JP2000227676A - Negative triboelectric charge type toner and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a negative triboelectric charge type toner having good low temperature fixability and not causing the contamination of a fixing member independently of the heating system of a fixing apparatus. SOLUTION: The negative triboelectric charge type toner contains a bonding resin, a colorant, a wax and an organometallic compound and has 5-35 mgKOH/ g acid value. The bonding resin is a vinyl polymer having 3-50 wt.% chloroform- insoluble component and a tetrahydrofuran-soluble component of the polymer has a main peak in the molecular weight range of 5,000-30,000 and a sub-peak and/or a shoulder in the molecular weight range of 200,000-1,500,000 in the chromatogram and contains 15-70% component whose molecular weight is 10,000-100,000. The organometallic command is an organozirconium compound obtained by the coordination and/or bonding of zirconium and an aromatic compound selected from the group consisting of aromatic diols, aromatic hydroxycarboxylic acids or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used in a recording method utilizing an electrophotographic method, an electrostatic recording method, an electrostatic printing method, a toner jet recording method, or the like.

[0002]

2. Description of the Related Art An electrophotographic method is disclosed in U.S. Pat.
Numerous methods are known as described in Japanese Patent Publication No. 7,691, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748. Generally, a photoconductive substance is used to form an electrostatic charge image on a photoreceptor by various means,
Then, the electrostatic image is developed using toner, and if necessary, a toner image is transferred to a transfer material such as paper, and then fixed by heating, pressure, heat and pressure, or solvent vapor to obtain a toner image. is there.

Various methods and apparatuses have been developed for fixing the toner image onto a sheet such as paper, which is the above-mentioned final step. The most common method at present is a fixed heat generation through a heat roller or a heat-resistant film. This is a compression heating method using a heater.

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

Since the surface of the heating roller and the toner image in the softened and melted state come into contact with each other under pressure, a part of the toner image adheres to and transfers to the surface of the fixing roller, and is transferred again to the next sheet to be fixed. And the offset phenomenon occurs, which stains the sheet to be fixed. This offset phenomenon is greatly affected by the fixing speed and the fixing temperature. Generally, when the fixing speed is slow,
The surface temperature of the heating roller is set relatively low, and when the fixing speed is high, the surface temperature of the heating roller is set relatively high. This is because the amount of heat applied from the heating roller to the toner to fix the toner is made substantially constant regardless of the fixing speed.

The toner on the sheet to be fixed forms several toner layers. Therefore, in a system in which the fixing speed is high and the surface temperature of the heating roller is high, the temperature difference between the toner layer in contact with the heating roller and the lowermost toner layer in contact with the sheet to be fixed increases. When the surface temperature of the heating roller is high, the uppermost toner layer is excessively softened and melted, and the offset phenomenon is easily caused.
When the surface temperature of the heating roller is low, the toner in the lowermost layer does not melt sufficiently, so that a phenomenon of low-temperature offset in which the toner is not fixed on the sheet to be fixed is likely to occur.

As a method for solving this problem, when the fixing speed is high, a method of increasing the pressure at the time of fixing and anchoring the toner to the sheet to be fixed is usually used. According to this method, the temperature of the heating roller can be reduced to some extent, and the high-temperature offset phenomenon of the toner can be prevented. However, since the shearing force applied to the toner is very large, the sheet to be fixed wraps around the fixing roller, causing a winding offset, or after separation of the separation claw for separating the sheet to be fixed from the fixing roller. Easily appear in the fixed image. Furthermore, because of the high pressure, the line image is crushed or the toner is scattered at the time of fixing, and the image quality of the fixed image is likely to deteriorate.

Various additives added during the production of the toner,
In particular, it is difficult to uniformly disperse the wax, so that not only the fixing performance of the toner but also the developability tend to be problematic. In particular, this problem is remarkable particularly in the case of fine particles of toner.

JP-A-6-214421 discloses an image forming method using a toner containing an aluminum complex and a charge accelerating additive.

JP-A-8-196199 discloses a toner having a peak in a specific molecular weight range and a specific THF-insoluble content.

Japanese Patent Application Laid-Open No. 10-10785 discloses a toner containing a metal complex type monoazo compound and a metal complex of an aromatic hydroxycarboxylic acid as charge control agents.

JP-A-10-90939 discloses a toner in which a binder resin does not substantially contain a THF-insoluble component, has a peak in a specific molecular weight range, and has a specific acid value.

Japanese Patent Application Laid-Open No. Hei 9-146292 discloses a toner containing polyalkylene fine particles having a specific dynamic friction coefficient, wherein the contact angle of the solid image surface fixed on an OHP sheet is within a specific range. I have.

Japanese Patent Application Laid-Open No. 9-244294 discloses a toner containing fine particles of polyalkylene having a specific dynamic friction coefficient, wherein the contact angle of the toner and the dielectric loss tangent of the toner satisfy a specific relationship.

Although these toners can improve the fixability to some extent, they are insufficient to prevent the toner from offsetting to a heating roller or a heat-resistant film as a heating member of a fixing device.

[0016]

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

It is an object of the present invention to provide a low-temperature machine which is suitable for a medium-to-high-speed machine using a hot-roll fixing device, or a medium-to-low-speed machine using a press-bonding heat-fixing system using a fixed heating heater via a heat-resistant film. An object of the present invention is to provide a toner and an image forming method which exhibit fixability and do not cause contamination of a heating member due to offset from a low temperature to a high temperature.

An object of the present invention is to provide a low-temperature fixing device which exhibits good fixability of a halftone portion even when used as a binder resin for a toner having a reduced particle size and an increased content of a coloring agent (particularly a magnetic substance). An object of the present invention is to provide a toner and an image forming method which have excellent properties.

An object of the present invention is to provide a toner capable of maintaining a sufficient offset prevention effect even for a fixing member and a cleaning member which have been aged and deteriorated due to durability, and having both a releasing property and a developing property of the toner. And an image forming method.

[0020]

According to the present invention, there is provided a negative triboelectric charging toner containing at least a binder resin, a colorant, a wax and an organometallic compound, wherein (a) the toner has an acid value of 5 to 35 mgKOH / g. (B) the binder resin of the toner is a vinyl polymer; (c) the binder resin of the toner has a chloroform-insoluble content of 3 to 50% by weight;
(D) In a chromatogram obtained by gel permeation chromatography (GPC) measurement, the tetrahydrofuran (THF) soluble component of the toner has a main peak in a molecular weight region of 5,000 to 30,000, and a molecular weight of 200,000 to 1
It has at least one sub-peak and / or shoulder in a region of 500,000, and a component having a molecular weight of 10,000 to 100,000
(E) an aromatic compound selected from the group consisting of zirconium and aromatic diols, aromatic hydroxycarboxylic acids, aromatic monocarboxylic acids and aromatic polycarboxylic acids. Is a coordinated and / or bound organic zirconium compound.

Further, the present invention provides (I) a developing step of developing an electrostatic charge image carried on an image carrier for carrying an electrostatic charge image with a negatively triboelectric charging toner to form a toner image; II) a transfer step of transferring the toner image formed on the image carrier to or from a recording material via an intermediate transfer member; and (III) recording the toner image transferred to the recording material. A fixing step of heating and fixing to a material, wherein the toner having the above-mentioned configuration is used as the negative frictionally chargeable toner.

[0022]

DETAILED DESCRIPTION OF THE INVENTION The present inventors have developed zirconium,
Organic zirconium compounds (eg, organic zirconium) in which an aromatic compound selected from the group consisting of aromatic diols, aromatic hydroxycarboxylic acids, aromatic monocarboxylic acids, and aromatic polycarboxylic acids is coordinated and / or bound. Complex, organic zirconium complex salt, organic zirconium salt) as a negative charge control agent, and further adjust the acid value and molecular weight distribution of the toner binder resin to a specific range using a vinyl polymer as the toner binder resin. By doing so, it is possible to obtain a high charge amount even in a high-temperature and high-humidity environment while maintaining good rise of toner charge.
Even in a low temperature and low humidity environment, there is no overcharging,
Further, regardless of the fixing method of the fixing device, the heating member is less likely to be contaminated by the offset due to the offset, and the fixing member and the cleaning member are deteriorated due to durability (aging) by achieving both the releasing property of the toner and the developing property of the toner. It has been found that a sufficient offset prevention effect can be maintained even with respect to.

Hereinafter, the toner of the present invention will be described in detail.

According to the study of the present inventors, in order to prevent the fixing member from being contaminated by offset regardless of the heating method of the fixing device, it is not enough to improve the low-temperature fixing property and the high-temperature offset resistance of the toner. It was sufficient, and it was found that it was important to improve the releasability of the toner from the fixing member.

Conventionally, improvement of the toner offset phenomenon and improvement of the fixability of the toner have been regarded as the same. However, fixing by improving a binder resin and a releasing agent such as wax contained in the toner has been considered. The improvement of the offset accompanying the improvement of the performance is limited and insufficient.

Further, if the releasability of the toner is insufficient even if the releasability of the fixing member and the cleaning member is improved, a sufficient offset prevention effect can be expected in the initial stage of use of these members. However, when used for a long period of time, each member may deteriorate over time, and eventually an offset may occur.

