement in durability when used in an electrophotographic apparatus having a large print volume. In addition, when used in a machine using a fixing device without using a fixing web or the like or a high-speed machine, there is still room for improvement in the offset resistance.

On the other hand, the toner needs to have a positive or negative charge according to the charge polarity of the electrostatic latent image to be developed.
For this purpose, it is generally known to add dyes, pigments or charge control agents. Among these, as the positive charge control agent, quaternary ammonium salts and their lake pigments, polymers having tertiary amino groups or quaternary ammonium salts in the side chains, triphenylmethane dyes and these lake pigments, nigrosine and fatty acids Modified products such as metal salts are known.

However, in these conventional positive charge control agents,
Even if a sufficient amount of charge is not given to the toner, or even if a sufficient amount of charge is given to the toner, the image density is reduced due to the influence of other toner constituent materials and excessive triboelectric charging or uneven charging. Deterioration of development characteristics such as fogging and fogging is likely to occur, and this tendency is particularly remarkable in a positively chargeable toner having an acid group. When an induction heating fixing device is used, a high-frequency electromagnetic field generated by applying a high-frequency current to the coil leaks slightly from the shield member, disturbing the unfixed toner image on the transfer sheet immediately before entering the fixing device. It is easy to cause fixing scattering and fixing tailing. This fixing scattering and fixing tailing tend to occur more frequently as the printing speed increases,
In particular, the more the chargeability of the toner is non-uniform, the more noticeable it appears.
This problem can be solved by increasing the electrostatic attraction force between the toner on the transfer sheet and the transfer sheet. For example, if a measure is taken by increasing the transfer current in the transfer process, This causes adverse effects such as discharge.

[0035]

SUMMARY OF THE INVENTION An object of the present invention is to provide an image forming method which solves the above-mentioned problems.

That is, an object of the present invention is to provide an image forming method in which a toner image on a recording material is heated and pressurized and fixed by an electromagnetic induction heating method to form a fixed image without deteriorating the developing property. The system also exhibits excellent low-temperature fixability and high-temperature offset resistance from low to high speeds, provides high durability and stable high image density and low fog, and has excellent photoreceptor cleaning properties, especially during high-speed printing. Also, no scattering or fixing tailing occurs during fixing,
That is, an object of the present invention is to provide an image forming method capable of obtaining good image characteristics stably for a long period of time.

It is a further object of the present invention to provide an image forming method capable of achieving both energy saving (low power consumption) of a fixing device and improvement of user operability (on-demand printing).

[0038]

SUMMARY OF THE INVENTION The present invention relates to an image forming method for forming a fixed image on a recording material by heating and fixing a toner image on a recording material by heating and pressing means. The toner contains at least a binder resin, an imidazolium salt and a colorant, and as the binder resin, a mixture of a vinyl resin having a carboxyl group and a vinyl resin having a glycidyl group, and a vinyl resin having a carboxyl group and a glycidyl group. , And at least one or more vinyl resins selected from the group consisting of vinyl resins in which carboxyl groups and glycidyl groups have reacted,
The imidazolium salt is a polymer having, as a structural unit, an imidazolium salt represented by the following general formula (1) or an imidazolium salt represented by the following general formula (2),

[0039]

Embedded image (In the above general formula (1), R ₁ , R ₄ and R ₅ represent hydrogen, an alkyl group having a substituent, an alkyl group having no substituent, a cycloalkyl group having a substituent, a cycloalkyl having no substituent, An alkyl group, an aryl group having a substituent,
Aryl group having no substituent, allyl group having a substituent, allyl group having no substituent, aralkyl group having a substituent, aralkyl group having no substituent, alkoxy group having a substituent, having no substituent An alkoxy group, an amino group having a substituent, an amino group having no substituent, a halogen or a heterocyclic ring, which may be the same or different; R ₂ and R _{3 each} represent hydrogen or a substituent Alkyl group, an alkyl group having no substituent, a cycloalkyl group having a substituent, a cycloalkyl group having no substituent, an aryl group having a substituent, an aryl group having no substituent, an allyl group having a substituent, Unsubstituted allyl group, substituted aralkyl group, unsubstituted aralkyl group, substituted alkoxy group, unsubstituted alkoxy group R ₁ and R ₂ , or R ₁ and R ₃ , may be mutually connected to form a ring; R ₄ and R ₅ may form an interconnected aromatic or heterocyclic ring; such substituents include hydrogen, alkyl, cycloalkyl, aryl, aryl, aralkyl, An alkoxy group, an amino group, an amide group, a halogen or a heterocyclic ring, which may have an ether structure or a sulfide structure; m represents a positive integer of 1 or more, and X ^m- represents a counter anion. Wherein the general formula (2) represents a polymer having an imidazolium salt as a constitutional unit. In the general formula (2), R ₆ , R ₇ and R _{8 each} represent hydrogen or an alkyl group having a substituent. , An unsubstituted alkyl group and a substituted cycloalkyl group An unsubstituted cycloalkyl group, an substituted aryl group,
Aryl group having no substituent, allyl group having a substituent, allyl group having no substituent, aralkyl group having a substituent, aralkyl group having no substituent, alkoxy group having a substituent, having no substituent An alkoxy group, an amino group having a substituent, an amino group having no substituent, a halogen or a heterocyclic group, which may be the same or different; R ₇ and R ₈ are R ₉ represents a linking group, and may form an aromatic ring or a heterocyclic ring; a phenylene group which may contain an ether bond;
A propenylene group, a vinylene group or an alkylene group,
The polymer may contain an imidazolium salt as a constituent unit. In that case, the linking groups may form a ring structure with each other, or may be bonded to the binder resin main chain as a graft chain; as a substituent, hydrogen, an alkyl group, a cycloalkyl group, an aryl group, There are an allyl group, an aralkyl group, an alkoxy group, an amino group, an amide group, a halogen or a heterocyclic ring, which may have an ether structure or a sulfide structure; m represents a positive integer of 1 or more;
n represents a positive integer of 1 or more, and X ^m- represents a counter anion. )

The heating and pressurizing means includes (i) a magnetic field generating means, and (ii) 0.01 to 20 which generates heat by electromagnetic induction.
(iii) a heating and pressing means having at least a heating and pressing member forming a nip having a width of 1 to 20 mm with the heating and heating member having at least a heat generating layer and a release layer having a width of 1 mm. And fixing the toner image on the recording material by heating and pressing at a fixing speed of 10 to 600 mm / sec while pressing the rotating heating member through the recording material at a total pressure of 45 to 1000 N by the rotating pressure member. And an image forming method for forming an image.

[0041]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have (i) a magnetic field generating means and (ii) at least heat generated by electromagnetic induction.
A heating and pressurizing means having at least a rotary heating member having a heat generating layer and a release layer having a thickness of 01 to 20 mm, and (iii) a rotary pressing member forming a nip having a width of 1 to 20 mm with the heating member. The toner image on the recording material is heated and pressed and fixed at a fixing speed of 10 to 600 mm / sec while the rotary heating member is pressed at a total pressure of 45 to 1000 N by the rotary pressing member via the recording material. A mixture of a vinyl resin having a carboxyl group and a vinyl resin having a glycidyl group, which contains at least a binder resin, an imidazolium salt, and a colorant as a toner applicable to an image forming method for forming an image. , Selected from the group consisting of a vinyl resin having a carboxyl group and a glycidyl group, and a vinyl resin having a carboxyl group and a glycidyl group reacted. By containing at least one kind of vinyl resin and containing a specific imidazolium salt or a polymer having a specific imidazolium salt as a constituent unit, light charging without impairing the charging characteristics and powder characteristics of the toner is achieved. It has been found that good low-temperature fixability and offset resistance can be obtained even under pressure fixing conditions, and further good blocking resistance can be achieved.

Further, the excellent charging characteristics and powder characteristics prevent the toner from being fused or leaked to the photoreceptor due to excessive charging or non-uniform charging in the cleaning step, and the toner has excellent charging uniformity. In addition to preventing problems such as fusing, poor cleaning, and toner conveyance clogging due to the deterioration of cohesiveness and fluidity, it is suitable for induction heating and fixing equipment, and even when printing at high speed,
It is possible to effectively suppress disturbance of an unfixed toner image during fixing.

Further, the soluble component of the toner has a specific acid value, the molecular weight distribution measured by GPC of the THF-soluble component in the toner has a specific molecular weight distribution, The above effect can be further improved by containing a specific THF-insoluble component in the binder resin and by containing the metal oxide particles in the toner.

The reason for exhibiting the effect in the present invention will be described below.

First, the toner contains a mixture of a vinyl resin having a carboxyl group and a vinyl resin having a glycidyl group, a vinyl resin having a carboxyl group and a glycidyl group, or a carboxyl group and a glycidyl group. Having at least one vinyl resin selected from the group consisting of a vinyl resin reacted with an imidazolium salt represented by the general formula (1) or an imidazolium salt represented by the general formula (2) as constituent units Is excellent in uniform triboelectrification, and on the other hand, has excellent characteristics of suppressing excessive charging, and has a good balance between low-temperature fixability and offset resistance as described later. It was found to have As a result, as a toner particularly suitable for the induction heating fixing method, good developing property and high durability and fixing /
The anti-offset performance can be obtained.

The mechanism by which excessive charging is suppressed in the toner used in the present invention has not been sufficiently elucidated. However, a resin having a carboxyl group or a glycidyl group or a resin reacted therewith, and a specific imidazolium salt or imidazoline Some interaction has occurred between the polymer having a lithium salt as a constituent unit, and as a result, it is considered that the polymer has an appropriate charge leakage property. Thereby, for example, localization of the charge amount due to charge-up in the cleaning process is less likely to occur, fusion and leak spots on the photoreceptor, cleaning failure due to deterioration of toner cohesiveness and fluidity, toner conveyance clogging, and the like. Is suppressed. Also, even when a stainless steel having a strong charge-imparting property is used for the developing sleeve which is a charge-imparting member,
Since the toner has a stable chargeability, the occurrence of blotting, which is defective in toner coating, is suppressed.

In the toner used in the present invention, a metal oxide having a weight-average particle diameter of 0.4 to 5.5 μm is added, so that better charging characteristics are exhibited and the above effect is promoted. In particular, it has been found that when applied to an induction heating fixing device, the occurrence of fixing scattering and fixing tailing can be suppressed. This is because the metal oxide added to the toner acts as a microcarrier, giving a charge-imparting effect to the toner particles having a low charge amount, and at the same time transferring the toner particles by the action of the metal oxide particles attached to the toner. In the process, the toner transferred onto the transfer sheet is given an appropriate electrostatic cohesion, the electrostatic attraction between the transfer sheet and the toner is increased, and even when the transfer sheet enters the induction heating fixing device, This is because the unfixed toner image is less susceptible to the electromagnetic field leaking out of the fixing device, and the scattering of the fixing and the tailing of the fixing due to the disorder of the unfixed toner image are less likely to occur.

The toner used in the present invention containing the imidazolium salt represented by the general formula (1) or the polymer having the imidazolium salt represented by the general formula (2) as a constituent unit can be used in a high or low humidity environment. In addition, there is little fluctuation in charging characteristics, and stable development characteristics can be maintained,
Since the imidazolium salt or the polymer having the imidazolium salt as a constituent unit is small from toner using a resin having a carboxyl group or a glycidyl group or a resin obtained by reacting the resin, the occurrence of development sleeve contamination can be suppressed. In addition, stable charging durability can be maintained.

The reason why the imidazolium salt or the polymer having the imidazolium salt as a structural unit is prevented from being lost from the toner is that the imidazolium salt or the amine in the polymer having the imidazolium salt as a structural unit is suppressed. And the carboxyl group and epoxide in the resin.

The toner used in the present invention hardly causes localization of the charge amount regardless of the material of the developer carrying member in the frictional charging process with the developer carrying member (developing sleeve). For example, it shows good triboelectric charging performance even when using general stainless steel, aluminum, or metal plating, but conventionally, a developer carrying member having a coating layer containing a resin that is difficult to perform positive triboelectric charging is used. Also exhibits excellent charging performance in contact with.

It is known that a toner containing nigrosine, which is a conventionally known general positively chargeable charge control agent, exhibits good positively chargeable properties when it comes into contact with stainless steel. However, when the toner is brought into contact with a developer carrying member having a coating layer (for example, a carbon black dispersed resin coating layer) on the surface layer, the positive chargeability is slightly reduced, and when the binder resin has a carboxyl group, In addition, the charging performance is further reduced. Further, sleeve contamination occurs when nigrosine is missing from the toner and adheres to the surface of the sleeve as the developer carrying member.

On the other hand, when a specific imidazolium salt or a polymer having an imidazolium salt as a structural unit used in the toner of the present invention is used, a specific charge leak characteristic and a localization of the charge amount are obtained. Properties to suppress
It shows good charging performance even when it comes in contact with stainless steel due to its property of less loss of imidazolium salts, etc., but it is also excellent when it comes in contact with a developer carrier at least on the surface of which is formed of a resin-containing material. It shows the charging performance. This tendency is particularly effective when the binder resin has a carboxyl group, and exhibits a much higher charging performance as compared with the case where the binder resin is brought into contact with stainless steel.

As a result, the developing ability of the toner is improved, a high-quality image having a high image density and little fog is obtained, and the proper charge amount is maintained even after the image is transferred to the transfer sheet and becomes an unfixed toner image. And moderate cohesion,
Even if it is applied to the induction heating fixing method, it is hardly affected by the leakage electromagnetic field, and the disturbance of the unfixed toner image in the fixing step is suppressed regardless of low-speed / high-speed printing.

The toner used in the present invention is melted and kneaded in a kneading step or the like in the toner manufacturing process, and all effects are exhibited by a crosslinking reaction of the binder resin. By including a copolymer having a carboxyl group unit and a copolymer having a glycidyl group unit in the binder resin, a THF-insoluble component that promotes a crosslinking reaction by a heating step and exhibits effects such as anti-offset and Produce a crosslinked resin component that will be a high molecular weight component. As a result, even when applied to a light pressure fixing system using an electromagnetic induction heating method, excellent low-temperature fixing properties and good print quality with less occurrence of offset can be achieved, and when applied to a high-speed machine,
Even when the copy volume increases, stable print durability can be achieved.

Further, the charging characteristics of the whole toner can be stabilized by the reaction and interaction of the imidazole unit, carboxyl unit, epoxide unit and hydroxy unit. In addition, since the charge stability of the imidazole unit portion is further improved, when the imidazole compound is added in an amount that can function as a positive charge control agent, good positive charge as a positive charge toner can be obtained. . Furthermore, it is also possible to reduce the charge inhibition such as excessive charging and charge release of the carboxyl unit, epoxide unit and hydroxy unit, and it is particularly effective in the case of positive charging.

The toner used in the present invention exhibits offset resistance and blocking resistance more effectively than the reaction of only the copolymer having a carboxyl group unit and the copolymer having a glycidyl group unit. Moreover, it has a characteristic that does not adversely affect the fixing property. Therefore, as an effect at the time of fixing, the low-temperature fixing property is excellent, and the offset of the toner to the fixing roller hardly occurs. .

Further, the toner transferred to the fixing roller is easily removed by a cleaning member such as a web, and the transfer to the fixing roller hardly occurs. Further, since the toner is hardly offset to the fixing roller, it is possible to contribute to elimination and simplification of a cleaning member such as a web. Further, the fixed image becomes robust, which contributes to the improvement of the fixing property and prevents the detachment of the toner from the fixing sheet.

Compared with the reaction of only the carboxyl group-containing resin and the glycidyl group-containing resin or the reaction with the metal compound,
The present invention has an excellent balance between the fixing property and the anti-offset property, and particularly in a light-pressure fixing system using an induction heating method, it is possible to more effectively improve these performances.

In the present invention, the acid value of the THF-soluble component of the toner indicates the acid value of the component soluble in a tetrahydrofuran (THF) solvent. The acid value of the THF-soluble component of the toner of the present invention is preferably 0.1 to 50 mgKOH / g, more preferably 0.5 to 50 mgKOH / g.
Particularly preferably, it is 0.5 to 40 mgKOH / g.
When the THF-soluble component has a desired acid value, the toner of the present invention can achieve better developability, an effect of preventing sleeve contamination, and contamination of a heating member such as a fixing roller.

When the carboxyl group reacts with the glycidyl group, the number of carboxyl groups in the binder resin may decrease and the acid value may not be measured. In this case, since a hydroxyl group is present in the binder resin, the same as described above. The effect can be expected.
To achieve these effects more effectively, the toner T
The acid value of the HF-soluble component is preferably 0.5 to 30 mg.
KOH / g, more preferably 0.5 to 25 mg KOH
/ G, more preferably 0.5 to 20 mg KOH / g
Is good.

The THF-soluble component of the toner has an acid value of 0.1 m.
If the amount is less than gKOH / g, the fixing property, the development stability due to the interaction with the imidazole unit compound and the effect of preventing sleeve contamination tend to decrease, and the acid value of the THF-soluble component of the toner exceeds 50 mgKOH / g. If
In the case of a positively chargeable toner, the negative chargeability of the binder resin in the toner particles becomes strong, and the durability of development becomes unstable.

Further, in the present invention, the THF
In the molecular weight distribution measured by GPC of the soluble component,
The number average molecular weight is preferably 1,000 to 40,00
0, more preferably 2,000 to 20,000, particularly preferably 3,000 to 15,000, and the weight average molecular weight is preferably 10,000 to 1
The content is preferably 0,000,000, more preferably 20,000 to 5,000,000, and particularly preferably 30,000 to 1,000,000.

In the GPC chromatogram of the THF-soluble component of the toner of the present invention, when the above average molecular weight is indicated, the balance between the fixing property, the anti-offset property and the anti-blocking property can be achieved, and the lightness by the induction heating method can be obtained. Most suitable for pressure fixing system.

When the number average molecular weight is less than 1,000 or when the weight average molecular weight is less than 10,000, blocking resistance is deteriorated, and when the number average molecular weight exceeds 40,000 or when the weight average molecular weight is 10 If it exceeds 3,000,000, it is difficult to obtain a sufficient improvement in fixing property, and it is not suitable for a light pressure fixing system.

In the present invention, in the molecular weight distribution measured by GPC of the THF-soluble portion of the toner, it is preferable that the toner has a main peak in a molecular weight region of 4,000 to 30,000, and more preferably a molecular weight of 5 , 0
It is preferable to have a main peak in the range of 00 to 20,000. Thereby, the fixing property, the offset resistance and the blocking resistance can all be improved.

When the main peak has a molecular weight of less than 4,000, the blocking resistance tends to deteriorate, and
If it exceeds 000, the fixability tends to deteriorate.

In the molecular weight distribution measured by GPC of the THF-soluble portion of the toner, the peak area having a molecular weight of 30,000 or less is preferably 60 to 10% with respect to the entire peak area.
The ratio is preferably 0%, more preferably 70 to 100%, and particularly preferably 75 to 100%.
Preferably, the ratio is in the range of 100% to 100%. 6 peak areas
If it is less than 0%, it will be difficult to obtain an excellent effect of improving the fixing property.

In the molecular weight distribution measured by GPC of the THF-soluble component in the toner of the present invention, the toner has at least one peak at a molecular weight of 4,000 to 30,000 and a molecular weight of 100,000 to 10,000, 00
0 preferably has at least one or more peaks, more preferably a molecular weight of 800,000 to 10,
1,000,000. Furthermore, molecular weights of 100,000 to 800,000 and 800,000 to 10,
It is preferred to have at least one peak in each of the millions.

When the above-mentioned peak profile is shown in the GPC chromatogram of the THF-soluble component of the toner of the present invention, all of the fixing property, offset resistance and blocking resistance can be improved, and the light pressure fixing system can be used. , Good fixing performance can be obtained.

By having at least one peak at a molecular weight of 4,000 to 30,000, good fixability and blocking resistance can be achieved, and the molecular weight is preferably 5,000 to 20,000. The peak does not exist in the molecular weight range of 4,000 to 30,000,
If it exists in a region having a molecular weight of less than 4,000, the blocking resistance tends to deteriorate, and if it exists in a region having a molecular weight of more than 30,000, it becomes difficult to obtain good fixability. Molecular weight 100,000 to 10,000
If there is at least one peak at 0000, good offset resistance is achieved.

Further, the peak area having a molecular weight of 100,000 or more preferably accounts for 5 to 40% of the entire peak area. If the peak area is less than 5%,
When the toner is easily peeled off from the transparency (trapene), if it exceeds 40%, it tends to be difficult to achieve excellent fixability.

In the present invention, the entire peak area means a peak area of a region having a molecular weight of 800 or more.

It is preferable that the peak in the molecular weight range of 4,000 to 30,000 is the largest peak (main peak) from the viewpoint of improving fixability.

The molecular weight is 800,000 to 10,000,
The sub-peak in the region of 000 is a component generated by the crosslinking reaction of the binder resin, and can have a sufficient effect on the offset resistance, and further has a molecular weight of 100,000.
When the polymer has a peak in the range of from 800 to less than 800,000, the molecular weight having a large difference in melt viscosity is from 4,000 to 30,000.
And a molecular weight of 800,000 to 10,000,
By improving the dispersibility of the 000 component and the THF-insoluble component in the toner, the developability is improved, and each fixing property is effectively exhibited.

The resin component of the toner of the present invention may contain a THF-insoluble component at 0.1 to 60% by mass, so that the offset resistance is improved.

The THF insoluble content in the resin component of the toner is 5
When the content is from 60 to 60% by mass, good releasability from a heating member such as a fixing roller is exhibited. In particular, for example, when applied to a machine equipped with a heat roll fixing device using an induction heating fixing method, the amount of toner offset to a heating member such as a fixing roller and a pressure roller is drastically reduced, and virtually no stain is generated. There is no need to attach a web as a cleaning member, and a fixing device without a cleaning member can be realized. Due to such advantages, the fixing method using a film other than the heat roll method is also preferably used in a surf fixing method without a web. Further, the releasability of the fixed image from the fixing roller is good, and the occurrence of a jam or the like due to poor fixing separation can be prevented even if the image comes to the leading end. By any chance
Even if a jam occurs in the fixing unit and toner adheres to the fixing roller or the fixing film, most of the adhered toner can be discharged by passing only one sheet to be fixed, and the back stain can be minimized. Can be stopped.

When the THF-insoluble content in the resin component of the toner is 5 to 60% by mass, the fixability and the offset resistance can be improved in a well-balanced manner, preferably 7 to 55% by mass, more preferably 9 to 55% by mass. The content is preferably 50% by mass, more preferably 10 to 45% by mass, and exhibits good releasability from a heating member such as a fixing roller. In particular, when applied to a high-speed machine, the amount of toner offset to a heating member such as a fixing roller is reduced, which is effective in reducing the consumption of the cleaning member web and the like and extending the life. Conversely, it is also effective against back contamination caused by retransfer of toner from the cleaning member in the morning. Further, the releasability of the fixed image from the fixing roller is good, so that even if an image comes to the leading end, it is possible to prevent the occurrence of a jam or the like due to defective fixing separation. Even if a jam occurs in the fixing section and toner adheres to the fixing roller and is collected in a large amount by the cleaning member, retransfer to paper is small and back contamination can be minimized.

When the THF-insoluble content is less than 5% by mass, the manifestation of the above excellent effects starts to decrease, and the content of 60% by mass is reduced.
When the ratio exceeds, not only the fixability is deteriorated, but also the chargeability in the toner tends to be non-uniform.

Glass transition temperature (Tg) of the toner of the present invention
Is preferably 50 to 70 ° C. When Tg is less than 50 ° C.,
The blocking resistance is deteriorated, and if it exceeds 70 ° C., the fixing property is lowered.

In the present invention, the T of the toner and the binder resin
The molecular weight distribution by GPC using HF as a solvent is measured under the following conditions.

<Measurement of molecular weight distribution by GPC>
Stabilize the column in a heat chamber at
In the column at a flow rate of 1 ml / min of THF as a solvent.
Flow at high speed, inject about 100 μl of THF sample solution and measure
I do. When measuring the molecular weight of a sample, the molecules of the sample
Quantitative distributions were generated using several monodisperse polystyrene standards.
Calculated from the relationship between the logarithmic value of the calibration curve generated and the count value
did. As standard polystyrene samples for creating calibration curves,
For example, Tosoh or Showa Denko has a molecular weight of 10
^Two-10⁷Use at least 10 markers
Suitably a quasi-polystyrene sample is used. In addition, inspection
An RI (refractive index) detector is used as the output device. In addition, column
In addition, a set of multiple commercially available polystyrene gel columns
It is good to combine them. For example, show made by Showa Denko
x GPC KF-801, 802, 803, 804,
805, 806, 807, 800P combination, East
TSKgel G1000H (H_XL), G2
000H (H_XL), G3000H (H_XL), G4000
H (H _XL), G5000H (H_XL), G6000H (H
_XL), G7000H (H_XL), TSKguard col
umn can be mentioned.

A sample is prepared as follows.

After placing the sample in THF and leaving it to stand for several hours, it is shaken well, mixed well with THF (until the sample is no longer united), and left still for 12 hours or more. Then TH
The time of leaving in F is set to 24 hours or more. After that, sample processing filter (pore size 0.2 ~
0.5 μm, for example, Mysholi Disc H-25-2
(Manufactured by Tosoh Corporation) can be used. ) Is used as a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

In the present invention, the T of the resin component in the toner
The HF insoluble content and the THF insoluble content of the raw material binder resin are measured as follows.

<Measurement of THF Insoluble Content> 0.5 to 1.0 g of the binder resin and the toner were weighed (W1 g), and a cylindrical filter paper (for example, No. 86R manufactured by Toyo Roshi Kabushiki Kaisha) was put into the soxhlet extractor. Using 200 ml of THF as
After extracting for 0 hours and evaporating the soluble component solution extracted by the solvent, the solution was dried under vacuum at 100 ° C. for several hours.
The amount of the HF-soluble resin component is weighed (W2 g). The weight of the residual combustion ash in the toner is determined (W3g).

The residual ash content of the combustion is obtained by the following procedure. About 2.0 g of a sample is placed in a 30 ml magnetic crucible precisely weighed in advance and precisely weighed, and the weight (Wa) g of the sample is precisely weighed. The crucible is placed in an electric furnace, heated at about 900 ° C. for 3 hours, allowed to cool in an electric furnace, allowed to cool in a desiccator at room temperature for one hour or more, and then accurately weighed. From here, the residual combustion ash (W
b) Obtain g. (Wb / Wa) × 100 = residual ash content (% by mass)

From this content, the weight of the residual combustion ash in the sample is determined. The THF-insoluble content is obtained from the following equation.

[0088]

(Equation 1)

In the case of a binder resin, the THF-insoluble content may be determined from the following equation.

[0090]

(Equation 2)

In the present invention, the THF soluble component of the toner and the acid value (JIS acid value) of the binder resin are determined by the following method.

<Measurement of Acid Value> The basic operation is JIS K-0.
070. 1) The sample is used after removing additives other than the soluble component in advance, or the content of the soluble component in the toner and the binder resin (colorant, insoluble content in the binder resin, etc.) is determined in advance. deep. A crushed sample of 0.5 to 2.0 (g) is precisely weighed, and the weight of the soluble component of the toner or the binder resin is defined as W (g). 2) The sample is placed in a 300 (ml) beaker, and 150 (ml) of a mixed solution of toluene / ethanol (4/1) is added and dissolved. 3) Using an ethanol solution of 0.1 mol / l KOH, titrate with a potentiometric titrator (for example, a potentiometric titrator AT-400 manufactured by Kyoto Electronics Co., Ltd. (win)
workstation) and automatic titration using an ABP-410 motorized burette is available). 4) The amount of the KOH solution used at this time is defined as S (ml), a blank is measured at the same time, and the amount of the KOH solution used at this time is defined as B (ml). 5) Calculate the acid value by the following equation. f is a factor of KOH. Acid value (mgKOH / g) = ｛(S−B) × f × 5.6
1｝ / W

The method for measuring the glass transition temperature of the toner of the present invention is described below.