Conventionally, the fact that the binder resin of the toner has an insoluble content in an organic solvent such as chloroform and THF is as follows.
Although proposed from the viewpoint of improving the hot offset resistance of the toner, even with such a toner, aged fixing members,
In some cases, a sufficient offset prevention effect is not exerted on the cleaning member. Toners may contain wax for the purpose of imparting releasability, but it is necessary to contain a large amount of wax in order to maintain a sufficient offset prevention effect for aged fixing members and cleaning members. is there. In this case, problems such as a reduction in image density due to the developing property of the toner, that is, a decrease in image density due to durability, and an increase in fog density may occur. Further, it is difficult to control the dispersion state of the wax contained in the toner particles, and the toner contains a large amount of the released wax.
As a result, the toner on the photoconductor may not be sufficiently cleaned and may remain, resulting in an image defect.

In a toner using a vinyl polymer as a binder resin, in order to maintain a sufficient offset prevention effect even on an aged fixing member and cleaning member, it is necessary to improve the toner releasability and develop the toner. It is necessary to balance gender.

According to the study of the present inventors, in a toner containing an organic zirconium compound, the toner has a specific acid value, the binder resin contains a specific chloroform-insoluble component, and the binder resin of the toner. Is achieved by having a main peak, a sub-peak and / or a shoulder in a specific molecular region.

In the toner of the present invention, the acid value of the toner is 5 to 35 mgKOH / g, preferably 10 to 30 mKOH / g.
It is preferably gKOH / g. If the acid value of the toner is less than 5 mgKOH / g and 35 mgKOH / g
In any case where the value exceeds g, in a toner containing an organic zirconium compound described later, the image density may decrease due to durability.

In the toner of the present invention, the binder resin contained in the toner preferably contains 3 to 50% by weight of a chloroform-insoluble component, more preferably 5 to 45% by weight.
%, More preferably 10 to 40% by weight. If the amount of chloroform-insoluble content contained in the binder resin contained in the toner is less than 3% by weight or more than 50% by weight, an organic zirconium compound described later is contained. In the toner, it is difficult to keep the dispersion of the wax contained in the toner in an optimum state, and the toner adhesion to the fixing member may become apparent due to durability.

In the toner of the present invention, the THF-soluble component of the binder resin contained in the toner has a molecular weight range of 5,000 to 30,000, preferably a molecular weight range of 7000 to 25,000 in a chromatogram measured by GPC. More preferably has a main peak in the molecular weight region of 9000 to 20,000, and has at least one or more subpeaks or shoulders in the region of molecular weight of 200,000 to 1.5 million, preferably in the region of molecular weight of 300,000 to 1.2 million, and It is desirable that a component having a molecular weight of 10,000 to 100,000 be contained in an amount of 15 to 70%, preferably 20 to 60%. In both the case where the main peak is in a region having a molecular weight of less than 5,000 and the case where the main peak is in a region having a molecular weight of more than 30,000, it is possible to maintain the dispersion of an organic zirconium compound described later contained in the toner in an appropriate state. It is difficult, and the image density may decrease due to durability, which is not preferable. Molecular weight 2
If there is no sub-peak or shoulder in the region of more than 100,000, it is difficult to keep the dispersion of the zirconium compound contained in the toner in an appropriate state, the image density may be reduced due to durability, When the sub-peak or the shoulder is not present in the molecular weight range of 200,000 to 1.5 million and has a sub-peak or the shoulder in the region exceeding the molecular weight of 1.5 million, the dispersion of the organic zirconium compound and other additives contained in the toner is relatively small. In general, it is difficult to keep the high molecular weight component and the low molecular weight component in an appropriate state, and the durability of the toner reduces the cleaning property of the toner on the photoconductor. When the content of the component having a molecular weight of 10,000 to 100,000 is less than 15%, it is difficult to maintain the dispersion of the organic zirconium compound contained in the toner in an appropriate state, which adversely affects the developability of the toner. When the image density decreases and exceeds 70%, it is difficult to maintain the dispersion of the organic zirconium compound and other additives contained in the toner in an appropriate state, and the toner develops due to its durability. Becomes unstable, and the image density becomes unstable due to durability.

In the toner of the present invention, the THF-soluble component of the binder resin contained in the toner contains 25 to 5 components having a molecular weight of more than 100,000 in a chromatogram measured by GPC.
It is better to contain 0% by weight. Both when the content of the component having a molecular weight of more than 100,000 is less than 25% by weight and when the content of the component having a molecular weight of more than 100,000 is more than 50% by weight, the dispersion of the organic zirconium compound contained in the toner is reduced. Is difficult to maintain in a proper state, and the image density may be lowered due to durability, which is not preferable.

In the toner of the present invention, the binder resin of the toner copolymerizes a monomer having a carboxyl group and / or an anhydrous carboxyl group as a substituent (hereinafter, referred to as an acid monomer), and has a carboxyl group and / or Or a zirconium element of the organic zirconium compound contained in the toner, wherein the zirconium element of the organic zirconium compound contained in the toner is a carboxyl group which is contained as a substituent of the vinyl polymer which is a binder resin. Interacts with a group and / or an anhydrous carboxyl group to form a chloroform-insoluble component.

In the toner of the present invention, zirconium and an aromatic compound selected from the group consisting of aromatic diols, aromatic hydroxycarboxylic acids, aromatic monocarboxylic acids and aromatic polycarboxylic acids are coordinated and / or synthesized. It contains a bound organic zirconium compound as a negative charge control agent.

The term "organic zirconium compound" refers to a compound obtained by reacting an aromatic diol, an aromatic monocarboxylic acid, an aromatic polycarboxylic acid or / and an aromatic hydroxycarboxylic acid with a zirconium compound (for example, an organic zirconium complex compound ( Complex, complex salt) or organic zirconium salt).

As the organic zirconium compound used in the toner of the present invention, preferably, the zirconium compound forms a zirconium complex and / or complex salt coordinated with an aromatic diol, an aromatic hydroxycarboxylic acid or an aromatic carboxylic acid. More preferably, the zirconium compound is added as a charge control agent containing as a main component a zirconium complex or a complex salt in which an aromatic diol, an aromatic hydroxycarboxylic acid or an aromatic carboxylic acid is coordinated in two molecules. . In this case, an interaction between a carboxyl group and / or an anhydrous carboxyl group contained as a substituent of the vinyl polymer and a zirconium element, that is, a kind of complex formation reaction (hereinafter, referred to as a ligand exchange reaction) (Referred to as a complex formation reaction with zirconium) makes it possible to localize a charge control agent suitable for the toner of the present invention. In this case,
It is presumed that at least a part of the organic zirconium compound does not exist as a zirconium complex or complex salt coordinated with an aromatic diol, an aromatic hydroxycarboxylic acid or an aromatic carboxylic acid.

In the toner of the present invention, the organic zirconium compound contained in the toner is preferably contained in a chloroform-insoluble content as zirconium element in an amount of 30% by weight or more, more preferably 4% by weight of the total amount.
The content is preferably 0% by weight or more, more preferably 50% by weight or more of the total amount. If the content is less than 30% by weight, the localization of the charge control agent becomes insufficient as a result, and the charge stability of the toner tends to be unstable, and the image density may be lowered due to durability.

In the binder resin of the toner according to the present invention, the difference (Av · G−Av · S) between the acid value (Av · S) of the chloroform-soluble component and the acid value (Av · G) of the chloroform-insoluble component.
Is preferably from 10 to 150 mgKOH / g, more preferably from 20 to 130 mgKOH / g,
More preferably, it is 30 to 100 mgKOH / g. If this difference (Av · G−Av · S) is 1
When the amount is less than 0 mgKOH / g, the complex formation reaction with zirconium may be insufficient, and this difference (Av.
When G-Av · S) exceeds 150 mgKOH / g, the complexation reaction with zirconium may be excessive, and in any case, the dispersion state of the charge control agent must be maintained in an optimum state. Is difficult, the charging stability of the toner tends to be unstable, and the image density may decrease due to durability.

In the toner of the present invention, the acid value (Av · S) of the chloroform-soluble component is 10 to 50 mgKOH / g.
And more preferably 15 to 45 m
gKOH / g, more preferably 20-40 mgKOH
/ G. If the acid value (Av · S) of the chloroform-soluble component is less than 10 mgKOH / g, the complexation reaction with zirconium is insufficient, and the acid value (Av · S) of the chloroform-soluble component is 50 mgKOH / g. g
If it is higher than the above, the complex formation reaction with zirconium tends to be excessive.

In a toner using a vinyl polymer as a binder resin, in order to maintain a sufficient offset prevention effect even on an aged fixing member and a cleaning member, the toner is defined by a contact angle of the toner with water. It is necessary to improve the mold releasability.

In the toner of the present invention, the contact angle of the toner with water is preferably 105 to 130 degrees, more preferably 107 to 127 degrees, and further preferably 110 to 125 degrees. If the contact angle of the toner is less than 105 degrees, it is difficult to maintain a sufficient offset prevention effect on the fixing member and the cleaning member that have deteriorated in durability, and when the contact angle of the toner exceeds 130 degrees. In some cases, problems may occur in the developing property of the toner and the cleaning property of the toner remaining on the photoconductor.

The toner having the above-mentioned contact angle can be achieved by a binder resin having a specific acid value, a specific organic zirconium compound as a crosslinking agent, and a wax having a specific peak molecular weight and a specific structure. Is done.

The vinyl polymer, which is a binder resin of the toner of the present invention, reacts with a zirconium element contained in the organic zirconium compound to form a complex with the zirconium element. KO, more preferably 7 to 35 mg KO
It preferably has an acid value of H / g, more preferably 10 to 30 mgKOH / g. If the acid value of the vinyl polymer is less than 5 mgKOH / g, the complex formation reaction with zirconium is insufficient, and 40 mgKOH / g.
If it exceeds g, an excessive complexation reaction with zirconium proceeds, and in either case, it is difficult to control the dispersion state of the wax.