<Measurement of Glass Transition Temperature of Toner> The glass transition temperature (Tg) of the toner was measured by a differential scanning calorimeter (DSC).
Measurement is performed according to ASTM D3418-82 using DEC-7 (manufactured by PerkinElmer).

The measurement sample is 5 to 20 mg, preferably 10
Weigh the mg precisely. This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and the measurement is performed at a temperature rising rate of 10 ° C./min under a normal temperature and a normal humidity in a measurement temperature range of 30 to 200 ° C. In this heating process, the temperature is 40 to 10
A specific heat change is obtained in the range of 0 ° C. The intersection of the line at the midpoint of the baseline before and after the specific heat change occurs and the differential heat curve is defined as the glass transition temperature Tg of the toner in the present invention.

In the present invention, the toner contains a vinyl resin having a carboxyl group and a vinyl resin having a glycidyl group, a vinyl resin having a carboxyl group and a glycidyl group, or a resin obtained by reacting these functional groups.

The following are examples of monomers having a carboxyl group constituting the vinyl resin having a carboxyl group.

Examples of the monomer having a carboxyl group unit include acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, cinnamic acid, vinyl acetic acid, and the like.
Isocrotonic acid, unsaturated monocarboxylic acids such as tiglic acid and angelic acid, and their α- or β-alkyl derivatives, fumaric acid, maleic acid, citraconic acid, alkenyl succinic acid, itaconic acid, mesaconic acid, dimethyl maleic acid, Examples include unsaturated dicarboxylic acids such as dimethyl fumaric acid, monoester derivatives thereof, anhydrides, and α- or β-alkyl derivatives.

Such a carboxyl group-containing monomer can be used alone or as a mixture and copolymerized with a vinyl monomer by a known polymerization method to obtain the carboxyl group-containing vinyl resin.

The acid value of the carboxyl group-containing vinyl resin is preferably 0.5 to 60 mgKOH / g. 0.5mg
If it is less than KOH / g, the number of crosslinking reaction sites between the carboxyl group and the glycidyl group is reduced, so that the crosslinking structure is small and good offset resistance is hardly achieved. In such a case, glycidyl having a high epoxy value is used. By using a vinyl resin having a group, some compensation can be made. When it exceeds 60 mgKOH / g, when it is applied to a positively chargeable toner, the negative chargeability of the binder resin in the toner particles becomes strong, and the image density tends to decrease and fog tends to increase. The glass transition temperature (Tg) of the vinyl resin having a carboxyl group is preferably from 40 to 70C. Tg is 4
When the temperature is lower than 0 ° C., the blocking resistance of the toner deteriorates,
If the temperature is higher than 70 ° C., the fixability of the toner deteriorates.

In the vinyl resin having a carboxyl group, the number average molecular weight is preferably
It is preferably from 1,000 to 40,000, and the weight average molecular weight is preferably from 10,000 to 10,000,000 in order to achieve good offset resistance and blocking resistance.

In the vinyl resin having a carboxyl group, the peak molecular weight of the low molecular weight component is preferably from 4,000 to 30,000 in order to achieve good fixability.
The peak molecular weight of the high molecular weight component is preferably from 100,000 to 1,000,000 in order to achieve good offset resistance and blocking resistance. When both the low molecular weight component and the high molecular weight component satisfy the range of the molecular weight distribution,
Both low-temperature fixability and offset resistance can be achieved to a higher degree.

Further, in order to improve the dispersion of the toner components, the vinyl resin preferably has a THF-insoluble content of 10% by mass or less, more preferably 5% by mass or less.

The polymerization method which can be used in the present invention as a method for synthesizing the high molecular weight component copolymer includes a bulk polymerization method, a solution polymerization method, an emulsion polymerization method and a suspension polymerization method.

Among them, the emulsion polymerization method is a method in which a monomer (monomer) almost insoluble in water is dispersed as small particles in an aqueous phase with an emulsifier, and polymerization is carried out using a water-soluble polymerization initiator. . In this method, the reaction heat can be easily adjusted, and the phase in which the polymerization is performed (oil phase composed of a polymer and a monomer)
And the aqueous phase are separate, so that the termination reaction rate is low, resulting in a high polymerization rate and a high degree of polymerization. Further, due to the relatively simple polymerization process and the fact that the polymerization product is fine particles, in the production of toner,
There is an advantage as a method for producing a binder resin for a toner because it is easy to mix with a colorant, a charge control agent and other additives.

However, the polymer tends to be impure due to the added emulsifier, and it is necessary to perform an operation such as salting out to remove the polymer. To avoid such inconvenience, the suspension polymerization method is convenient.

In the suspension polymerization method, the polymerization is preferably carried out at 100 parts by mass or less (preferably 10 to 90 parts by mass) with respect to 100 parts by mass of the aqueous solvent. Examples of usable dispersants include polyvinyl alcohol, partially saponified polyvinyl alcohol, and calcium phosphate, and are generally used in an amount of 0.05 to 1 part by mass based on 100 parts by mass of the aqueous solvent. The polymerization temperature is suitably from 50 to 95 ° C,
It is appropriately selected depending on the initiator used and the intended polymer.

The high molecular weight polymer used for preparing the resin composition may be used alone or in combination with a monofunctional polymerization initiator as exemplified below in order to achieve the object of the present invention. It is preferable to generate it.

Specific examples of the polyfunctional polymerization initiator having a polyfunctional structure include 1,1-di-t-butylperoxy-
3,3,5-trimethylcyclohexane, 1,3-bis- (t-butylperoxyisopropyl) benzene,
2,5-dimethyl-2,5- (t-butylperoxy)
Hexane, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, tris- (t-butylperoxy) triazine, 1,1-di-t-butylperoxycyclohexane, 2,2 -Di-t-butylperoxybutane, 4,4-di-t-butylperoxyvaleric acid-n-butyl ester, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate , Di-t-butylperoxytrimethyladipate, 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane, 2,2-t-
Polyfunctional polymerization initiators having a functional group having a polymerization initiation function such as two or more peroxide groups in one molecule such as butylperoxyoctane and various polymer oxides, diallyl peroxydicarbonate, t-butyl peroxide In one molecule such as oxymaleic acid, t-butyl peroxyallyl carbonate and t-butyl peroxyisopropyl fumarate, a compound having both a functional group having a polymerization initiation function such as a peroxide group and a polymerizable unsaturated group in one molecule. It is selected from functional polymerization initiators.

Of these, more preferred are 1,
1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, di-tert-butylperoxyhexahydroterephthalate, di-tert-butylperoxy Azelate and 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane, and t-butylperoxyallyl carbonate.

These polyfunctional polymerization initiators are preferably used in combination with a bifunctional or monofunctional polymerization initiator in order to satisfy various performances required as a binder for a toner. In particular, the half-life of the polyfunctional polymerization initiator is 10
It is preferable to use together with a polymerization initiator having a half life of 10 hours lower than the decomposition temperature for obtaining time.

Specifically, benzoyl peroxide,
1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-di (t
-Butylperoxy) valerate, dicumyl peroxide, α, α'-bis (t-butylperoxydiisopropyl) benzene, t-butylperoxycumene, di-t
Organic peroxides such as -butyl peroxide; azo and diazo compounds such as azobisisobutyronitrile and diazoaminoazobenzene.

These polymerization initiators may be added to the monomer at the same time as the above-mentioned polyfunctional polymerization initiator. However, in order to maintain the efficiency of the polyfunctional polymerization initiator properly, it is necessary to add the polymerization initiator in the polymerization step. It is preferably added after the half-life of the polyfunctional polymerization initiator has elapsed.

These initiators are preferably used in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the monomer from the viewpoint of efficiency.

As a method for synthesizing the low molecular weight component, a known method can be used. However, in the bulk polymerization method, the termination reaction rate is increased by polymerizing at a high temperature,
Although a low molecular weight polymer can be obtained, there is a problem that the reaction is difficult to control. In this regard, in the solution polymerization method, a low molecular weight polymer can be easily obtained under mild conditions by utilizing the difference in chain transfer of radicals depending on the solvent, and by adjusting the amount of the initiator and the reaction temperature, It is preferable to obtain a low molecular weight component in the carboxyl group-containing vinyl resin.

As a solvent used in the solution polymerization, xylene,
Toluene, cumene, cellosolve acetate, isopropyl alcohol or benzene is used. If a styrene monomer is used, xylene, toluene or cumene is preferred. The solvent is appropriately selected depending on the polymer to be polymerized.
The reaction temperature varies depending on the solvent used, the polymerization initiator, and the polymer to be polymerized, but is usually preferably from 70 to 230 ° C. In the solution polymerization, it is preferable to perform the polymerization at 30 to 400 parts by mass of the monomer with respect to 100 parts by mass of the solvent.

It is also preferable to mix another polymer in the solution at the end of the polymerization, and several types of polymers can be mixed.

As the monomer having a glycidyl group unit constituting the vinyl resin having a glycidyl group, any compound having a vinyl group and an epoxide may be used. For example, esters of glycidyl alcohol and unsaturated carboxylic acid, unsaturated glycidyl ether, etc. It is. For example,
Examples include glycidyl acrylate, glycidyl methacrylate, β-methyl glycidyl acrylate, β-methyl glycidyl methacrylate, allyl glycidyl ether, allyl β-methyl glycidyl ether, and the like.

Particularly, a glycidyl monomer represented by the following general formula (3) is preferably used.

[0120]

Embedded image (In the formula, R ′ ₁ , R ′ ₂ and R ′ ₃ represent hydrogen, an alkyl group, an aryl group, an aralkyl group, a carboxyl group, and an alkoxycarbonyl group.)

The glycidyl group-containing vinyl resin can be obtained by copolymerizing a monomer having such a glycidyl group unit alone or as a mixture with a vinyl monomer by a known polymerization method.

The vinyl resin having a glycidyl group has a weight average molecular weight (Mw) of preferably 2,000 to 10
0000, more preferably 2,000 to 50,000
0, more preferably 3,000 to 40,000. When Mw is less than 2,000, even if the molecular weight increases in the cross-linking reaction in the binder resin, the molecular chain breakage in the kneading step is large, and the effect on the offset resistance may be reduced. When Mw exceeds 100,000, the fixing property may be affected. A vinyl resin having a glycidyl group has an epoxy value of 0.0
Those having 5 to 5.0 eq / kg are preferable. 0.05e
When the amount is less than q / kg, the crosslinking reaction hardly occurs, the amount of the high molecular weight component and the amount of the THF-insoluble component generated is small, and the effect on the offset resistance decreases. If it exceeds 5.0 eq / kg, the crosslinking reaction is likely to occur, but the molecular chain breakage in the kneading step is large, and the effect on the offset resistance is reduced.

In order to carry out the crosslinking reaction more effectively,
The vinyl resin preferably has a THF-insoluble content of 10% by mass or less, and more preferably 5% by mass or less.

The glycidyl group-containing vinyl resin of the present invention has a glycidyl group content of 0.01 to 10 per equivalent of the carboxyl group in the carboxyl group-containing vinyl resin.
It is preferable to use a mixing ratio of 0.0 equivalent, preferably 0.03 to 10.0 equivalent, more preferably 0.05 to 5.0 equivalent.

When the glycidyl group is less than 0.01 equivalent, the number of cross-linking points in the binder resin is reduced, and it is difficult to exhibit the effect of the cross-linking reaction such as offset resistance. If the amount exceeds 100 equivalents, the crosslinking reaction is likely to occur, but the developability may be affected.

The epoxy value of the glycidyl group-containing vinyl resin is determined by the following method.

<Measurement of Epoxy Value> The basic operation is based on JIS
According to K-7236. (1) A sample is precisely weighed at 0.5 to 2.0 (g), and the weight of the binder resin is defined as W (g). (2) A sample is placed in a 300 (ml) beaker and dissolved in 10 ml of chloroform and 20 ml of acetic acid. (3) 10 ml of tetraethylammonium bromide acetic acid solution is added to this solution. (4) Using a 0.1 mol / l acetic acid solution of perchloric acid,
Titrate using a potentiometric titrator. (For example, a potentiometric titrator AT-400 manufactured by Kyoto Electronics Co., Ltd. (win w
or an ABP-410 motorized burette. (5) At this time, the used amount of the perchloric acid acetic acid solution is S (ml).
The blank is measured at the same time, and the amount of the perchloric acid acetic acid solution used at this time is defined as B (ml). (6) Calculate the epoxy value by the following equation. f is a factor of the perchloric acetic acid solution. Epoxy value (eq / kg) = ｛0.1 × f × (S−
B)｝ / W

The vinyl resin having a carboxyl group and a glycidyl group preferably has a number average molecular weight of 1,000 to 40,000 in order to achieve good fixability. The weight average molecular weight is preferably from 10,000 to 10,000,000 in order to achieve good offset resistance and blocking resistance. By introducing an acid value and an epoxy value as described above into the resin having these molecular weights, a desired resin can be obtained. In the vinyl resin, THF is used to improve the dispersibility of the toner constituent materials.
The insoluble content is preferably 10% by mass or less, and more preferably 5% by mass or less.

The vinyl monomers to be copolymerized with the carboxyl group-containing monomer and the glycidyl group-containing monomer include the following.