The vinyl polymer does not have to contain a THF-insoluble component before being converted into a toner, but is preferably 2 to 35% by weight, more preferably 5 to 30% by weight before being converted into a toner. It is good to contain. If the content of the THF-insoluble content before the toner conversion exceeds 35% by weight, the THF contained in the toner when the toner conversion is performed.
The insoluble content may exceed 40% by weight, and the object of the present invention cannot be achieved.

The toner of the present invention preferably contains the organic zirconium compound in an amount of 0.5 to 10 parts by weight, preferably 1.0 to 8.8 parts by weight, based on 100 parts by weight of the binder resin.
0 parts by weight, more preferably 1.5 to 5 parts by weight. If the content of the organic zirconium compound is less than 0.5 parts by weight, the complex formation reaction between the binder resin and zirconium is insufficient, and if it exceeds 10 parts by weight, the binder resin and zirconium The complexation reaction with the excess becomes excessive, and in either case, it is difficult to control the dispersion state of the wax.

In the toner of the present invention, the THF-insoluble content contained in the binder resin in the toner after the toner formation not only imparts hot offset resistance to the toner, but also binds in the kneading step during toner production. TH contained in resin
Since the F-insoluble matter can control the melt viscosity of the kneaded material, it is also important for controlling the dispersion of the wax. Therefore, the binder resin in the toner after the toner conversion is THF
The insoluble content is preferably 5 to 60% by weight, more preferably 7 to 55% by weight, and even more preferably 10 to 50% by weight. If the THF-insoluble content of the binder resin is less than 5% by weight, not only the hot offset resistance of the toner is deteriorated, but also the melt viscosity in the kneading step becomes too low and the wax is re-used. When coagulation occurs and the dispersion state cannot be controlled well, and the content exceeds 60% by weight, not only low-temperature offset tends to occur, but also components having high and low melt viscosities in the kneading step are mixed. As a result, the dispersion particle size of the wax becomes wide, and the dispersion state cannot be controlled well.

The wax contained in the toner of the present invention is:
In the chromatogram by GPC measurement, the maximum peak molecular weight (Mp) is 300 to 5000, and the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) is 1.2 to 1
5, more preferably Mp is 350
Mw / Mn is preferably 1.3 to 10, more preferably Mp is 400 to 4000, and Mw / Mn is preferably 1.3 to 10.
It is preferable that w / Mn is 1.4 to 8. If Mp
Is less than 300 or Mw / Mn is less than 1.2, the dispersed particle size of the wax in the toner particles is too small, and if Mp is more than 5000 or Mw / Mn is more than 15, the dispersed particles are too small. The diameter becomes too large, and in either case, it is difficult to control the dispersed particle diameter of the wax.

The toner of the present invention may contain two or more different waxes, and in such a case, the molecular weight (Mp) of the maximum peak in the chromatogram of all the waxes contained in the toner by GPC measurement. ) Is 30
0 to 5000, the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) is preferably from 1.2 to 15, and more preferably Mp is from 350 to 4500, Mw / Mn.
Mn is preferably 1.5 to 12, more preferably Mp is 400 to 4000, and Mw / Mn is 2 to 10
Good to be. If Mp is less than 300, Mw / M
n is less than 1.2, Mp is more than 5000, and (Mw / M
In any case where n) is more than 15, the particle size distribution of the wax in the toner particles becomes wide and it is difficult to control.

The wax contained in the toner of the present invention comprises:
It is preferable that the wax is selected from hydrocarbon wax, polyethylene wax and polypropylene wax.

The wax contained in the toner of the present invention is:
A wax such as a synthetic hydrocarbon synthesized from a mixed gas composed of carbon monoxide and hydrogen by the Age method, a distillation residue of the synthetic hydrocarbon, or a synthetic hydrocarbon obtained by hydrogenating them is preferred. Further, those obtained by performing separation of hydrocarbon wax by use of a press sweating method, a solvent method, vacuum distillation, or a separation crystallization method are more preferably used.

The wax contained in the toner of the present invention is:
Those having a structure represented by the formula (a) are preferable.

[0053]

Embedded image In the formula, A represents a hydroxyl group or a carboxyl group;
It represents an integer of 0 to 60, preferably A represents a hydroxyl group, and a represents an integer of 30 to 50.

The wax contained in the toner of the present invention is
When it is an acid-modified polyethylene, it preferably has an acid value of 1 to 20 mgKOH / g, more preferably 1.5 to 15 mgKOH / g, and is made of maleic acid, maleic acid half ester, maleic anhydride. And those modified with an acid monomer selected from at least one of them.

The wax contained in the toner of the present invention is
When it is an acid-modified polypropylene, it preferably has an acid value of 1 to 20 mgKOH / g, more preferably an acid value of 1.5 to 15 mgKOH / g, and uses polyethylene as maleic acid, maleic acid half ester, maleic anhydride. And those modified with an acid monomer selected from at least one of them.

When two kinds of waxes are contained in the toner of the present invention, it is preferable that at least one kind of wax uses the above-mentioned wax.

Preferred combinations of the waxes when the toner of the present invention contains two types of waxes are shown in Table 1 below.

[0058]

[Table 1]

The toner of the present invention preferably has an endothermic main peak in a temperature range of 70 to 140 ° C. in a DSC curve measured by a differential scanning calorimeter (DSC) of the wax-containing toner. It is preferable to have an endothermic main peak in a temperature range of 75 to 135 ° C, and more preferable to have an endothermic main peak in a temperature range of 80 to 130 ° C and to have an endothermic subpeak or endothermic shoulder at the same time. If there is an endothermic main peak outside the above temperature range, it is difficult to satisfy all of the low-temperature fixing property, hot offset resistance and blocking resistance.

In the toner of the present invention, the wax is added and dispersed in the toner in the kneading step. Preferably, the wax is added by dissolving a vinyl polymer as a binder resin in an organic solvent such as xylene. It is. In this case, uniform dispersion of the wax is further facilitated.

When two or more different waxes are contained in the toner of the present invention, the wax added when the vinyl polymer is dissolved in an organic solvent such as xylene is preferably a hydrocarbon wax, Polyethylene polymer, polypropylene polymer, 1 to 20 mg KO
It is preferably an acid-modified polypropylene having an acid value of H / g or an acid-modified polyethylene having an acid value of 1 to 20 mgKOH / g.

In the toner of the present invention, the total content of these waxes is preferably 0.2 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the binder resin.
It is effective that the amount is by weight.

Next, the organic zirconium compound used in the present invention will be described.

The organic zirconium compound used in the present invention is, specifically, (i) zirconium as a metal element and an aromatic diol, an aromatic hydroxycarboxylic acid or an aromatic polycarboxylic acid as a ligand. A coordinating zirconium complex; (ii) a zirconium complex salt having zirconium as a metal element and coordinating an aromatic diol, an aromatic hydroxycarboxylic acid or an aromatic polycarboxylic acid as a ligand; or (iii) A) Zirconium carboxylate having zirconium ion as a metal ion and aromatic carboxylate, aromatic hydroxycarboxylate or aromatic polycarboxylate as an acid ion.

As the ligand, a zirconium complex or zirconium complex salt in which 1 to 4 aromatic diols, aromatic hydroxycarboxylic acids and aromatic polycarboxylic acids are chelated is preferable. To these zirconium complexes or complex salts, the carboxy anion of aromatic hydroxycarboxylic acid, aromatic carboxylic acid or aromatic polycarboxylic acid is 1 to
Six may be coordinated.

In the case of the organic zirconium salt, those having 1 to 4 aromatic carboxylic acid ions, aromatic hydroxy carboxylic acid ions and aromatic polycarboxylic acid ions are preferable, and those having 1 to 3 aromatic carboxylic acid ions are more preferable. Are preferred.
It may be a complex, a complex salt having a different number of chelates or a mixture of complexes or complex salts having different ligands. Further, a mixture of salts having different numbers of acid ions may be used.

The organic zirconium compound may be a mixture of an organic zirconium complex compound and an organic zirconium salt.

Further, it has been found that excellent developability can be obtained by using the above-mentioned zirconium compound in a magnetic toner containing a magnetic substance, or by applying a toner containing an organic zirconium compound to a one-component developing method. Was. That is, the organic zirconium compound used in the present invention is suitable for a negative charge control that satisfies these requirements for a magnetic toner or a one-component developing toner that requires a rapid rise of charging with a small amount of frictional charging and a high charge amount. It becomes an agent. It is most suitable for a non-magnetic toner used in a non-magnetic one-component developing method.

When the organic zirconium compound is used together with a binder resin having an acid value, the organic zirconium compound can make a large contribution to the effect of enhancing the charge by utilizing the polarity of water molecules held by the constituents of the toner. it can. By using two or more waxes having different melting points or different composition components, the dispersibility can be made very good, and the durability and the uniformity of charging can be improved.

The toner using the organic zirconium compound not only has a sufficient charge amount in a low-humidity or high-humidity environment, but also suppresses a decrease in density during long-term durability. The use of an organic zirconium compound is particularly suitable for magnetic toners containing magnetic iron oxides having various different elements. Oxides of different elements, hydroxides, iron oxides incorporating different elements, and iron oxides mixed with different elements adsorb water molecules,
The improvement and stabilization of charging utilizing the polarity of water molecules can be effectively performed. In particular, when used together with the binder resin having an acid value used in the present invention, the charge can be more effectively improved and stabilized.

In the organic zirconium compound used in the present invention, the zirconium ion easily takes eight coordinations and easily coordinates or bonds oxygen of a carboxyl group or a hydroxyl group. When a binder resin having an acid value such as a styrene resin having a carboxyl group as a functional group is used as the binder resin, the binder resin has good compatibility with the resin, has excellent dispersibility, and prevents falling off from the toner particles. Uniform charging and stable durability of charging can be obtained.
Further, the organic zirconium compound has a small effect on the transparency of the toner, and is preferable for forming a color toner expressing a vivid color. Furthermore, since the polymer chain can be cross-linked through the coordination of the carboxyl group and the hydroxyl group of the binder resin to the zirconium ion, the binder resin can have a large rubber elasticity, and the releasability can be improved. Excellent, it is possible to effectively prevent the fixing member from being stained. Therefore, it is preferable that the crosslinking is performed to such an extent that the binder resin has a THF-insoluble component. Furthermore, it is possible to apply a shear to the kneaded material at the time of melt kneading at the time of toner production, to improve the dispersion of a coloring agent such as a magnetic substance, a pigment and a dye, and to obtain a toner having a high coloring power and a clear color. can do.

The organic zirconium compound used in the present invention is excellent in triboelectric charging ability and can obtain a high charge amount, so that it is a suitable charge control agent for a magnetic toner requiring a high charge amount. Furthermore, in addition to the good dispersibility of the organic zirconium compound itself in the binder resin, the use of a binder resin having an acid value works to improve the dispersibility of the magnetic substance, so that durability and uniformity of charging can be obtained. It becomes like that.

It has been found that the organic zirconium compound used in the present invention has some influence on the surface tension of the binder resin used in the toner, and that when used with a plurality of types of waxes, it has extremely excellent releasability. This makes it possible to form a toner that is excellent in offset resistance and effective in preventing fixing member contamination. This effect is particularly remarkable when used together with the binder resin having an acid value used in the present invention.

The organic zirconium compound of the present invention is characterized by a small decrease in toner developability due to standing. For example, when used under high humidity, paused, left for a while, and then resumed use, a decrease in image density can be reduced.

Further, the organic zirconium compound of the present invention is characterized in that toner particles with a poor charge amount are less generated and that toner particles scatter are less. For example, in magnetic toner, scattering increases under low humidity where cohesion decreases, and in the corona charging method, scattering toner adheres to a charging wire, causing abnormal discharge.In primary charging, streaking occurs due to abnormal charging of an electrostatic image. An abnormal image is generated in the shape of the image, and a streak-like transfer failure is likely to occur in the transfer charging. However, the toner of the present invention can reduce these phenomena.
In the contact charging system, stains due to scattered toner may be transferred to a transfer paper or the like in a contact transfer portion and cause back stains. The toner of the present invention can also reduce these phenomena.

The scattering phenomenon of toner particles is more remarkable in high humidity because non-magnetic toner is restrained by the toner carrier only by electrostatic force, but this scattering phenomenon is also reduced by the toner of the present invention. This can reduce image contamination due to scattering inside the machine. Non-magnetic toner may cause density unevenness in halftone or the like due to the generation of poorly charged particles under low humidity. This phenomenon can be reduced by the toner of the present invention.

The organic zirconium compound such as a zirconium complex, a zirconium complex salt or an organic zirconium salt of an aromatic diol, an aromatic hydroxycarboxylic acid or an aromatic polycarboxylic acid used in the present invention will be specifically described below.

A preferred zirconium complex or complex salt is shown in the general formula (1) or (2).

[0079]

Embedded image In the general formula (1), Ar represents an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group,
Having an alkenyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acyloxy group, a carboxyl group, a halogen, a nitro group, a cyano group, an amino group, an amide group or a carbamoyl group. X and Y represent -O-, -CO-O-, X and Y may be the same or different, and L is a neutral ligand, water Represents an alcohol, ammonia, an alkylamine or pyridine, C ₁ represents a monovalent cation, hydrogen, a monovalent metal ion, ammonium or alkylammonium, and C ₂ represents a divalent cation or a divalent metal ion. , N represents 2, 3 or 4, m represents 0, 2 or 4
Represents In each complex or each complex salt, the aromatic carboxylic acids and aromatic diols serving as ligands may be the same or different, and may be a mixture of complex compounds having different numbers of n and / or m. There may be. A mixture of complex salts having different counter ions C ₁ and C ₂ may be used. From the viewpoint of improving the dispersibility of the complex or complex salt in the binder resin or improving the chargeability, the aromatic residue (Ar) includes
A benzene ring, a naphthalene ring, an anthracene ring or a phenanthrene ring is preferable, an alkyl group, a carboxyl group or a hydroxyl group is preferable as a substituent, L is preferably water, and C ₁ is hydrogen, sodium, potassium, ammonium, or alkyl ammonium. preferable.

[0080]

Embedded image In the general formula (2), Ar is an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group,
Having an alkenyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acyloxy group, a carboxyl group, a halogen, a nitro group, a cyano group, an amino group, an amide group or a carbamoyl group. X and Y represent -O-, -CO-O-, X and Y may be the same or different, and L is a neutral ligand, water A represents an anion, a halogen, a hydroxide ion, a carboxylate ion, a carbonate ion, a nitrate ion, a sulfate ion, a cyanide ion or a thiocyan ion, and A represents a mutually different ion. And C ₁
Represents a monovalent cation, hydrogen, a monovalent metal ion, ammonium or alkylammonium, C ₂ represents a divalent cation or a divalent metal ion, and n represents 1,2,3
Or 4; k represents 1, 2, 3, 4, 5 or 6; and m represents 0, 1, 2, 3, or 4. The anions A, aromatic carboxylic acids and aromatic diols serving as ligands in each complex or each complex salt may be the same or different, and complex compounds having different numbers of n and / or m May be used as a mixture. A mixture of complex salts having different counter ions C ₁ and C ₂ may be used. From the viewpoint of improving the dispersibility of the complex or the complex salt in the binder resin or improving the chargeability, the aromatic residue (Ar) is preferably a benzene ring, a naphthalene ring, an anthracene ring or a phenanthrene ring. Is preferably an alkyl group, a carboxyl group or a hydroxyl group, L is preferably water, C ₁ is preferably hydrogen, sodium, potassium, ammonium or alkyl ammonium, and A is preferably a hydroxyl ion or a carboxylate ion. When A is a divalent anion, the coefficient k of the counter cation is doubled.

Further, preferred zirconium complexes or complex salts are represented by formulas (3), (4), (5), (6), (7) and (8).

[0082]

Embedded image In the general formulas (3), (4) and (5), R is hydrogen,
Alkyl group, aryl group, aralkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryloxy group, hydroxyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, carboxyl group, halogen, nitro group, amino Or a carbamoyl group, which may be connected to each other to form an aliphatic ring, an aromatic ring, or a heterocyclic ring. In this case, the ring may have a substituent R; May have the same or different, and C ₁ represents a monovalent cation, hydrogen, an alkali metal, ammonium or alkylammonium;
An integer of 8, n represents 2, 3 or 4, m represents 0, 2 or 4, and the aromatic carboxylic acids or aromatic diols serving as ligands in each complex or complex salt are the same. Or a mixture of complex compounds having different numbers of n and / or m. Also, a mixture of complex salts having different counter ions C ₁ may be used. From viewpoints of or charge enhancing dispersibility of the complex or complex salt improvement in the binder resin, a substituted alkyl group as group R, an alkenyl group, a carboxyl group or a hydroxyl group are preferred, hydrogen, sodium as C _1, potassium , Ammonium or alkylammonium is preferred.

Particularly preferred is a zirconium neutral complex having no complex compound represented by the general formula (4) or a counter ion and having n = 2 in the general formulas (3), (4) or (5). And excellent environmental stability, excellent dispersibility in a binder resin, and good durability can be obtained.

[0084]

Embedded image In the general formulas (6), (7) and (8), R represents hydrogen,
Alkyl group, aryl group, aralkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryloxy group, hydroxyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, carboxyl group, halogen, nitro group, amino Or a carbamoyl group, which may be connected to each other to form an aliphatic ring, an aromatic ring, or a heterocyclic ring. In this case, the ring may have a substituent R; A to A may be the same or different, and A represents an anion, a halogen, a hydroxyl ion, a carboxylate ion, a carbonate ion, a nitrate ion, a sulfate ion, a cyanide ion or a thiocyanate. represents an ion, a is may have a mutually different ion, C ₁ represents a monovalent cation, hydrogen, a monovalent metal Represents ON, the ammonium or alkyl ammonium, n represents 1, 2, 3 or 4, k represents 2, 3, 4, 5 or 6, m is 0,
Represents 1, 2, 3 or 4. In each complex or each complex salt, the aromatic carboxylic acids and aromatic diols serving as ligands may be the same or different, and may be a mixture of complex compounds having different numbers of n and / or m. There may be. 2 different cations C ₁ and / or anions A
It may be a mixture of more than one complex compound. When A is a divalent anion, the coefficient k of the counter cation is 2
Multiply.

[0085] From the viewpoint of the viewpoint or electrification enhancer to improve the dispersibility of the complex or complex salt of the binder resin, examples of the substituent R, an alkyl group, an alkenyl group, a carboxyl group, a hydroxyl group are preferred, the C ₁ is Hydrogen, sodium, potassium, ammonium and alkylammonium are preferred, and A is preferably a hydroxyl ion or a carboxylate ion.

Particularly preferred is a complex compound represented by the general formula (7) or a compound having no counter ion.
This is a zirconium neutral complex in the case where n = 2 in the general formula, has excellent environmental stability, is excellent in dispersibility in a binder resin, and has good durability.