For example, styrene; o-methylstyrene, m
-Methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene,
2,4-dimethylstyrene, pn-butylstyrene,
Styrene derivatives such as p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene and pn-dodecylstyrene; ethylene, propylene,
Ethylenically unsaturated monoolefins such as butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl acetate, vinyl propionate and benzoe Vinyl esters such as vinyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, (2-ethylhexyl) methacrylate,
Α-methylene aliphatic monocarboxylic esters such as stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic Acrylates such as propyl acrylate, n-octyl acrylate, dodecyl acrylate, acrylic acid (2-ethylhexyl), stearyl acrylate, acrylic acid (2-chloroethyl), phenyl acrylate; vinyl methyl ether, vinyl ethyl ether , Vinyl ethers such as vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole; - vinyl indole, N- vinylpyrrolidone, such as N- vinyl compounds, vinyl naphthalenes; acrylonitrile, methacrylonitrile, include such acrylic acid derivatives or methacrylic acid derivatives of acrylamide. These vinyl monomers are used alone or as a mixture of two or more monomers.

Of these, a combination of monomers that will form a styrene-based copolymer and a styrene-acrylic-based copolymer is preferred. In this case, at least the styrene-based copolymer component or the styrene-acrylic-based copolymer component may be used in combination. It is preferred that the content be not less than% by mass in terms of fixability and mixing property.

As the binder resin used in the toner of the present invention, the following polymers can also be used.

For example, homopolymers of styrene and its substituted substances such as polystyrene, poly-p-chlorostyrene and polyvinyl toluene; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene Copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-
Styrene such as vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer Copolymers: polyvinyl chloride, phenolic resin, natural modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin , Xylene resin, polyvinyl butyral, terpene resin, coumarone indene resin and petroleum resin.

When an imidazolium salt is used in the toner of the present invention, an imidazolium salt represented by the following general formula (1) or (2) or a polymer having an imidazolium salt as a constituent unit is used.

[0135]

Embedded image

R ₁ , R ₄ and R ₅ in the general formula (1) are
Hydrogen, an alkyl group having a substituent, an alkyl group having no substituent, a cycloalkyl group having a substituent, a cycloalkyl group having no substituent, an aryl group having a substituent, an aryl group having no substituent, Allyl group having a group, allyl group having no substituent, aralkyl group having a substituent, aralkyl group having no substituent, alkoxy group having a substituent, alkoxy group having no substituent, amino group having a substituent And a group selected from an amino group having no substituent, a halogen and a heterocyclic group, which may be the same or different. R ₂ and R ₃ are hydrogen, an alkyl group having a substituent, an alkyl group having no substituent, a cycloalkyl group having a substituent, a cycloalkyl group having no substituent, an aryl group having a substituent,
Aryl group having no substituent, allyl group having a substituent, allyl group having no substituent, aralkyl group having a substituent, aralkyl group having no substituent, alkoxy group having a substituent, having no substituent It represents a group selected from an alkoxy group and a heterocyclic ring, which may be the same or different. Further, R ₁ and R ₂ or R ₁ and R ₃ may be mutually connected to form a ring. Also, R ₄ , R ₅
May be connected to each other to form an aromatic ring or a heterocyclic ring. Examples of the substituent include hydrogen, an alkyl group, a cycloalkyl group, an aryl group, an allyl group, an aralkyl group, an alkoxyl group, an amino group, an amide group, a halogen, and a heterocyclic group. These may have an ether or sulfide structure. m is a positive integer of 1 or more, and X ^m- represents a counter anion.

The general formula (2) represents an imidazolium salt
A polymer as a structural unit is shown, and R in the general formula₆,
R₇, R₈Is hydrogen, an alkyl group having a substituent, a substituent
Having no alkyl group or cycloalkyl having a substituent
Group, unsubstituted cycloalkyl group, having a substituent
Aryl group, unsubstituted aryl group,
Having an allyl group, an unsubstituted allyl group,
Aralkyl group having, aralkyl group having no substituent,
Alkoxy groups having substituents, alcohols having no substituents
Xy group, substituted amino group, unsubstituted amino group
Mino groups, halogens or heterocycles, each being the same
May be different. Also, R ₇, R₈Are mutually
They may be linked to form an aromatic ring or a heterocyclic ring. R
₉Represents a linking group and may contain an ether bond
Phenylene, propenylene, vinylene, alkylene group
is there. This polymer is composed of imidazolium salts as structural units.
It should just be included. In that case, the linking groups are
And a graft chain may be added to the binder resin main chain.
May be combined. As the substituent, hydrogen, alkyl
Group, cycloalkyl group, aryl group, allyl group, ara
Alkyl group, alkoxy group, amino group, amide group, halogen
And heterocycles. These are ethers, sulfides
It may have a structure. m is a positive integer of 1 or more;
Is a positive integer of 1 or more, preferably 2 to 100
Is an integer of X^m-Represents a counter anion.

In the polymer having the imidazolium salt represented by the general formula (1) or the imidazolium salt represented by the general formula (2) as a constitutional unit, the kind of the imidazolium salt and the kind of the counter anion are selected. Thereby, excellent charging characteristics and excellent dispersion characteristics in the toner can be realized. As a result, the developing characteristics are also excellent.

Although these combinations cannot be uniquely limited, in order to impart high positive chargeability to the toner, in the general formula (1), R ₁ , R ₂ , R ₃ , R ₄ ,
R ₅ is preferably hydrogen, an alkyl group, a cycloalkyl group, an aryl group, an allyl group, an aralkyl group, or a heterocyclic group;
Each may be the same or different, each may have a substituent, and each preferably has 1 to 40 carbon atoms. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an allyl group, an aralkyl group, an alkoxyl group, an aromatic ring and a heterocyclic ring, and halogen. It is also preferable that R ₁ and R ₂ or R ₁ and R ₃ are mutually connected to form a ring to form a 4- or 5-membered ring. Further, it is also preferable that R ₄ and R ₅ are connected to each other to form an aromatic ring or a heterocyclic ring.

In the general formula (2), R ₆ , R ₇ , R
₈ is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an allyl group, an aralkyl group, or a heterocyclic ring. Each may be the same or different, each may have a substituent, and each preferably has 1 to 40 carbon atoms. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an allyl group, an aralkyl group, an alkoxyl group, an aromatic ring and a heterocyclic ring, and halogen. Further, it is also preferable that R ₇ and R ₈ are connected to each other to form an aromatic ring or a heterocyclic ring. R ₉ is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms containing an ether bond, and is preferably bonded to the polymer main chain to a graft chain.

The polymers to which the imidazolium salts are grafted include polystyrene, poly-p-chlorostyrene,
Styrene such as polyvinyltoluene and its substituted homopolymer; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylate copolymer, styrene -Methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone Styrene-based copolymers such as copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers and styrene-acrylonitrile-indene copolymers; polyvinyl chloride; phenolic resins; natural modified phenolic resins; Acid resin; Polyurethane; Polyamide resin; Furan resin; Epoxy resin; Xylene resin; Polyvinyl butyral; Rosin resin; Modified rosin resin; Terpene resin; Coumarone indene resin; Petroleum resins can be used.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
If the carbon number of each of the above exceeds 40, the softening point of the imidazolium salt or the polymer itself having the imidazolium salt as a constituent unit decreases, so that in the melt-kneading step at the time of toner production, the melting of the polymer The viscosity is reduced, and the dispersion in the toner is likely to be non-uniform, and as a result, the image characteristics are likely to deteriorate.

Further, the imidazolium salt or the polymer having the imidazolium salt as a constitutional unit in the present invention has a counter anion.

For example, as an inorganic anion, F^-, C
l^-, Br^-, I^-Halogen ions such as OH^-, S
O_Four ^2-, NO_Three ^-, PO_Four ^3-, CH_ThreeCOO^-, CH_ThreeS
O_Three ^-, CH_ThreeC₆H _FourSO_Three ^-, C_TwoH_FiveOSO_Three ^-, BF_Four ^-,
MoO_Four ^2-, WO_Four ^2-, ClO_Four ^-, SiF₆ ^2-,Also,
[TeMo₆O_{twenty four}]^6-, [H_TwoW₁₂O₄₂]^Ten-, [PMo
₁₂O₄₀]^3-, [PW₁₂O_Four]^3-Polyacid ions such as
Lopoly acid ions and the like. Organic anions
C1-C24 sulfonic acid ion, C1-C1
24 carboxylic acid ions, sulfuric acid monomers having 1 to 24 carbon atoms
Alkyl ester anion, tetraphenyl boron ion
And the like. Among these, halogen ions, S
O _Four ^2-, MoO_Four ^2-, WO_Four ^2-, CH_ThreeC₆H_FourSO_Three ^-, Hid
Roxynaphthosulfonate ion, benzoate ion, carbon
Monoalkyl sulfate anions of Formulas 1 to 6 are produced
This is preferred from the viewpoint of ease of storage and storage stability of the compound.

In the present invention, the imidazolium salt represented by the general formula (1) or the polymer having the imidazolium salt represented by the general formula (2) as a constituent unit is 100 parts by mass of the binder resin in terms of the imidazolium salt. Parts to 0.01 to 20.0 parts by mass, preferably 0.1 to 10.
0 parts by mass, more preferably 0.5 to 7.0 parts by mass is added. When the addition amount is less than 0.01 parts by mass, the toner cannot have a sufficient charge amount, and the effect of adding imidazolium salts or a polymer containing imidazolium salts as a structural unit is not exhibited. On the other hand, when the addition amount is 2
If the amount is more than 0.0 parts by mass, it will be excessively added, causing poor dispersion in the toner and presenting as aggregates,
The amount of imidazolium salts per individual toner particle tends to be non-uniform, which is not preferable.

In the toner of the present invention, a binder resin containing a resin obtained by reacting a vinyl resin having a carboxyl group with a vinyl resin having a glycidyl group as a component, and an imidazolium salt represented by the general formula (1) By containing a polymer having an imidazolium salt represented by (2) as a constituent unit, it is possible to prevent excessive charging in the cleaning step. As a result, it is possible to reduce electrostatic adhesion to the photosensitive drum, prevent electrostatic aggregation of waste toner, and prevent discharge of excessively charged waste toner to the photosensitive drum.

By reducing the electrostatic adhesion to the photoreceptor drum, it is easy to clean even if a toner lump is generated, and the occurrence of fusion can be prevented. By preventing electrostatic agglomeration of the waste toner, lifting of the cleaning blade due to generation of toner agglomerates is suppressed, and defective cleaning is prevented. By preventing the discharge of the excessively charged waste toner to the photosensitive drum, it is possible to prevent the electrostatic breakdown of the drum and prevent the occurrence of leak spots.

The above effects are further enhanced when metal oxide particles are contained.

On the other hand, the toner transferred onto the transfer sheet through the transfer step has a moderate level of electrostatic cohesion due to the action of the added metal oxide particles. It is less susceptible to the leaked electromagnetic field and can prevent the unfixed toner image from being disturbed.

Further, the imidazolium salt or the polymer having imidazolium salt as a constituent unit used in the present invention can be used in combination with a conventionally known charge control agent.

The toner of the present invention contains the imidazolium salt or a polymer having the imidazolium salt as a constitutional unit, so that they function as a positive charge control agent and can be used as a positively chargeable toner. It is also possible to add a conventionally known positive charge control agent. Alternatively, the toner can be used as a negatively chargeable toner by adding a conventionally known negative charge control agent.

As a method for incorporating the charge control agent into the toner, there are a method of adding it inside the toner and a method of adding it externally.
The amount of use of these charge control agents is determined by the type of the binder resin, the presence or absence of other additives, the toner manufacturing method including the dispersion method, and is not uniquely determined, but is preferably determined. 0.1 to 100 parts by mass of binder resin
It is used in an amount of 10 parts by mass, more preferably 0.1 to 5 parts by mass.

The imidazolium salts used in the present invention are synthesized as follows.

The imidazolium salts represented by the general formula (1) can be synthesized by several methods. For example, 1,3-unsubstituted imidazole is synthesized, and the 1,3-position is alkylated with an alkylating agent. It can be obtained by alkylation and finally exchanging the counter anion (see formula below).

[0155]

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Although many kinds of 1,3-unsubstituted imidazoles are commercially available, they can be obtained, for example, by reacting a 1,2-dicarbonyl compound with aldehyde and ammonia (see the following formula).

[0157]

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Examples of the 1,2-dicarbonyl compound include glyoxal, methylglyoxal, dimethylglyoxal, benzyl and the like. Aldehydes include formaldehyde, acetaldehyde, benzaldehyde and the like. Examples of the ammonia include alcoholic ammonia and a method using ammonium acetate in glacial acetic acid.

1,3-unsubstituted benzimidazoles are
It is obtained by heating o-phenylenediamines and carboxylic acid (see the following formula).

[0160]

Embedded image (X represents an alkyl group (eg, a methyl group or an ethyl group), a nitro group, an acetoxyl group, etc.)

The o-phenylenediamines include o-phenylenediamines
Phenylenediamine, 3,4-diaminotoluene, 3,
4-diaminonitrobenzene and the like.

Examples of the carboxylic acids include fatty acids (formic acid, acetic acid, propionic acid, stearic acid) and aromatic carboxylic acids (benzoic acid, p-hydroxybenzoic acid, etc.).

The reaction is usually carried out in dilute hydrochloric acid, but may give a sufficient yield in the absence of a solvent or even in water. The reaction is usually carried out at a temperature of from 80 to 100 ° C. In the case of aromatic carboxylic acids, a high temperature of from 150 to 200 ° C is often required.

[0164] The imidazolium salts can be obtained by reacting the 1,3-imidazoles obtained as described above with an alkylating agent. In the alkylation, only the 1-position can be alkylated by reacting the imidazoles with an equimolar alkylating agent, or the 1- and 3-positions can be simultaneously alkylated by reacting with a 2-fold molar alkylating agent. .