The zirconium complex or complex salt used in the present invention is a hexacoordinate or octacoordinate complex compound. In the octacoordinate, a dinuclear complex compound in which a ligand is bridged becomes a hexanuclear complex compound. There are complex compounds that are coordinated, and there is also a dinuclear complex compound in which a ligand such as a hydroxyl group is crosslinked to polymerize the complex compound one after another.

Typical structures of such complex compounds are exemplified by the following general chemical formulas (9) to (33). The following structures include those having no ligand L. In the general formulas (30) to (33), the counter cation is omitted.

[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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A complex compound having a structure in which a hydroxyl group or a carboxyl group of an aromatic ring is coordinated to different zirconium may be used, for example, a compound represented by the formula (34) as a partial structure.

[0096]

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The specific structure is represented by equation (35).

[0098]

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Here, p represents an integer of 1 or more, q represents an integer of 2 or more, and in formula (35), an anionic ligand, a neutral ligand and a counter cation are omitted.

The preferred zirconium salts of aromatic carboxylic acids used in the present invention are represented by formulas (36) and (37).

[0101]

Embedded image In the general formulas (36) and (37), Ar represents an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an acyloxy group, an alkoxycarbonyl group, an aryl group as a substituent. Oxycarbonyl group, acyl group, carboxyl group, halogen, nitro group, cyano group, amino group,
A ₁ represents an aromatic residue which may have an amide group or a carbamoyl group, A ₁ represents a monovalent anion, a halogen ion, a hydroxyl ion, a nitrate ion or a carboxylate ion, and A ₂ represents a divalent anion , A sulfate ion, a hydrogen phosphate ion or a carbonate ion, and n is 1, 2, 3, or 4.
Represents In each metal salt, the anion A ₁ , the anion A ₂ , the aromatic carboxylic acid and the aromatic hydroxycarboxylic acid serving as an acid ion may be the same or different. Further, a mixture of salts having different numbers of n may be used. From the viewpoint of improving the dispersibility or chargeability of the metal salt in the binder resin, the aromatic residue is preferably a benzene ring, a naphthalene ring, an anthracene ring or a phenanthrene ring, and the substituent is an alkyl group. A carboxyl group, a hydroxyl group or an acyloxy group is preferred.

More preferred metal salts are zirconium salts represented by the general formulas (38) and (39).

[0103]

Embedded image In the general formulas (38) and (39), R represents hydrogen, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group,
Represents a hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, a carboxyl group, a halogen, a nitro group, an amino group, an amide group or a carbamoyl group, and is connected to an aliphatic ring, an aromatic ring or a heterocyclic ring May be formed. In this case, the ring may have a substituent R, may have 1 to 8 substituents R, and may be the same or different, A ₁ represents a monovalent anion, a halogen ion, a hydroxyl ion, a nitrate ion or a carboxylate ion;
₂ represents a divalent anion, sulfate ion, hydrogen phosphate ion or carbonate ion, 1 represents an integer of 1 to 8, and n represents 1, 2, 3, or 4. In each metal salt, the anion A ₁ , the anion A ₂ and the aromatic carboxylic acid serving as the acid ion may be the same or different. Further, a mixture of salts having different numbers of n may be used. From the viewpoint of improving the dispersibility of the metal salt in the binder resin or improving the chargeability, the substituent is preferably an alkyl group, an alkenyl group, a carboxyl group, a hydroxyl group, or an acyloxy group, and excellent environmental stability is obtained. Also, it is excellent in dispersibility in a binder resin, and excellent durability can be obtained.

More preferred metal salts are zirconium salts represented by the general formulas (40) and (41).

[0105]

Embedded image In the general formulas (40) and (41), R represents hydrogen, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group,
Represents a hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, a carboxyl group, a halogen, a nitro group, an amino group, an amide group or a carbamoyl group, and is connected to an aliphatic ring, an aromatic ring or a heterocyclic ring May be formed in this case, the ring may have a substituent R, and the substituent R may have 1 to 8 substituents, which may be the same or different, A1 represents a monovalent anion, a halogen ion, a hydroxyl ion, a nitrate ion or a carboxylate ion;
2 represents a divalent anion, sulfate ion, hydrogen phosphate ion or carbonate ion, 1 represents an integer of 1 to 7, and n represents 1, 2, 3, or 4. In each metal salt, the anion A1, the anion A2, and the aromatic carboxylic acid serving as the acid ion may be the same or different.
Further, a mixture of salts having different numbers of n may be used. From the viewpoint of improving the dispersibility of the metal salt in the binder resin or improving the chargeability, the substituent is preferably an alkyl group, an alkenyl group, a carboxyl group, a hydroxyl group, or an acyloxy group, and excellent environmental stability is obtained. Also, it is excellent in dispersibility in a binder resin, and excellent durability can be obtained.

The organic zirconium compound of the present invention is obtained by dissolving a zirconium compound such as zirconium chloride, zirconium sulfate, or zirconium organic acid in water, an alcohol, or an aqueous alcohol solution to obtain an aromatic carboxylic acid, an aromatic diol or an alkali metal salt thereof. Or an aromatic carboxylic acid, an aromatic diol and an alkali agent. These organic zirconium compounds are recrystallized with an alcohol aqueous solution or the like, and purified by washing with alcohol. In the case of a complex salt, a complex salt having various counter ions can be obtained by treating the product with a mineral acid, an alkali agent, or an amine agent. In the present invention, a zirconium complex salt having a plurality of counter ions, such as hydrogen ions, alkali metal ions, and ammonium ions, is also included.

Hereinafter, specific examples of the organic zirconium compound used in the present invention will be described. Although those which coordinate 2 to 4 water molecules are also included,
Here, the description of the water molecule is omitted. In addition, although the counter ions include those having a plurality of types, only the most common counter ions are described here.

[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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[0115]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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The method of adding the organic zirconium compound used in the present invention to the toner includes a method of adding (internal addition) to the inside of the toner particles and a method of adding (external addition) to the outside of the toner particles. When added internally to the toner particles, the amount is preferably 0.5 to 10 parts by weight, more preferably 1.0 to 10 parts by weight, based on 100 parts by weight of the binder resin.
8.0 parts by weight, more preferably 1.5 to 5 parts by weight. When externally added to the toner particles, the amount is preferably 0.01 to 5 parts by weight, and it is particularly preferable to fix the toner particles to the surface of the toner particles mechanochemically. In the present invention, it is preferable to add the compound internally to the toner particles in that the interaction with the vinyl polymer having a carboxyl group is sufficiently performed throughout the toner particles.

The organic zirconium compound used in the present invention can be used in combination with other known charge control agents as described in the prior art. For example, other charge control agents include organometallic complexes, metal salts or chelate compounds. Specifically, a monoazo metal complex, an acetylacetone metal complex, a hydroxycarboxylic acid metal complex,
Examples thereof include polycarboxylic acid metal complexes and polyol metal complexes. Other examples include carboxylic acid derivatives such as metal salts of carboxylic acids, carboxylic anhydrides and carboxylic esters, condensates of aromatic compounds, and phenol derivatives such as bisphenols and calixarenes.

It has been found that the toner of the present invention exhibits excellent charging ability in the process of frictional charging with the developer carrying member. That is, regarding the toner containing the binder resin having an acid value and the organic zirconium compound, when the charging ability with the material of the developer carrier is observed, a large amount of charge can be generated even with a small contact with the surface of the developer carrier. all right.

As monomers for adjusting the acid value of the binder resin, acrylic acid such as acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, cinnamic acid, vinyl acetic acid, isocrotonic acid, angelic acid and the like, Or β-alkyl derivatives; fumaric acid, maleic acid, citraconic acid, alkenyl succinic acid, itaconic acid, mesaconic acid,
Examples include unsaturated dicarboxylic acids such as dimethylmaleic acid and dimethylfumaric acid, and monoester derivatives or anhydrides thereof. Such a monomer can be used alone or as a mixture and copolymerized with another monomer to produce a desired binder resin. Among them, it is particularly preferable to use a monoester derivative of an unsaturated dicarboxylic acid for controlling the acid value.

For example, monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monoallyl maleate, monophenyl maleate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monophenyl fumarate, and the like. Monoesters of α, β-unsaturated dicarboxylic acids such as monobutyl n-butenylsuccinate, monomethyl n-octenylsuccinate, monoethyl n-butenylmalonate, monomethyl n-dodecenylglutarate and monobutyl n-butenyladipate Monoesters of alkenyl dicarboxylic acid and the like can be mentioned.

The carboxyl group-containing monomer as described above may be added in an amount of 0.1 to 20 parts by weight, preferably 0.2 to 15 parts by weight, based on 100 parts by weight of all the monomers constituting the binder resin.

The reason that the monoester monomer of dicarboxylic acid is selected as described above is that it has low solubility in an aqueous suspension, but has high solubility in organic solvents and other monomers. It is because it is preferable to use.

In the present invention, the carboxylic acid groups and carboxylic acid ester sites in the copolymer obtained by the above method may be subjected to an alkali treatment to be saponified. That is, a carboxylic acid group or a carboxylic acid ester site may be changed to a polar functional group by reacting with a cation component of an alkali.

In the alkali treatment, after the production of the binder resin, the mixture is introduced as an aqueous alkali solution into the solvent used during the polymerization,
It may be performed while stirring. Examples of the alkali that can be used in the present invention include Na, K, Ca, Li, Mg, B
hydroxides of alkali metals and alkaline earth metals such as a; hydroxides of transition metals such as Zn, Ag, Pb and Ni; hydroxides of quaternary ammonium salts such as ammonium salts, alkylammonium salts and pyridinium salts Is mentioned. Particularly preferred examples include NaOH and KOH.

In the present invention, the saponification reaction does not need to be carried out over all of the carboxylic acid groups and carboxylic acid ester sites in the copolymer. I just need to change.

The amount of the alkali used in the saponification reaction is difficult to determine unconditionally depending on the type of the polar group in the binder resin, the dispersion method, and the type of the constituent monomers. What is necessary is just to 5 times equivalent. When the amount is less than 0.02 equivalent, the saponification reaction is not sufficient, and the number of polar functional groups generated by the reaction decreases, and as a result, the crosslinking reaction by the subsequent saponification becomes insufficient. On the other hand, when the amount exceeds 5 times equivalent, the functional group such as a carboxylic acid ester site is adversely affected by hydrolysis of the ester, generation of a salt by a saponification reaction, and the like.

When an alkali treatment of 0.02 to 5 times equivalent of the acid value is performed, the residual cation concentration after the treatment is 5 to 100%.
It is contained between 0 ppm and can be preferably used to regulate the amount of alkali.

The binder resin of the toner and the composition containing the binder resin have a glass transition temperature (T
g) is 45-75 ° C, preferably 50-70 ° C.
If the Tg is lower than 45 ° C., the toner tends to deteriorate in a high-temperature atmosphere, and offset tends to occur during fixing.
When Tg exceeds 75 ° C., the fixability tends to decrease.

As a polymerization method which can be used in the present invention as a method for synthesizing the binder resin of the present invention, there are 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 in an aqueous phase as small particles 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 can be easily mixed with a colorant, a charge control agent and other additives.

However, the resulting polymer tends to be impure due to the added emulsifier, and an operation such as salting out is required to take out the polymer. To avoid this inconvenience, suspension polymerization is convenient.

In the suspension polymerization, 100 parts by weight or less of the monomer (preferably 1 part by weight) is added to 100 parts by weight of the aqueous solvent.
(0 to 90 parts by weight). Examples of usable dispersants include polyvinyl alcohol, partially saponified polyvinyl alcohol, calcium phosphate, and the like, and generally 0.05 to 1 part by weight based on 100 parts by weight of the aqueous solvent. The polymerization temperature is suitably from 50 to 95 ° C, but is appropriately selected depending on the polymerization initiator used and the polymer to be produced.

The binder resin used in the present invention is preferably formed by using a polyfunctional polymerization initiator alone or in combination with a monofunctional polymerization initiator as exemplified below.

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-butylperoxytrimethyl adipate, 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane and 2,2-t
A polyfunctional polymerization initiator having a functional group having a polymerization initiation function such as two or more peroxide groups in one molecule such as -butylperoxyoctane; and diallyl peroxydicarbonate, t-butyl peroxymaleic acid , T
In one molecule such as -butyl peroxyallyl carbonate and t-butyl peroxyisopropyl fumarate;
A polyfunctional polymerization initiator having both a functional group having a polymerization initiation function such as a peroxide group and a polymerizable unsaturated group is exemplified.

Of these, more preferred are 1,1
-Di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, di-tert-butylperoxyhexahydroterephthalate, di-tert-butylperoxyase 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 monofunctional polymerization initiator in order to satisfy various properties required as a binder resin for a toner.
In particular, it is preferable to use the polyfunctional polymerization initiator together with a polymerization initiator having a half life of 10 hours lower than the decomposition temperature for obtaining a half life of 10 hours.

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 monofunctional polymerization initiators may be added to the monomer simultaneously with the above-mentioned polyfunctional polymerization initiator. However, in order to keep the efficiency of the polyfunctional polymerization initiator properly,
It is preferable to add the compound after the half-life of the polyfunctional polymerization initiator has passed in the polymerization step.

In the toner of the present invention, when the vinyl polymer constituting the binder resin is produced by solution polymerization or bulk polymerization, it can be produced by a usual radical polymerization method. Having two or more groups in the molecule, in which a cleavage reaction of each peroxide group occurs.
Using a radical polymerization initiator having a temperature difference of 0 hour half life of 5 ° C. or more, preferably 7 ° C. or more, more preferably 10 ° C. or more, the reaction temperature difference of radical polymerization is 5 ° C. or more, preferably 7 ° C. or more. , More preferably at least 10 ° C,
At each polymerization temperature, a polymer produced by adding a monomer composition can also be used.

These initiators are preferably used in an amount of 0.05 to 2 parts by weight based on 100 parts by weight of the monomer from the viewpoint of efficiency.

The vinyl polymer used in the present invention is preferably crosslinked with a crosslinking monomer.

As the crosslinkable monomer, a monomer having two or more polymerizable double bonds is mainly used. Specific examples include aromatic divinyl compounds (eg, divinylbenzene, divinylnaphthalene, etc.); diacrylate compounds linked by an alkyl chain (eg, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4 -Butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6
Hexanediol diacrylate, neopentyl glycol diacrylate, and methacrylates instead of the above compounds; diacrylate compounds linked by an alkyl chain containing an ether bond (for example, diethylene glycol diacrylate, triethylene glycol) Diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and those obtained by replacing the acrylate of the above compound with methacrylate); Diacrylate compounds linked by a chain containing, for example, polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propanediacryle DOO, polyoxyethylene (4) -
2,2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylate of the above compound with methacrylate; and polyester type diacrylate compounds (for example, trade name MANDA (Nippon Kayaku)). Can be As multifunctional crosslinking agents, pentaerythritol acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and acrylates of the above compounds to methacrylate Alternatives: triallyl cyanurate and triallyl trimellitate.

[0163] These cross-linking agents are
It is preferably used in the range of 0.0001 to 1 part by weight, preferably 0.001 to 0.5 part by weight with respect to 0 part by weight.

Among these crosslinkable monomers, those which are preferably used from the viewpoint of fixing property and offset resistance of the toner include an aromatic divinyl compound (for example, divinylbenzene), a chain containing an aromatic group and an ether bond. Diacrylate compounds.

As other synthesis methods, a bulk polymerization method and a solution polymerization method can be used. However, in the bulk polymerization method, any polymer can be obtained by increasing the termination reaction rate by polymerizing at a high temperature, but 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 compound in the resin composition used in the present invention. In particular, a solution polymerization method under a pressurized condition is also preferable from the viewpoint of minimizing the amount of the initiator used and minimizing the influence of the residual initiator.

Examples of the vinyl monomer for obtaining the vinyl polymer used in the present invention include the following.

Styrene: o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,
4-dichlorostyrene, p-ethylstyrene, 2,4-
Dimethylstyrene, pn-butylstyrene, p-te
rt-butylstyrene, pn-hexylstyrene, p
-N-octylstyrene, pn-nonylstyrene, p
Styrene derivatives such as -n-decylstyrene, pn-dodecylstyrene; ethylene, propylene, butylene,
Ethylenically unsaturated monoolefins such as isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyls such as vinyl acetate, vinyl propionate and vinyl benzoate Esters: methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, methacrylic acid (2-ethylhexyl), stearyl methacrylate, phenyl methacrylate, Α such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate
-Methylene aliphatic monocarboxylic acid esters; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, acrylic acid (2-
Ethyl hexyl), stearyl acrylate, acrylic acid (2-chloroethyl), acrylates such as phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl Vinyl ketones such as ketones; N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole and N-vinylpyrrolidone; vinylnaphthalenes; acrylic acid derivatives or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide Is mentioned. These vinyl monomers are used alone or as a mixture of two or more monomers.

Of these, a combination of monomers that results in a styrene copolymer or a styrene-acrylic copolymer is preferred.

The binder resin of the present invention preferably contains at least 65 parts by weight of a styrene-based polymer component or a styrene-based copolymer component from the viewpoint of miscibility with an organic zirconium compound.

As a method for producing a binder resin, a high-molecular-weight polymer and a low-molecular-weight polymer are separately synthesized by a solution polymerization method, then mixed in a solution state, and then the solvent is removed. The low-molecular-weight polymer obtained by the solution blending method is melt-kneaded in a dry-blending method, and the low-molecular-weight polymer is dissolved in the monomer constituting the high-molecular-weight polymer, suspension polymerization is performed, and the resin composition is washed and dried. The resulting two-stage polymerization method is also included. However, the dry blending method has problems in terms of uniform dispersion and compatibility, and although the two-stage polymerization method has many advantages in uniform dispersibility, it is possible to increase a low molecular weight component to a high molecular weight component or more. Difficult,
In the presence of low molecular weight polymer components, not only is it difficult to synthesize a high molecular weight polymer having a large molecular weight, but also there is a problem that unnecessary low molecular weight polymers are by-produced. It is suitable. As a method for introducing a predetermined acid value into the low molecular weight polymer component, solution polymerization in which the acid value can be easily set as compared with an aqueous polymerization method is preferable.

The magnetic material used as a coloring agent in the present invention includes magnetite, maghemite,
Magnetic iron oxides such as ferrite and mixtures thereof are preferably used.

Among them, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, sulfur,
Germanium, titanium, zirconium, tin, lead, zinc,
Calcium, barium, scandium, vanadium, chromium, manganese, cobalt, copper, nickel, gallium,
Magnetic iron oxide containing at least one element selected from indium, silver, palladium, gold, platinum, tungsten, molybdenum, niobium, osmium, strontium, yttrium, technetium, ruthenium, rhodium and bismuth is preferable. Especially lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium,
Tin, sulfur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper,
Zinc and gallium are preferred. Most preferably, it is a magnetic iron oxide containing an element selected from the group consisting of magnesium, aluminum, silicon, phosphorus and zirconium as a different element. These elements may be taken into the iron oxide crystal lattice, may be taken into the iron oxide as an oxide, or may exist as oxides or hydroxides on the surface. It is a preferred embodiment that it is contained as an oxide.