Examples of the alkylating agent include alkyl halides (eg, methyl chloride, butyl bromide, benzyl chloride, xylylene dichloride), dialkyl sulfates (eg, dimethyl sulfate, diethyl sulfate, etc.), and trialkyl phosphates (eg, trimethyl phosphate, etc.). ) And the like.

Examples of the reaction solvent include alcohols such as methanol, ethanol and isopropanol; ketones such as acetone and methyl ethyl ketone; aprotic polar solvents such as dimethylformamide, dimethylacetamide and dimethylsulfoxide; and carbonized solvents such as benzene, toluene and xylene. Hydrogen; halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, and tetrachloroethane;
And mixed solvents thereof, and alcohols and other mixtures thereof are preferred from the viewpoint of the solubility of the raw materials and products and the reaction yield.

The reaction temperature is usually from 0 to 150 ° C. To stop the reaction when only position 1 is alkylated, 5
The reaction is carried out at 0 ° C. or less, and the reaction is carried out at 50 ° C. or more to alkylate the 3-position. Further, in order to neutralize the hydrogen halide generated in the reaction system, a strong alkali (NaOH, K
OH, etc.) can also be allowed to coexist. It is preferable to coexist a strong alkali from the viewpoint of yield.

Further, the counter anion of the imidazolium salt obtained by the above method is converted into a strong alkali salt (sodium p-toluenesulfonate, hydroxynaphthosulfonic acid, sodium, potassium tetrafluoroborate, sodium tetraphenylborate, (Sodium molybdate, sodium tungstate, etc.) can be changed to a structure other than the counter anion obtained.

The polymer having an imidazolium salt represented by the general formula (2) as a constitutional unit is synthesized by reacting an imidazole and a dihalide (see the following formula). At this time, the polymer terminal may be bonded as a graft chain to the binder resin main chain, or may be connected to form a ring structure.

[0170]

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Examples of the dihalides include alkylene dihalides (ethylene dichloride, ethylene dibromide, 1,3-dibromopropane, 1,4-dichlorobutane, 1,4-dibromobutane, 1,6-dibromohexane, , 8-dibromooctane and the like); alkylene dihalides containing an ether bond in the group (β, β'-dichloroethyl ether, β, β'-dichloroethylformal, etc.) are preferred.

When the binder resin has a halomethyl group or an amino group as a functional group, it can react with the functional group and bond. In this case, the imidazolium salt is bonded as a graft chain having a constitutional unit.

A monohalide or imidazole can be used in combination to block the polymerization terminal (see the following formula).

[0174]

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Examples of the monohalides include methyl chloride, methyl iodide, methyl bromide, butyl chloride, benzyl bromide and the like. Examples of imidazoles include 1-methylimidazole, 1-ethylimidazole, 1-benzylimidazole and the like.

In order to make the counter anion an anion other than the above-mentioned halogens, alkali metal and ammonium salts of anions other than the halogens can be used in combination.

In this synthesis reaction, it is preferable to use an alkali in combination for the purpose of neutralizing hydrogen halide generated by the reaction. Examples of the alkali include sodium hydroxide, potassium hydroxide and sodium carbonate.

The reaction temperature is usually 30 to 200 ° C., preferably 60 to 180 ° C. If the temperature is lower than 30 ° C., the reaction rate is low. The reaction time depends on the reaction temperature,
Usually 2 to 20 hours.

This synthesis method does not limit the imidazolium salts used in the present invention at all. Examples of the imidazolium salts used in the present invention are shown below, but these are representative examples in consideration of ease of handling, and do not limit the toner of the present invention at all.

[0180]

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[0181]

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[0182]

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[0183]

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The following is an example of a polymer having an imidazolium salt as a constitutional unit used in the present invention. However, this is a typical example in consideration of ease of handling, and similarly does not limit the toner of the present invention. Absent.

[0185]

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[0186]

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[0187]

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[0188]

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[0189]

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In the present invention, the following waxes are preferably contained in order to impart releasability to the toner. It is a wax having a melting point of 70 to 165 ° C. and a melt viscosity at 160 ° C. of 1000 mPa · s or less, and specific examples thereof include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, montan wax, ethylene, propylene, butene, and pentene. , Hexene, heptene, octene, nonene, linear α-olefins such as decene and branched α-olefins having a branched terminal, and homopolymers of olefins having different positions of these unsaturated groups or These copolymers are exemplified. In addition, alcohol wax,
Fatty acid waxes, ester waxes and natural waxes are also used.

Further, a block copolymer with a vinyl monomer, a modified wax subjected to graft modification, or an oxidized wax may be used.

[0192] These waxes are used in the production of toner.
It may be added and mixed in the polymer component in advance.
In such a case, it is preferable to preliminarily dissolve the wax and the high molecular weight polymer in a solvent at the time of preparing the polymer component, and then mix with a low molecular weight polymer solution. This alleviates phase separation in a micro region, controls reaggregation of high molecular weight components, and provides a good dispersion state with a low molecular weight polymer.

The amount of the wax is preferably 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass, per 100 parts by mass of the binder resin.
Incidentally, two or more kinds of waxes may be added in combination.

As the colorant that can be used in the toner of the present invention, any suitable pigment or dye can be used. For example, as pigments, carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, bengara,
Examples include phthalocyanine blue and indanthrene blue. These are used in an amount necessary to maintain the optical density of the fixed image, and are used in an amount of 0.1 to 100 parts by mass of the binder resin.
An addition amount of 20 parts by mass, preferably 0.2 to 10 parts by mass is good.

For the same purpose, a dye is further used. For example, there are azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes, and 0.1 to 20 parts by mass, preferably 0.3 to 1 part by mass per 100 parts by mass of the binder resin.
The addition amount of 0 parts by mass is good.

Further, in the toner of the present invention, a magnetic substance can be used as a colorant and used as a magnetic toner.

In a toner containing a binder resin of the present invention and a polymer having imidazole salts or imidazolium salts as constituent units, when applied to a magnetic toner containing a magnetic material as a colorant, the magnetic toner particles This is particularly effective because it is possible to suppress the lack of the image.

The reason why the loss of the magnetic substance from the toner particles can be suppressed is not clearly understood, but the amine in the polymer having imidazole salts or imidazolium salts as constituent units and the carboxyl in the binder resin are not clearly understood. Group,
Interaction with glycidyl groups, hydroxyl groups or acid anhydride groups prevents imidazole salts or polymers having imidazolium salts as constituent units in the toner particles from being lost from the toner particles. It is presumed that this is because the loss of the magnetic material from the toner particles caused by the loss of the polymer having a lithium salt as a constituent unit from the toner particles is also suppressed.

The magnetic material used in the present invention includes iron oxides such as magnetite, maghemite and ferrite;
Metals such as iron, cobalt, nickel or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium Metal alloys and mixtures thereof are used, and those containing a silicon element on the surface or inside of the magnetic material are preferable.

The average particle size of the magnetic material is preferably 0.05 to 1.0 μm, more preferably 0.1 to 0.6 μm.
μm, and more preferably 0.1 to 0.4 μm.

In the present invention, the amount of the magnetic substance contained in the toner is from 10 to 200 parts by mass, preferably from 20 to 170 parts by mass, more preferably from 30 to 150 parts by mass, per 100 parts by mass of the binder resin.

In the toner of the present invention, charging stability,
In order to improve developability, fluidity and durability, it is preferable to add silica fine powder.

[0203] Silica fine powder used in the present invention has a specific surface area by the BET method by nitrogen adsorption 30 m ² / g or more, particularly in the range of 50 to 400 m ² / g give good results. It is preferable to use 0.01 to 8 parts by mass, preferably 0.1 to 5 parts by mass, of silica fine powder with respect to 100 parts by mass of the toner.

When the content of the silica fine powder in the toner is less than 0.01 part by mass, it is difficult to obtain sufficient fluidity and durability stability, and when the content of the silica fine powder in the toner exceeds 8 parts by mass. In this case, the amount of free silica fine powder increases, and the charging of the toner tends to become unstable.

The silica fine powder used in the present invention may be used, if necessary, for the purpose of hydrophobicity, charge control, etc., with silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane coupling agents, It is also preferable that the treatment is performed with a treating agent such as a silane compound having a functional group or another organosilicon compound, or in combination with various treating agents.

The toner of the present invention may contain other external additives as required.

For example, there are resin fine particles and inorganic fine particles which function as a charge assisting agent, a conductivity-imparting agent, a fluidity-imparting agent, a caking preventing agent, a releasing agent at the time of fixing with a heat roller, a lubricant, an abrasive and the like.

For example, in order to impart fluidity to the toner,
Fine resin particles such as fluororesin powder and polyvinylidene fluoride; metal oxides such as alumina, titania, germanium oxide and zirconium oxide; carbides such as silicon carbide and titanium carbide; and inorganics such as nitrides such as silicon nitride and germanium nitride Compounds may be used in combination.

Further, the toner used in the present invention preferably contains metal oxide particles having a weight average particle diameter of 0.4 to 5.5 μm. Thereby, the metal oxide acts as a microcarrier for the toner, enables an effective charge imparting action to the toner having a low charge amount, and can maintain good charging characteristics and powder characteristics, and at the same time, The unfixed toner image transferred onto the transfer sheet is given an appropriate degree of electrostatic cohesion by the metal oxide particle component adhering to the toner, and leaks from the fixing device even in the fixing step using the induction heating fixing device. A high-quality fixed image from a low speed to a high speed can be obtained without being affected by the applied electromagnetic field and without causing disturbance of the unfixed toner image.

The weight average particle diameter of the metal oxide particles is 0.4 μm.
When the value is less than m, components adhering to the toner increase, and the overall charge amount may decrease.Also, due to poor cleaning due to slipping through the cleaning plate or remaining on the latent image carrier. In some cases, charging inhibition may occur. On the other hand, if it exceeds 5.5 μm,
The components released from the toner are not developed and are not consumed, so that they are accumulated in the developing device, which may hinder development.

The metal oxides usable in the present invention include:
The following are mentioned. For example, alkaline earth metals,
Oxides of rare earth metals and transition metals, specifically, oxide fine particles of alkali metals such as barium, magnesium, calcium and strontium; oxide fine particles of rare earth metals such as yttrium, europium, cerium and lanthanum ; Scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper,
Examples include oxide fine particles of a transition metal such as zinc.

The metal oxide fine particles usable in the present invention may be composite metal oxide fine particles.

To prepare the toner of the present invention, a binder resin, an imidazolium salt, a colorant and, if necessary, a magnetic substance, a wax, a metal salt or metal complex, a pigment or a dye, and other additives are added to Henschel. After sufficiently mixing with a mixer such as a mixer or a ball mill, the mixture is melt-kneaded using a hot kneader such as a heating roll, a kneader, or an extruder, and after cooling and solidification, pulverized and classified, and further, if necessary, desired additives. Is sufficiently mixed with a mixer such as a Henschel mixer to obtain the toner of the present invention.

For example, as a mixer, a Henschel mixer (Mitsui Mining); a super mixer (Kawata); a ribocorn (Okawara Seisakusho); a Nauta mixer, a turbulizer, a cyclomix (Hosokawa Micron); Spiral pin mixers (manufactured by Taiheiyo Kiko Co., Ltd.); Reedige mixers (manufactured by Matsubo Co., Ltd.); kneading machines include KRC kneader (manufactured by Kurimoto Tekkosho); bus co-kneader (manufactured by Buss); TEM Mold extruder (manufactured by Toshiba Machine Co., Ltd.); TEX twin-screw kneader (manufactured by Nippon Steel Works); PCM kneader (manufactured by Ikegai Iron Works); three roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho); Decks (manufactured by Mitsui Mining Co., Ltd.); MS-type pressurized kneader, nider ruder (manufactured by Moriyama Seisakusho); Banbury mixer (Kobe Steel, Ltd.) Ltd.). Examples of the pulverizer, a counter jet mill, micron jet, Inomizer (manufactured by Hosokawa Micron); IDS type mill, P
JM jet crusher (manufactured by Nippon Pneumatic Industries, Ltd.);
Cross Jet Mill (Kurimoto Iron Works); ULMAX (Nisso Engineering); SK Jet O.
Mills (manufactured by Seishin Enterprise Co., Ltd.); Kryptron (manufactured by Kawasaki Heavy Industries, Ltd.); Turbo Mill (manufactured by Turbo Kogyo Co., Ltd.). Turbo Classifier (Nisshin Engineering); Micron Separator, Turboplex (ATP), TSP Separator (Hosokawa Micron); Elbow Jet (Nisshin Mining), Dispersion Separator (Nihon Pneumatic) ; Y
M microcut (manufactured by Yasukawa Shoji Co., Ltd.) is mentioned. As a sieving device used for sifting coarse particles, etc.,
Ultrasonic (made by Koei Sangyo Co., Ltd.); resonator sieve, gyro shifter (made by Tokuju Kogyo Co., Ltd.); Vibrasonic system (made by Dalton); Sonic Clean (made by Shinto Kogyo); turbo screener (made by Turbo Kogyo); Micro shifter (manufactured by Makino Sangyo Co., Ltd.);

The toner of the present invention preferably has a weight average particle size of 3 to 10 μm, more preferably 4 to 9 μm. When the weight-average particle diameter of the toner is less than 3 μm, durability stability is poor, high image density is hardly obtained, fogging easily occurs, and the weight-average particle diameter of the toner is 10 μm.
When m exceeds m, it is difficult to obtain a high-definition image, and toner consumption increases.

The weight average particle size of the toner and the metal oxide particles is measured using a Coulter Counter TA-II (manufactured by Coulter), but a Coulter Multisizer (manufactured by Coulter) can also be used. The electrolyte is 1
A 1% NaCl aqueous solution is prepared using graded sodium chloride. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and the measurement sample is further added to 2 to
Add 20 mg. The electrolytic solution in which the sample was suspended was subjected to a dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser, and the measurement apparatus used a 100 μm aperture as an aperture.
The volume distribution and the number distribution were calculated by measuring the volume and the number of the toner having a size of 2.00 μm or more. Then, the weight-based weight average particle size (D4; the median value of each channel is a representative value for each channel) obtained from the volume distribution according to the present invention was obtained.