These elements can be incorporated into the particles by mixing the salts of the respective elements during the formation of the magnetic material and adjusting the pH. In addition, precipitation can be performed on the particle surface by adjusting the pH after the formation of the magnetic particles or adjusting the pH by adding a salt of each element.

The magnetic material containing these elements is well compatible with the binder resin and has very good dispersibility. Further, this good dispersibility can improve the dispersibility of the organic zirconium compound used in the present invention, and the effect of the organic zirconium compound of the present invention can be sufficiently exhibited.
The magnetic material functions as a dispersion medium, and the dispersion of the organic zirconium compound is assisted by the good dispersibility of the magnetic material, and the dispersibility of the organic zirconium compound is improved. In addition, these magnetic substances adsorb water molecules, and the organic zirconium compound is
It has the effect of making it easier to emphasize the electrification by water molecules. This effect can be exhibited more effectively when used together with a binder resin having an acid value.

These magnetic materials have a uniform particle size distribution.
In combination with the dispersibility in the binder resin, the chargeability of the toner can be stabilized. In recent years, the toner particle diameter has been reduced in order to achieve higher image quality. Even when the weight average particle diameter of the toner is 2.5 to 10 μm, the charging uniformity is promoted and the toner Cohesiveness is also reduced, and developability such as improvement in image density and fog is improved. In particular, the effect is remarkable in a toner having a weight average particle diameter of 2.5 to 6.0 μm, and an extremely high-definition image can be obtained. It is preferable that the weight average particle size is 2.5 μm or more, since sufficient image density can be obtained. On the other hand, as the particle size of the toner progresses, release of the zirconium compound also easily occurs.However, the toner of the present invention is excellent in charge uniformity, so that the toner is less susceptible to sleeve contamination even if some zirconium compound is present. Become. The magnetic toner preferably has a weight average particle size of 2.5 to 10 μm, more preferably 2.5 to 6.0 μm. Even in the case of a non-magnetic toner, the weight average particle size is preferably 2.5 to 10 μm, more preferably 2.5 to 6.0 μm.

The content of these different elements is preferably 0.05 to 10% by weight based on the iron element of the magnetic iron oxide. More preferably 0.1 to 7% by weight,
More preferably, it is 0.2 to 5% by weight, most preferably 0.3 to 4% by weight. If the content of the different element is less than 0.05% by weight, the effect of containing these elements cannot be obtained, and good dispersibility and uniform charging cannot be obtained. When the content of the different element is more than 10% by weight, the discharge of electric charge is increased and insufficient charging is caused, so that the image density may be lowered or fog may increase.

[0177] In the content distribution of these different elements, those which are present more in the vicinity of the surface of the magnetic material are preferable.
For example, the dissolution rate of the dissimilar element of the magnetic iron oxide in which the dissolution rate of the iron element is up to 20% is preferably 20% to 100% of the total amount of the dissimilar elements contained in the magnetic iron oxide, and more preferably. It is preferably from 25% to 100%, more preferably from 30% to 100%. By increasing the surface abundance of the different elements, the dispersion effect and the electric diffusion effect can be further improved.

These magnetic materials preferably have a number average particle size of 0.05 to 1.0 μm, more preferably 0.1 to 0.1 μm.
5 μm is preferable. The magnetic material preferably has a BET specific surface area of ² to 40 m ² / g, more preferably 4 to ²⁰ m ² / g.
Is good. The shape of the magnetic material is not particularly limited, and any shape may be used. Regarding the magnetic properties of the magnetic material, a saturation magnetization is preferably from 10 to ²⁰⁰ Am ² / kg, more preferably from 70 to 10 under a magnetic field of 795.8 kA / m.
0 Am ² / kg, and the residual magnetization is preferably 1 to 10
0Am ² / kg, more preferably from 2~20Am ² / kg, a coercive force of preferably 1~30kA / m, more preferably those good a 2~15kA / m. These magnetic materials are used in an amount of 20 to 200 parts by weight based on 100 parts by weight of the binder resin.

As the colorant that can be used in the toner of the present invention, any suitable pigment or dye can be used. As the pigment, for example, carbon black, aniline black, acetylene black, naphthol yellow, Hansa yellow, rhodamine lake, alizarin lake, bengalara,
Phthalocyanine blue and indanthrene blue are mentioned. These are used in an amount necessary to maintain the optical density of the fixed image, and preferably 0.1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the binder resin.
Good addition amount by weight. Examples of the dye include, for example, an azo dye, an anthraquinone dye, a xanthene dye, and a methine dye, preferably 0.1 to 20 parts by weight, more preferably 0.3 to 100 parts by weight based on 100 parts by weight of the binder resin. 1
The addition amount of 0 parts by weight is good.

In the present invention, it is preferable that an inorganic oxide such as silica, alumina, or titanium oxide, or an inorganic fine powder having a small particle diameter such as carbon black or carbon fluoride be externally added to the toner particles.

The fine silica powder, fine alumina powder or fine titanium oxide powder is preferably formed into fine particles when dispersed on the surface of the toner particles, since the fluidity-imparting property becomes higher.
The number average particle diameter is preferably 5 to 100 nm, more preferably 5 to 50 nm. BET as a base fine powder
Surface area by nitrogen adsorption measured by the method is preferably 30
m ² / g or more, particularly preferably good in the range of 60~400m ² / g, as the surface-treated fine powder, preferably 20 m ² / g or more, particularly preferably 40 to 300
Those having a range of m ² / g are good.

The external addition amount of these fine powders is
An appropriate surface coverage is obtained when 0.03 to 5 parts by weight is added to 00 parts by weight.

The degree of hydrophobicity of the inorganic fine powder used in the present invention is preferably 30% or more in methanol wettability, more preferably 50% or more. As the hydrophobizing agent, a silane compound which is a silicon-containing surface treating agent and silicone oil are preferable.

For example, alkylalkoxysilanes such as dimethyldimethoxysilane, trimethylethoxysilane and butyltrimethoxysilane; dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, allylphenyldichlorosilane, benzyldimethyl Silane coupling agents such as chlorosilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, divinylchlorosilane, and dimethylvinylchlorosilane can be used.

As additives for imparting various properties used in the toner of the present invention, for example, the following are used.

(1) Abrasive: metal oxide (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide), nitride (silicon nitride) / carbide (silicon carbide), metal salt (calcium sulfate, sulfuric acid) Barium, calcium carbonate).

(2) Lubricant: fluororesin powder (polyvinylidene fluoride, polytetrafluoroethylene), fatty acid metal salt (zinc stearate, calcium stearate).

(3) Charge controllable particles: metal oxides (tin oxide, titanium oxide, zinc oxide, silicon oxide, aluminum oxide), carbon black, resin fine particles.

These additives are used in an amount of 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the toner particles. These additives are
They may be used alone or in combination.

In the case of a magnetic toner, it is preferable to use fine powders of two or more kinds of inorganic oxides or metal oxides in order to obtain the durability stability of development and the development stability after standing. In the case of a non-magnetic one-component developing method, it is preferable to use titanium oxide or alumina in order to improve fluidity and obtain image uniformity.

The method for producing the toner of the present invention includes the following.
After sufficiently mixing the above-mentioned toner constituent materials with a ball mill or other mixer, the mixture is kneaded well using a heat kneader such as a hot roll kneader or an extruder, and after cooling and solidifying, mechanically pulverized to obtain a pulverized powder. A method of obtaining a toner by classification is preferable. Another method is a polymerization method in which a predetermined material is mixed with a monomer to constitute a binder resin to form an emulsified suspension and then polymerized to obtain a toner. In the microcapsule toner, a method in which a predetermined material is contained in a core material or a shell material, or both of them; a method in which a constituent material is dispersed in a binder resin solution and then spray-dried to obtain a toner. Further, if desired, the desired additive and toner particles are sufficiently mixed by a mixer such as a Henschel mixer to produce the toner of the present invention.

The toner of the present invention may be mixed with a carrier and used as a two-component developer. The resistance value of the carrier is preferably adjusted to 10 ⁶ to 10 ¹⁰ Ω · cm by adjusting the degree of unevenness of the carrier surface and the amount of resin to be coated.

Examples of the resin for coating the carrier surface include a styrene-acrylate copolymer, a styrene-methacrylate copolymer, an acrylate copolymer, a methacrylate copolymer, a silicone resin,
Fluorine-containing resin, polyamide resin, ionomer resin,
Polyphenylene sulfide resin or a mixture thereof can be used.

As the magnetic material of the carrier core, oxides such as ferrite, iron-rich ferrite, magnetite, and γ-iron oxide, metals such as iron, cobalt, and nickel, or alloys thereof can be used. The elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin,
Examples include zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, and vanadium.

Next, a developing method in which the toner of the present invention is preferably used will be described.

In FIG. 1, an image carrier for carrying an electrostatic image formed by a known process, for example, an electrophotographic photosensitive drum 7 is rotated in the direction of arrow B. The developing sleeve 14 as a developer carrying member carries the toner 10 as a one-component developer supplied from the hopper 9 and rotates the developing sleeve 1 in a direction indicated by an arrow A.
The toner 10 is transported to the developing section D where the photosensitive drum 4 and the photosensitive drum 7 face each other. When the toner 10 is a magnetic toner, a magnet 11 is disposed in the developing sleeve 14 in order to magnetically attract and hold the toner 10 on the developing sleeve 14.
The toner 10 obtains a triboelectric charge capable of developing an electrostatic image on the photosensitive drum 7 by friction with the developing sleeve 14.