The channels are 2.00 to 2.52
less than 2.5 μm; less than 2.52 to 3.17 μm;
4. less than 4.00 μm; 4.00 to less than 5.04 μm;
04 to less than 6.35 μm; 6.35 to less than 8.00 μm; 8.00 to less than 10.08 μm; 10.08 to 1
2.70 μm or less; 12.70 to less than 16.00 μm;
16.00 to less than 20.20 μm; 20.20 to 25.
Less than 40 μm; 25.40 to less than 32.00 μm; 3
13 channels of 2.00 to less than 40.30 μm are used.

Next, an example of a schematic configuration of a developing device used in the image forming method of the present invention will be described. However, the scope of the present invention is not limited thereto.

In FIG. 1, a developing device X1 comprises an image carrier for carrying an electrostatic latent image formed by a known process,
For example, the electrophotographic photosensitive drum 7 is rotated in the direction of arrow B. The developing sleeve 14 as a developer carrier carries the magnetic toner 10 as a one-component magnetic developer supplied from the hopper 9 as a developing container, and rotates in the direction indicated by an arrow A to contact the developing sleeve 14 with the photosensitive drum. The magnetic toner 10 is transported to the developing unit D where the drum 7 faces. The magnetic toner 10 is placed inside the developing sleeve 14.
A magnet 11 is arranged for magnetically attracting and holding the magnet. The magnetic toner 10 obtains a triboelectric charge capable of developing the electrostatic latent image on the photosensitive drum 7 by friction with the developing sleeve 14.

In order to regulate the layer thickness of the magnetic toner 10 conveyed to the developing section D, a regulating blade 8 as a developer layer thickness regulating member made of a ferromagnetic metal is arranged to be about 200 to 300 μm from the surface of the developing sleeve 14. From the hopper 9 so as to face the developing sleeve 14 with a gap width of. The line of magnetic force from the magnetic pole N1 of the magnet 11 is
Is concentrated, a thin layer (developer layer) of the magnetic toner 10 is formed on the developing sleeve 14. A non-magnetic blade can also be used as the regulating blade.

The thickness of the thin layer of the magnetic toner 10 formed on the developing sleeve 14 is preferably smaller than the minimum gap between the developing sleeve 14 and the photosensitive drum 7 in the developing section D. The present invention is particularly effective for a developing device of a type that develops an electrostatic latent image with such a thin toner layer, that is, a non-contact type developing device. However, the present invention is also applicable to a developing device in which the thickness of the toner layer in the developing section is equal to or greater than the minimum gap between the developing sleeve 14 and the photosensitive drum 7, that is, a contact type developing device.

For the sake of simplicity, in the following description, a non-contact type developing device will be used as an example.

A developing bias voltage is applied to the developing sleeve 14 from a power supply 15 in order to fly the magnetic toner 10 as a one-component magnetic developer carried on the developing sleeve 14. When a DC voltage is used as the developing bias voltage, a voltage having a value between the potential of the image portion of the electrostatic latent image (the region where the magnetic toner 10 is adhered and visualized) and the potential of the background portion is used. Preferably, it is applied to the sleeve 14.
On the other hand, in order to increase the density of the developed image or improve the gradation, an alternating bias voltage may be applied to the developing sleeve 14 to form an oscillating electric field in which the direction is alternately reversed in the developing unit D. In this case, it is preferable to apply, to the developing sleeve 14, an alternating bias voltage on which a DC voltage component having a value between the potential of the image portion and the potential of the background portion is superimposed.

In so-called regular development in which toner is adhered to a high potential portion of an electrostatic latent image having a high potential portion and a low potential portion to visualize the toner, a toner charged to a polarity opposite to the polarity of the electrostatic latent image is used. On the other hand, in so-called reversal development, in which toner is adhered to a low potential portion of an electrostatic latent image to visualize the toner, a toner charged to the same polarity as the polarity of the electrostatic latent image is used.
Note that the high potential and the low potential are expressed by absolute values. In any case, the magnetic toner 10 is charged to a polarity for developing the electrostatic latent image by friction with the developing sleeve 14.

FIG. 2 is a block diagram showing another example of the present invention.

In the developing device X2 shown in FIG.
As a developer layer thickness regulating member for regulating the layer thickness of the magnetic toner 10 on the substrate 4, a material having rubber elasticity such as urethane rubber or silicone rubber, or a material having metal elasticity such as phosphor bronze or stainless steel is used. It is characterized in that an elastic plate 17 is used and this elastic plate 17 is pressed against the developing sleeve 14. In such a developing device, a thinner toner layer can be formed on the developing sleeve 8. Other configurations of the developing device X2 in FIG. 2 are basically the same as those of the developing device X1 shown in FIG. 1. In FIG. 2, the same reference numerals as those in FIG. 1 denote the same members.

In the developing device shown in FIG. 2 in which the toner layer is formed on the developing sleeve 14 as described above, the toner is rubbed on the developing sleeve 14 by the elastic plate 17, so that the amount of triboelectric charge of the toner is large. Thus, the image density is improved. In a non-magnetic one-component developer, a developing device using such an elastic plate is used.

Next, an example of the image forming method of the present invention will be described based on a schematic configuration diagram of an image forming method having a contact charging / contact transfer method shown in FIG.

Reference numeral 801 denotes a rotating drum type photosensitive member, which is rotated at a predetermined peripheral speed (process speed) clockwise in the drawing. Reference numeral 802 denotes a charging roller which is pressed against the surface of the photoconductor 801 with a pressing force, and is rotated by the rotation of the photoconductor 801. 803 denotes a charging bias voltage V ₂ for applying a voltage to the charging roller 802, a charging roller 802
Is applied, the surface of the photoconductor 801 is charged to a predetermined polarity and potential. Next, an electrostatic charge image is formed by the image exposure 804, and is sequentially visualized as a toner image by the developing unit 805.

A bias V ₁ is applied to the developing sleeve constituting the developing means 805 from the bias applying means 813. The toner image formed on the latent image bearing member by development is electrostatically transferred to the transfer sheet 808 by a transfer roller 806 as a contact transfer means that the transfer bias V ₃ is applied, the toner image on the transfer sheet, Heating and pressurizing means 811
Is heated and pressed. On the surface of the photoconductor 801 after the transfer of the toner image, adhered contaminants such as untransferred toner are cleaned and cleaned by a cleaning device 809 having an elastic cleaning blade pressed against the photoconductor 801 in a counter direction. It is negatively charged and repeatedly imaged.

The primary charging means has been described using the charging roller 802 as the contact charging means as described above, but may be a contact charging means such as a charging blade or a charging brush.
Further, non-contact corona charging means may be used. The transfer unit has been described using the transfer roller 806 as described above, but may be a contact charging unit such as a transfer roller or a non-contact corona transfer unit.

In the present invention, as the heating and pressurizing means,
(I) a rotating heating member having at least a magnetic field generating means, (ii) a heating layer having a thickness of 0.01 to 20 mm and a release layer that generates heat by electromagnetic induction, and (iii) a width 1 with the heating member.
A rotary pressurizing means having at least a rotary pressurizing member forming a nip of about 20 mm, while pressing the rotary heatable member by the rotary pressurizing member at a total pressure of 45 to 1000 N via a recording material. Fixing speed 10-600mm /
In seconds, the toner image on the recording material is heated and pressed to form a fixed image.

Next, an example of a schematic configuration of a heat-pressure fixing device used in the image forming method of the present invention will be described with reference to FIG. However, the scope of the present invention is not limited thereto.

FIG. 4 is a schematic sectional view of a fixing device used in the present invention.

The fixing roller 61 has an outer diameter of 40 mm, for example.
For example, PTFE 10 to 50 μm, PF 10
It is constituted by providing a layer of A10 to 50 μm. The pressure roller 62 includes a hollow core metal 74 and an elastic layer 75 which is a heat-resistant rubber layer having a surface release property formed on the outer peripheral surface thereof. Bearing portions are formed at both ends of the fixing roller 61 and the pressure roller 62, and are rotatably attached to a fixing unit frame (not shown), so that only the fixing roller 61 is driven. The pressure roller 62 is a fixing roller 61
And is arranged so as to be driven to rotate by frictional force at a pressure contact portion (nip portion). Pressing roller 6
Reference numeral 2 is pressed in the rotation axis direction of the fixing roller 61 by a mechanism (not shown) using, for example, a spring. The pressure roller 62 is loaded with, for example, 294 N (about 30 kg weight),
In this case, the width (nip portion) of the pressure contact portion is configured to be about 6 mm. Of course, the nip width may be changed by changing the load in consideration of use conditions and the like.

The temperature sensor 66 is disposed so as to abut (or non-contact with) the surface of the fixing roller 61, and based on a detection signal of the temperature sensor 66, an electric power to an exciting coil 63 as an exciting means is provided. By increasing or decreasing the supply,
Automatic control is performed so that the surface temperature of the fixing roller 61 becomes a predetermined constant temperature.

[0237] The conveyance guide 67 carries the unfixed toner image 6
The transfer sheet 76 conveyed while carrying the transfer roller 8 is arranged at a position where it is introduced into a nip portion between the fixing roller 61 and the pressure roller 62.

The separation claw 70 is disposed in contact with or close to the surface of the fixing roller 61 to prevent the transfer sheet 76 from being wound around the fixing roller 61.

The excitation coil 63 has a PPS, a PPS, and so on, so that a conductive wire is wound around a central projection of a magnetic core 64 (hereinafter, referred to as a core) having a T-shaped cross section, and extends along the inner peripheral surface of the fixing roller. It is provided outside a holder 65 made of a heat-resistant resin such as PEEK or phenol resin. A magnetic field induced by applying an alternating current of 10 to 100 kHz to the exciting coil 63 is guided to a core 64 as a magnetic field interrupting unit having a high magnetic permeability, and a magnetic flux and an inner surface of the fixing roller 61 as a heat generating unit. An eddy current is generated, and Joule heat is generated by the specific resistance of the fixing roller 61. In order to increase the heat generation, the number of turns of the exciting coil 63 may be increased, the core 64 may be made of ferrite or permalloy having a high magnetic permeability and a low residual magnetic flux density, or the frequency of the alternating current may be increased. The core 6
Reference numeral 4 denotes a T-shaped section extending in the rotation axis direction of the fixing roller 61. The section 4 blocks the magnetic field generated by excitation by the excitation coil 63, and concentrates the magnetic field toward the heating section.

When the surface temperature of the fixing roller 61 is controlled at a predetermined temperature optimum for fixing, for example, 190 ° C. with the above-described configuration, it is necessary to supply power of about 200 W to the exciting coil. The temperature of the exciting coil at that time is about 210
° C and the temperature of the magnetic core is about 200 ° C.

When a large amount of toner is continuously fixed at a speed of about 30 sheets per minute, power of about 450 W is required to be supplied to the exciting coil.
0 ° C. and the temperature of the magnetic core becomes about 220 ° C. Therefore, the Curie temperature of the magnetic core must be 220 ° C. or higher in consideration of the case where a large amount of toner is continuously fixed. If the temperature of the magnetic core exceeds its Curie temperature (the temperature at which transition from ferromagnetic to paramagnetic), the power-to-heat conversion efficiency will be extremely reduced.

In the above description, the case where the fixing roller is used as the heating member has been described. However, it is of course possible to adopt a configuration made of a thin metal film instead of the fixing roller.

[0243]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited thereto.

<Production Example A-1 of Carboxyl Group-Containing Vinyl Resin>-79 parts by mass of styrene-20 parts by mass of n-butyl acrylate-1 part by mass of methacrylic acid-2 parts by mass of di-t-butyl peroxide 2 parts by mass Was thoroughly purged with nitrogen while stirring 200 parts by mass of xylene in a four-necked flask,
And then added dropwise over 4 hours. Further, the polymerization was completed under reflux of xylene, and the solvent was distilled off under reduced pressure.
The resin thus obtained is designated as A-1.

The physical properties of this resin A-1 were Mn = 5,60
0, Mw = 41,000, Tg = 59 ° C., Av = 6.
4, THF insoluble content = 0% by mass.

<Production Example A-2 of Carboxyl Group-Containing Vinyl Resin>-78 parts by mass of styrene-20 parts by mass of n-butyl acrylate-2 parts by mass of acrylic acid-2 parts by mass of di-t-butyl peroxide 2 parts by mass of each of the above components Resin A-2 was obtained in the same manner as in Production Example A-1, except that the composition was changed to The physical properties of this resin A-2 were Mn = 4,
800, Mw = 45,000, Tg = 60 ° C., Av = 1
5.5, THF insoluble content = 0% by mass.

<Production Example A-3 of Carboxyl Group-Containing Vinyl Resin>-75 parts by mass of styrene-19 parts by mass of n-butyl acrylate-6 parts by mass of methacryloxyethyl succinic acid-2 parts by mass of di-t-butyl peroxide Part Resin A-3 was obtained in the same manner as in Production Example A-1, except that the above components were changed. The physical properties of this resin A-3 were Mn = 6,
100, Mw = 37,000, Tg = 58 ° C., Av = 2
8.9, THF-insoluble content = 0% by mass.

<Production Example A-4 of Carboxyl Group-Containing Vinyl Resin>-79 parts by mass of styrene-20 parts by mass of n-butyl acrylate-1 part by mass of monobutyl maleate-2 parts by mass of di-t-butyl peroxide Resin A-4 was obtained in the same manner as in Production Example A-1 except that the components were changed. The physical properties of this resin A-4 were Mn = 7,
200, Mw = 39,000, Tg = 58 ° C., Av =
3.2, THF insoluble content = 0% by mass.

<Production Example A-5 of Carboxyl Group-Containing Vinyl Resin>-74 parts by mass of styrene-19 parts by mass of n-butyl acrylate-7 parts by mass of acrylic acid-2 parts by mass of di-t-butyl peroxide 2 parts by mass of each of the above components Resin A-5 was obtained in the same manner as in Production Example A-1, except that the composition was changed to The physical properties of this resin A-5 are as follows: Mn = 5
200, Mw = 44,000, Tg = 58 ° C., Av = 5
4.3, THF insoluble content = 0% by mass.

<Production Example A-6 of Vinyl Resin>-80 parts by mass of styrene-20 parts by mass of n-butyl acrylate-2 parts by mass of di-t-butyl peroxide Production Example A- except that the above components were changed. Resin A-6 was obtained in the same manner as in 1. The physical properties of this resin A-6 were Mn = 6,
300, Mw = 46,000, Tg = 58 ° C., Av =
0, THF insoluble content = 0% by mass.

<Production Example A-7 of Carboxyl Group-Containing Vinyl Resin>-79.8 parts by mass of styrene-20 parts by mass of n-butyl acrylate-0.2 parts by mass of monobutyl maleate-di-t-butyl peroxide 2 Parts by mass Resin A-7 was obtained in the same manner as in Production Example A-1, except that the above components were changed. The physical properties of this resin A-7 were Mn = 7,
100, Mw = 39,000, Tg = 58 ° C., Av =
0.6, THF insoluble content = 0% by mass.

Table 1 summarizes the physical properties of these carboxyl group-containing vinyl resins.

<Production Example B-1 of Glycidyl Group-Containing Vinyl Resin>-80 parts by mass of styrene-18 parts by mass of n-butyl acrylate-2 parts by mass of glycidyl methacrylate-5 parts by mass of di-t-butyl peroxide The components were thoroughly purged with nitrogen while stirring 200 parts by mass of xylene in a four-neck flask,
And then added dropwise over 4 hours. Further, the polymerization was completed under reflux of xylene, and the solvent was distilled off under reduced pressure.
The resin thus obtained is referred to as B-1. The physical properties of this resin B-1 were Mw = 28,000, epoxy value =
0.14 eq / kg, THF insoluble content = 0 mass%.

<Production Example B-2 of Glycidyl Group-Containing Vinyl Resin>-78 parts by mass of styrene-18 parts by mass of n-butyl acrylate-4 parts by mass of glycidyl methacrylate-5 parts by mass of di-t-butyl peroxide Except having changed into the component, it carried out similarly to manufacture example B-1, and obtained resin B-2. The physical properties of this resin B-2 are Mw = 2
2,000, epoxy value = 0.28 eq / kg, THF
The insoluble content was 0% by mass.

<Production Example B-3 of Glycidyl Group-Containing Vinyl Resin>-74 parts by mass of styrene-18 parts by mass of n-butyl acrylate-8 parts by mass of glycidyl methacrylate-5 parts by mass of di-t-butyl peroxide Except having changed into the component, resin B-3 was obtained in the same manner as in Production Example B-1. The physical properties of this resin B-3 were Mw = 2
6,000, epoxy value = 0.56 eq / kg, THF
The insoluble content was 0% by mass.

<Production Example B-4 of Glycidyl Group-Containing Vinyl Resin> ・ Styrene 66 parts by mass ・ N-butyl acrylate 18 parts by mass ・ Glycidyl methacrylate 16 parts by mass ・ Di-t-butyl peroxide 5 parts by mass A resin B-4 was obtained in the same manner as in Production Example B-1 except for changing the components. The physical properties of this resin B-4 were Mw = 2
0000, epoxy value = 1.13 eq / kg, THF
The insoluble content was 0% by mass.

Table 2 summarizes the physical properties of these glycidyl group-containing vinyl resins.

[0258]

[Table 1]

[0259]

[Table 2]

(Production Example of Developer Carrier) <Development Sleeve Production Example 1>-Phenol resin intermediate 125 parts by mass-Carbon black 5 parts by mass-Crystalline graphite 45 parts by mass-Methanol 41 parts by mass-Isopropyl alcohol 284 parts by mass Part The methanol solution of the phenol resin intermediate was diluted with isopropyl alcohol (IPA), carbon black and crystalline graphite were added, and the mixture was dispersed by a sand mill using glass beads. Next, a resin layer was applied on the sleeve using this paint.

As the developing sleeve, the surface of a stainless steel cylindrical tube having an outer diameter of 32 mmφ was polished so that the cylindrical tube had a run-out of 10 μm or less and a surface roughness of 4 μm or less in Rz. The sleeve was set up vertically, rotated at a constant speed, masked at the upper and lower ends, and the coating material was applied while lowering the spray gun at a constant speed. The masking width at both ends of the sleeve was set to 3 mm.
This is dried and cured at 160 ° C. for 20 minutes in a drying oven, and then a band-shaped felt is applied to the surface of the resin-coated sleeve.
The surface was polished by rubbing with a pressing load of 9.2 N (4 kgf) to obtain a resin layer coated sleeve having a uniform film thickness.

The resin layer has a thickness of 10 μm and a surface roughness R
a was 0.86 μm on average at 6 points, the volume resistance was 4 Ω · cm, and the pencil hardness was further measured to be 2H.
A magnet was inserted into this sleeve, and flanges were attached to both ends to obtain a developing sleeve 1.

<Developing Sleeve Manufacturing Example 2> As a developing sleeve, the surface of a stainless steel cylindrical tube having an outer diameter of 32 mm was polished and the deflection of the cylindrical tube was 10 μm or less and the surface roughness was R.
What was reduced to 4 μm or less in z notation was subjected to masking on the upper and lower ends, and was subjected to 0.392 MPa (4.0 kgf / 4.0 kg) by a blast machine using amorphous alumina abrasive grains (# 300).
The blast treatment was performed at a blast pressure of ² cm ² ). The masking width at both ends of the sleeve was set to 3 mm. The surface roughness Ra of this blasting sleeve is 1.12 μ on average at six points.
m. A magnet was inserted into this sleeve, and flanges were attached to both ends to form a developing sleeve 2.

[Example 1] Binder resin A-1 95 parts by mass Binder resin B-1 5 parts by mass Magnetite 90 parts by mass (octahedral, average particle diameter 0.20 μm, BET = 8.7 m ²⁾ / G) ・ Polyethylene wax 4 parts by mass ・ Imidazolium salt compound example (1) 5 parts by mass After sufficiently premixing the above materials with a Henschel mixer,
Melt kneading was performed using a twin-screw kneading extruder set at 150 ° C. The obtained kneaded material was cooled, coarsely pulverized by a cutter mill, finely pulverized by a fine pulverizer using a jet stream, and the obtained finely pulverized material was further classified by an air classifier to obtain a weight average particle size. A classified fine powder (toner particles) of 7.5 μm was obtained.

THF of Raw Material Binder Resins A-1 and B-1
Although the insoluble content was 0% by mass, a reaction between the carboxyl group and the glycidyl group produced a cross-linking component, and a 10.8% by mass THF-insoluble content was produced in the binder component of the toner.

To 100 parts by mass of the obtained classified fine powder, silica fine powder (BET specific surface area 200 m
² / g) Amino-modified silicone oil (amine equivalent 830, viscosity 70 mm ^{2 at} 25 ° C.) per 100 parts by mass
/ S) 0.8 parts by mass of hydrophobic silica treated with 17 parts by mass was added, and 1.0 part by mass of strontium titanate fine powder (2.0 μm in weight average particle size) as composite metal oxide particles was further added. Mix with Henschel mixer, 150 openings
The mixture was sieved with a mesh of μm to obtain Toner 1. This toner 1
Table 3 summarizes the physical properties of the compound.

With respect to the obtained toner 1, the following evaluation tests were performed.

< Blocking resistance evaluation test > 20 g of toner
Was placed in a 100 ml polycup and left in a thermostat at 50 ° C. for 3 days, and then the toner state was visually evaluated.

Anti-blocking crank ◎ (excellent) No agglomerates, smooth ○ (good) Some agglomerates are seen, but easily collapsed △ (OK) Aggregates are seen, but collapse when shaken × ( Not possible) Aggregates can be grasped and do not collapse easily

< Evaluation Test for Offset Resistance > The electromagnetic induction heating fixing device having the structure shown in FIG. 4 can be operated outside the copying machine, the temperature of the fixing roller can be set arbitrarily, and the thickness of the heating layer of the heating member of the fixing roller can be adjusted. By passing an unfixed image using 50 g / m ² paper using an external fixing device prototyped so as to have a nip width of 6 mm, a nip width of 8.0 mm, a total pressure of 400 N, and a process speed of 300 mm / sec. The offset resistance was evaluated. In the evaluation, the temperature of the fixing roller was set to 24
The temperature was set to 0 ° C., the state of offset was observed, and evaluation was performed based on the following evaluation criteria (evaluation environment: room temperature / room temperature (23 ° C.)
/ 60% RH)).

Offset rank ◎ (excellent) No offset is seen at all ○ (good) Very slight offset is seen × (not acceptable) Offset occurs

< Fixing Property Evaluation Test > Using an external fixing device modified so as to have a process speed of 520 mm / sec using the above external fixing device, passing an unfixed image using 80 g / m ² paper. The low-temperature fixability was evaluated by the test.
At the time of evaluation, the temperature of the fixing roller was adjusted every 5 ° C. within a range of 120 to 200 ° C., and an unfixed image was fixed at each temperature, and the obtained image was subjected to a weight equivalent to 4.9 kPa. The paper was rubbed back and forth five times, and the point at which the image density reduction rate before and after rubbing was 10% or less was defined as the fixing start temperature. The lower the temperature, the more excellent the fixing property (evaluation environment: normal temperature / normal temperature (23 ° C./60% RH)).

< Actual Image Evaluation Test > A commercially available digital copying machine GP605 (manufactured by Canon Inc.) was used, the fixing unit was changed to an electromagnetic induction heating fixing device shown in FIG. 4, and the developing sleeve was developed according to the present invention. Replaced with sleeve production example 1 and modified so that the process speed became 520 mm / sec. Under normal temperature / humidity environment, copy 100,000 sheets of character image with 6% image ratio by A4 horizontal feed, normal temperature / low humidity Image ratio of 6 under environmental and high temperature / high humidity environment
% Of character images were copied 50,000 sheets by A4 landscape feed, and image evaluation was performed for image density, fog, poor cleaning, image fouling due to fusing, fusing member fouling, and fixing scattering / fixing tailing. The thickness of the heating layer of the heating member of the electromagnetic induction heating fixing device is 6 mm, and the nip width is 8.0 m.
m, and the total pressure was 400N. Further, the fixing member was visually evaluated, and the contamination level was classified into the following ranks (evaluation environment: normal temperature / normal humidity (23 ° C./60% RH), normal temperature / low humidity (23 ° C./5% RH), high temperature / High humidity (32.5 ° C / 80
% RH)).

In order to evaluate the ability of the fixing offset by increasing the temperature of the end of the fixing roller, a character image having an image ratio of 6% was subjected to A4 continuous vertical feeding under normal temperature / normal humidity environment.
000 sheets were copied, and immediately after that, 20 sheets of a solid black 50 mm band (horizontal) image were copied by A4 continuous horizontal feed, and the heated image stains (offset) at the front and back edges of the printed paper were observed. The level of image stain due to offset was classified into the ranks shown below. The temperature of the fixing roller was detected at the center in the longitudinal direction of the roller to control the temperature.

In this embodiment, a stainless steel cylindrical tube is used as the material (base tube) of the developing sleeve base.
Regarding the thermal deformation of the sleeve itself in the P605 modified machine, an experiment was performed under the condition without any influence.

The image density was evaluated by an average value obtained by measuring 10 points of a solid black image portion using a “Macbeth reflection densitometer” (manufactured by Macbeth).

The fog was copied using a “reflection densitometer” (manufactured by Tokyo Denshoku Technology Center Co., Ltd.) to an average value (Dr) of 10 points of the reflection density of the transfer paper before image formation and a solid white image. The reflection density (ds) of the subsequent transfer paper was measured, and the difference (Ds-Dr) was used as the fog value.

Image dirt (dirt due to poor cleaning or fusion) rank ◎ (excellent) Not generated at all ○ (excellent) Very rarely small spot-like contamination occurs / disappears △ (OK) Minor spot-like Repeated generation / disappearance due to linear contamination × (impossible) Dirt occurs and does not disappear

Fixed scattering / tailing rank ◎ (excellent) Neither scattering nor tailing occur at all ○ (good) Very slight scattering is observed, but no tailing occurs △ (acceptable) slight scattering / tailing Occurs, but there is no character collapse. × (impossible) Characters are partially crushed, resulting in an unclear image

Fixing member stain rank （(excellent) No contamination observed ○ (good) Slightly contaminated, but no image stains Δ (OK) No image stains due to contamination but poor separation X × (impossible) Image contamination due to contamination occurs

Edge temperature rise image stain (offset) rank （(excellent) No image stain on both surfaces (no stain on fixing roller) （(good) Very little image stain on either front or back surface Generated △ (Possible) Image stains occur on either front surface or back surface × (Not possible) Image stains occur on both front surface and back surface

Table 3 summarizes the results of these evaluations.

[Example 2] Production example of polymer (48) having imidazolium salt as a constitutional unit: Styrene 7
94 parts by mass, 160 parts by mass of butyl acrylate and 46 parts by mass of chloromethylstyrene are polymerized in toluene with 30 parts by mass of azobisisobutyronitrile under boiling point, and then the solvent is removed to obtain a number average molecular weight (Mn). 6000,
A styrene resin C-1 having halomethyl having a weight average molecular weight (Mw) of 17000 was obtained.

Styrene resin C- having a halomethyl group
1 in 128 parts by mass, heptadecylbenzimidazole 1
25 parts by mass, 68 parts by mass of 1,4-dibromobutane, and 18 parts by mass of sodium carbonate were added to dimethylformamide (DM
The reaction was carried out at 80 ° C. for 2 hours and under reflux for 4 hours in F).
Next, 5 parts by mass of benzyl chloride was added, and the mixture was refluxed for 4 hours. After the completion of the reaction, the reaction product was added to an aqueous solution in which 205 parts by mass of p-toluenesulfonic acid was dissolved in 2000 parts by mass of water while stirring with a homomixer. The precipitate was washed with water, filtered, and dried to obtain a graft polymer D-1. The graft copolymer D-1 was subjected to NMR measurement under the conditions shown below, and the chemical shift value of carbon specific to the imidazole ring was 136 based on TSM.
Since the peak intensities are found at around ppm and around 122 ppm, and the peak intensities have a relationship of 1: 2, the unit of the imidazolium salt shown in the general formula (2) is present in the graft copolymer D-1. Make sure you do. This is designated as Polymer Example (48) having the imidazolium salt of the present invention as a constitutional unit.

<NMR measurement> Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.) Measuring frequency: 400 MHz Pulse condition: 5.0 μs Data point: 32768 Delay time: 25 sec Frequency range: 10500 Hz Number of times of accumulation: 16 times Measurement Temperature: 40 ° C. Sample: 200 mg of a measurement sample is placed in a φ5 mm sample tube, and CDCl ₃ (TMS 0.05
%) Is added and dissolved in a constant temperature bath at 40 ° C. for adjustment.

In Example 1, the compound example (1) of the imidazolium salt was replaced with the polymer example (4) obtained in the above production example.
8) The same as Example 1 except that 3.0 parts by mass of cerium oxide fine powder (weight average particle size 2.2 μm) was added instead of the stylonium titanate fine powder which is the composite metal oxide particles. Thus, Toner 2 was obtained. Each evaluation similar to that of Example 1 was performed on this toner 2. Table 3 summarizes the toner properties and the evaluation results.

Example 3 The procedure of Example 1 was repeated except that the binder resin and the imidazolium salt compounds shown in Table 3 were used, and strontium titanate fine powder as composite metal oxide particles was not added. Thus, Toner 3 was obtained. This toner 3 was evaluated in the same manner as in Example 1. Table 3 summarizes the toner properties and the evaluation results.

[Examples 4 to 15] Toner 4 was prepared in the same manner as in Example 1 except that a binder resin and a compound of imidazolium salts or a polymer having imidazolium salts as constituent units shown in Table 3 were used. ~ 15. With respect to these toners 4 to 15, the developing sleeve manufacturing example Nos. Each evaluation was performed in the same manner as in Example 1 except that the developing sleeve was used. Table 3 summarizes the toner properties and the evaluation results.

Comparative Examples 1 and 2 Toner 16 having a weight average diameter of 7.5 μm was prepared in the same manner as in Example 1 except that the binder resin and the imidazolium salt compounds shown in Table 3 were used.
~ 17. Each of the toners 16 and 17 was evaluated in the same manner as in Example 1. Table 3 summarizes the toner properties and the evaluation results.

Comparative Example 3 Binder Resin A-1 95 parts by mass Binder Resin B-3 5 parts by mass Magnetite 90 parts by mass (octahedral, average particle size 0.20 μm, BET = 8.7 m ²⁾ / G) ・ 4 parts by mass of low molecular weight polypropylene wax (melting point: 130 ° C.) ・ 2 parts by mass of nigrosine compound After sufficiently mixing the above materials with a Henschel mixer,
In the same manner as in Example 1, a toner 18 having a weight average particle size of 7.5 μm was obtained. The same evaluation as in Example 1 was performed on the toner 18. Table 3 summarizes the toner properties and the evaluation results.

[0291]

[Table 3]

[0292]

According to the present invention, a rotary heating member having at least a rotary heating member having at least a heat generating layer and a release layer which generate heat by magnetic field generation, electromagnetic induction, and a rotary pressing member is used, In an image forming method in which a toner image on the recording material is heated and pressurized and fixed to form a fixed image while the rotation heating member is pressed by the rotation pressing member via the recording material, the toner is used as a binder resin. At least one selected from the group consisting of a mixture of a vinyl resin having a carboxyl group and a vinyl resin having a glycidyl group, a vinyl resin having a carboxyl group and a glycidyl group, and a vinyl resin having a carboxyl group and a glycidyl group reacted.
A toner containing a specific imidazolium salt or a polymer having a specific imidazolium salt as a constituent unit, the binder resin component of the toner having a specific acid value, The molecular weight distribution measured by GPC of the THF-soluble component in the toner has a specific molecular weight distribution, and the specific resin-insoluble content in the binder resin in the toner makes it possible to obtain charging characteristics and powder as a toner. It is possible to improve good low-temperature fixability and offset resistance even under light pressure fixing conditions without impairing physical properties, and further improve blocking resistance.

Further, when a metal oxide is added to the toner used in the present invention, the above characteristics are promoted, and the charging characteristics and the powder characteristics are further improved. Effectively prevents problems such as poor cleaning, toner conveyance clogging, and drum leak spots.Also in the fixing process using the induction heating method, high-definition images can be obtained from low to high speed without disturbing unfixed toner images. Images can be supplied stably.

Accordingly, it is possible to provide an image forming method capable of achieving both energy saving (low power consumption) of the fixing device and improvement of user operability (on-demand printing).

[Brief description of the drawings]

FIG. 1 is a schematic view illustrating an example of a magnetic developer supply system developing device of the present invention (using a magnetic blade as a regulating member).

FIG. 2 is a schematic diagram showing an example of a magnetic developer supply system developing device of the present invention (using an elastic blade as a regulating member).

FIG. 3 is a schematic diagram for explaining the image forming method of the present invention.

FIG. 4 is a schematic diagram of a cross section of the electromagnetic induction heating / pressing fixing device of the present invention.

[Explanation of symbols]

 7 Photosensitive Drum (Latent Image Holder) 8 Regulator Blade 9 Hopper 10 Magnetic Toner (Magnetic Developer) 11 Magnet 12 Cylindrical Substrate 13 Coating Layer (Resin Layer) 14 Developing Sleeve (Developer Carrier) 15 Power Supply 17 Elastic Blade A Rotating direction of developing sleeve B Rotating direction of photosensitive drum D Developing unit 801 Latent image carrier 801a Photoconductive layer 801b Conductive base layer 802 Charging roller 802a Conductive elastic layer 802b Core 803 Charge bias power supply 804 Image exposure 805 Developing roller 806 Transfer Roller 806a Conductive elastic layer 806b Core 807 Transfer bias power supply 808 Transfer sheet 809 Cleaning device 810 Static elimination exposure device 811 Heating and pressurizing means 813 Developing bias power supply 61 Rotary heating member (fixing roller) 62 Rotary pressing member (Pressing roller) 63 Excitation coil 4 core 65 the holder 66 temperature sensor 67 conveying guide 68 toner image 70 separation claw 71 heating layer 72 the release layer 73 fixed image 74 hollow metal core 75 elastic layer 76 the recording material (transfer sheet)

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroyuki Fujikawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Masaaki Taya 3-30-2 Shimomaruko, Ota-ku, Tokyo Non-corp. F term (reference) 2H005 AA01 AA08 CA02 CA28 CA30 CB00 DA03 EA05 EA06 EA10 FB04 2H033 AA02 AA20 BA58 BB06 BB13 BB29 BB30 BB33 BB34 BE06 CA07 CA13 CA27

Claims (12)

[Claims] 1. An image forming method for forming a fixed image on a recording material by heating and pressurizing and fixing a toner image on a recording material by a heating and pressing means, wherein the toner comprises at least a binder resin, an imidazolium salt, and a colorant. The binder resin comprises a mixture of a vinyl resin having a carboxyl group and a vinyl resin having a glycidyl group, a vinyl resin having a carboxyl group and a glycidyl group, and a vinyl resin having a carboxyl group and a glycidyl group reacted. At least one vinyl resin selected from the group, wherein the imidazolium salt is an imidazolium salt represented by the following general formula (1) or an imidazolium salt represented by the following general formula (2) A polymer having a structural unit, (In the above general formula (1), R ₁ , R ₄ and R ₅ represent hydrogen, an alkyl group having a substituent, an alkyl group having no substituent, a cycloalkyl group having a substituent, a cycloalkyl having no substituent, An alkyl group, an aryl group having a substituent,
Aryl group having no substituent, allyl group having a substituent, allyl group having no substituent, aralkyl group having a substituent, aralkyl group having no substituent, alkoxy group having a substituent, having no substituent An alkoxy group, an amino group having a substituent, an amino group having no substituent, a halogen or a heterocyclic ring, which may be the same or different; R ₂ and R _{3 each} represent hydrogen or a substituent Alkyl group, an alkyl group having no substituent, a cycloalkyl group having a substituent, a cycloalkyl group having no substituent, an aryl group having a substituent, an aryl group having no substituent, an allyl group having a substituent, Unsubstituted allyl group, substituted aralkyl group, unsubstituted aralkyl group, substituted alkoxy group, unsubstituted alkoxy group R ₁ and R ₂ , or R ₁ and R ₃ , may be mutually connected to form a ring; R ₄ and R ₅ may form an interconnected aromatic or heterocyclic ring; such substituents include hydrogen, alkyl, cycloalkyl, aryl, aryl, aralkyl, An alkoxy group, an amino group, an amide group, a halogen or a heterocyclic ring, which may have an ether structure or a sulfide structure; m represents a positive integer of 1 or more, and X ^m- represents a counter anion. The general formula (2) represents a polymer having an imidazolium salt as a constitutional unit. In the general formula (2), R ₆ ,
R ₇ and R ₈ are hydrogen, an alkyl group having a substituent, an alkyl group having no substituent, a cycloalkyl group having a substituent, a cycloalkyl group having no substituent, an aryl group having a substituent, a substituent Aryl group having no substituent, allyl group having a substituent, allyl group having no substituent, aralkyl group having a substituent, aralkyl group having no substituent, alkoxy group having a substituent, alkoxy group having no substituent , An amino group having a substituent, an amino group having no substituent, a halogen or a heterocyclic ring, which may be the same or different; and R ₇ and R ₈ are linked to each other to form an aromatic ring. Or may form a heterocyclic ring;
R ₉ represents a linking group, which is a phenylene group, a propenylene group, a vinylene group or an alkylene group which may contain an ether bond; the polymer may contain an imidazolium salt as a constituent unit. In that case, the linking groups may form a ring structure with each other, or may be bonded to the binder resin main chain as a graft chain; as a substituent, hydrogen, an alkyl group, a cycloalkyl group, an aryl group, There are an allyl group, an aralkyl group, an alkoxy group, an amino group, an amide group, a halogen or a heterocyclic ring, which may have an ether structure or a sulfide structure; m represents a positive integer of 1 or more; Represents a positive integer of 1 or more, and X ^m- represents a counter anion. And (i) magnetic field generating means;
i) a rotary heating member having at least a heat generating layer of 0.01 to 20 mm and a release layer that generate heat by electromagnetic induction;
(Iii) using a heating / pressurizing means having at least the heating member and a rotary pressing member forming a nip having a width of 1 to 20 mm, and applying a total pressure of 45 to the rotary heating member via a recording material;
An image forming method, wherein a fixed image is formed by heating and pressing the toner image on the recording material at a fixing speed of 10 to 600 mm / sec while being pressed by the rotary pressing member at a pressure of up to 1000 N. 2. The toner according to claim 1, wherein said toner is tetrahydrofuran (TH).
F) In the molecular weight distribution measured by gel permeation chromatography (GPC) of the soluble component, the number average molecular weight (Mn) is from 1,000 to 40,000, and the weight average molecular weight (Mw) is from 10,000 to 10,
The image forming method according to claim 1, wherein the number is 0,000,000. 3. The toner according to claim 1, wherein said toner is tetrahydrofuran (TH).
2. The method according to claim 1, wherein F) has at least one main peak in a molecular weight range of 4,000 to 30,000 in a molecular weight distribution measured by gel permeation chromatography (GPC) of a soluble component. Image forming method. 4. In the molecular weight distribution, a molecular weight of 30,0
The peak area of 00 or less is 60 to the total peak area.
The image forming method according to claim 3, wherein the ratio is in the range of 100% to 100%. 5. The toner according to claim 1, wherein said toner is tetrahydrofuran (TH)
F) In the molecular weight distribution measured by gel permeation chromatography (GPC) of the soluble component, a region having a molecular weight of 4,000 to 30,000 and a molecular weight of 10
The image forming method according to claim 1, wherein each of the image forming apparatuses has at least one peak in a range of 0000 to 10,000,000. 6. In the molecular weight distribution, a molecular weight of 4,000
0-30,000 region and molecular weight 800,000
The image forming method according to claim 5, wherein each of the regions has at least one peak in a region of 10 to 10,000,000. 7. In the molecular weight distribution, a molecular weight of 4,000
6. The method according to claim 5, wherein each of the regions has at least one peak in a region of 0 to 30,000, a region of a molecular weight of 100,000 to 800,000, and a region of a molecular weight of 800,000 to 10,000,000. The image forming method as described in the above. 8. In the molecular weight distribution, a molecular weight of 100,
The peak area of 000 or more is 5 to the total peak area.
The image forming method according to any one of claims 5 to 7, wherein the ratio is from 40 to 40%. 9. The image forming method according to claim 1, wherein the binder resin component of the toner contains 0.1 to 60% by mass of a THF-insoluble component. 10. The image forming method according to claim 1, wherein the THF-soluble component of the toner has an acid value of 0.1 to 50 mgKOH / g. 11. The toner has a weight average particle diameter of 0.4 to 0.4.
The image forming method according to claim 1, further comprising 5.5 μm metal oxide particles. 12. The image forming method according to claim 1, wherein the toner is a positively chargeable toner.