In order to regulate the layer thickness of the toner 10 conveyed to the developing section D, if the toner is a magnetic toner, the regulating magnetic blade 8 made of a ferromagnetic metal has a thickness of about 200 to 300 μm from the surface of the developing sleeve 14. It is suspended from the hopper 9 so as to face the developing sleeve 14 with a gap width. When the magnetic lines of force from the magnetic pole N1 of the magnet 11 concentrate on the blade 8, the toner 10
Is formed. As the blade 8, a non-magnetic blade can be used. When the toner 10 is a non-magnetic toner, an elastic blade such as urethane rubber, silicone rubber, or a chip blade is used.

Toner 1 formed on developing sleeve 14
0 is the thickness of the developing sleeve 14 in the developing section D.
It is preferable that the gap be smaller than the minimum gap between the photosensitive drum 7 and the photosensitive drum 7. The developing method of the present invention is particularly effective for a developing device of a system that develops an electrostatic image with such a thin toner layer (that is, a non-contact developing device). But,
In the developing section, the developing method of the present invention can also be applied to a developing device in which the thickness of the toner layer is equal to or greater than the minimum gap between the developing sleeve 14 and the photosensitive drum 7 (that is, a contact developing device). it can.

Hereinafter, an example of the non-contact type developing device will be described.

A developing bias voltage is applied to the developing sleeve 14 from a power source 15 in order to fly the toner 10 as a one-component developer carried on the developing sleeve 14. When using a DC voltage as the developing bias voltage,
It is preferable that a voltage having a value between the potential of the image portion of the electrostatic charge image (the region where the toner 10 adheres and is visualized) and the potential of the background portion is applied to the developing 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 charge 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 charge image is used. In the reversal development, toner is attached to the low potential portion of the electrostatic image to visualize the toner, and the toner used is charged to the same polarity as the polarity of the electrostatic image. The high potential and the low potential are expressed by absolute values. In any case, the toner 10 is charged to a polarity for developing an electrostatic image by friction with the developing sleeve 14.

In the developing device shown in FIG. 2, as a member for regulating the layer thickness of the toner 10 on the developing sleeve 14, a material having rubber elasticity such as urethane rubber or silicone rubber, or a metal elastic material such as phosphor bronze or stainless steel is used. An elastic plate 17 made of a material having the following characteristics 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 of FIG. 2 are basically the same as those of the developing device shown in FIG. 1, and the same reference numerals in FIG. 2 as those shown in FIG. 1 indicate 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. Such a developing device is used for a non-magnetic one-component toner.

[0204] The developing sleeve, which is a developer carrier used in the present invention, preferably has a cylindrical substrate and a coating layer (resin layer) covering the surface of the substrate. Its configuration is as shown in FIG. The resin layer 1 contains a binder resin 4, and in some cases, a conductive substance 2, a filler 3, a solid lubricant 5, and the like, and is coated on a cylindrical substrate 6. When the conductive material 2 is contained, the resin layer 1 is conductive, so that excessive charging of the toner can be prevented. When the filler 3 is contained, the abrasion of the resin layer 1 by the toner is prevented, and further, the charging of the filler 3 can appropriately control the toner charging. When the solid lubricant 5 is contained, the releasability of the toner and the developing sleeve is improved, and as a result, fusion of the toner onto the developing sleeve can be prevented.

In the sleeve of the present invention, when the resin layer contains a conductive substance, the volume resistance of the resin layer is 10 ⁶
Ω · cm or less, preferably 10 ³ Ω · cm or less is good. When the volume resistance of the resin layer exceeds 10 ⁶ Ω · cm, toner charge-up is likely to occur, which may cause the occurrence of blotches and the deterioration of development characteristics.

The surface roughness of the resin layer is preferably in the range of 0.2 to 3.5 μm in JIS center line average roughness (Ra). If Ra is less than 0.2 μm, the charge amount of the toner in the vicinity of the sleeve becomes too high, the toner is attracted to the sleeve by the mirroring power, new toner cannot be charged by the sleeve, and the developing property is reduced. Ra is 3.
If it exceeds 5 μm, the toner coating amount on the sleeve will increase too much, and the toner will not be able to obtain a sufficient charge amount, and will be non-uniformly charged, causing a reduction in image density and uneven density.

Next, each material constituting the resin layer 1 will be described.

In FIG. 3, the conductive substance 2 includes, for example, metal powders such as aluminum, copper, nickel and silver; metal oxides such as antimony oxide, indium oxide and tin oxide; carbon fibers, carbon black and graphite. And carbon allotropes. Among them, carbon black is particularly excellent in electric conductivity, and is preferably used because it can be filled with a polymer material to impart conductivity, or by controlling the amount of addition, a certain degree of conductivity can be obtained. The carbon black used in the present invention preferably has a number average particle size of 0.001 to 1.0 μm, and more preferably 0.01 to 0.8 μm.
If the number average particle size of the carbon black exceeds 1 μm, it becomes difficult to control the volume resistance of the resin layer, which is not preferable.

[0209] The content of the conductive substance is as follows.
The amount is preferably 0.1 to 300 parts by weight, more preferably 1 to 100 parts by weight, based on 00 parts by weight.

As the filler 3, a conventionally known negative charge control agent for toner or a positive charge control agent for toner may be added. Other substances include inorganic compounds such as alumina, asbestos, glass fiber, calcium carbonate, magnesium carbonate, barium carbonate, barium sulfate, silica, calcium silicate; phenolic resins, epoxy resins, melamine resins, silicone resins, P
MMA, terpolymer of methacrylate (for example, polystyrene / n-butyl methacrylate / silane terpolymer), styrene-butadiene copolymer, polycaprolactone; nitrogen-containing compounds such as polycaprolactam, polyvinylpyridine, polyamide; polyvinylidene fluoride;
Polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, perfluoroalkoxyltrifluoroethylene, polytetrafluoroalkoxyethylene, hexafluoropropylene-polytetrafluoroethylene copolymer, trifluorochloroethylene-
Highly halogenated polymers such as vinyl chloride copolymers; polycarbonates and polyesters.
Among them, silica and alumina are preferably used because they have their own hardness and charge controllability to the toner.

[0211] The content of the filler is as follows.
The amount is preferably 0.1 to 500 parts by weight, more preferably 1 to 200 parts by weight with respect to parts by weight.

Examples of the solid lubricant 5 include molybdenum disulfide, boron nitride, graphite, graphite fluoride, silver-niobium selenide, calcium chloride-graphite, and talc. Among these, graphite is preferably used because it has conductivity together with lubricity, and has a function of reducing toner having an excessively high charge and providing a charge amount suitable for development.

[0213] The content of the solid lubricant is as follows.
The amount is preferably 0.1 to 300 parts by weight, more preferably 1 to 150 parts by weight, based on 00 parts by weight.

In some cases, the conductive substance 2 and the filler 3
Examples of the binder resin 4 in which the solid lubricant 5 is dispersed include a phenolic resin, an epoxy resin, a polyamide resin, a polyester resin, a polycarbonate resin, a polyolefin resin, a silicone resin, a fluorine resin, and a styrene resin. Resin such as resin and acrylic resin is used.
Particularly, a thermosetting or photocurable resin is preferable.

In the present invention, in order to suitably expose the conductive material, filler or solid lubricant in the resin layer on the sleeve surface to the surface, or to smooth the surface to form a uniform uneven surface. Further, by performing a smoothing treatment on the surface by means such as polishing described below, it is possible to impart more preferable performance. In particular, it is effective for the vertical streak phenomenon that occurs in solid black and halftone images and the rise of the initial image density, and is particularly effective under high temperature and high humidity. Polishing with a belt-like abrasive material to which felt or abrasive grains are adhered makes it possible to finish the surface unevenness of the sleeve evenly, so that the amount of toner coating on the sleeve is uniform and as a result, triboelectric charging with the sleeve is reduced. Only the received toner is transported to the development area. Therefore, it is considered that the above effects can be obtained.

Even after performing the smoothing treatment as described above, the surface of the coat layer has a Ra of JIS B 0601 of 0.
It is preferable that irregularities in a range of 2 to 3.5 μm are maintained, and more preferably about 0.3 to 2.5 μm. The reason is the same as above.

As the cylindrical substrate 6, a non-magnetic metal cylindrical tube,
A resin cylinder is preferably used, and for example, a nonmagnetic cylindrical pipe such as a stainless steel cylindrical pipe, an aluminum cylindrical pipe, and a copper alloy cylindrical pipe is used. As a method of manufacturing a cylindrical tube, there are a drawing method and an extrusion method. In order to further increase the dimensional accuracy of the cylindrical tube itself, cutting or polishing is performed to obtain a predetermined dimensional accuracy. The straightness of the cylindrical tube is preferably 30 μm or less, more preferably 20 μm or less, and a good image is obtained. If necessary, a rough surface may be formed by sandblasting or polishing in order to impart appropriate unevenness to the surface. Abrasive grains used for blasting may be regular particles or irregular particles.

Next, an image forming method to which the developing method of the present invention can be applied will be described with reference to an image forming apparatus having a contact charging unit and a contact transfer unit schematically shown in FIG. The developing method of the present invention can also be applied to an image forming method using a corona charging method and / or a corona transfer method.

Photoconductive layer 801a and conductive base layer 801b
Is rotated at a predetermined peripheral speed (process speed) in the rotation direction of the clockwise hand on the drawing. A bias is applied to the charging roller 802 having the conductive elastic layer 802a and the core metal 802b by a charging bias power supply 803. The charging roller 802 is pressed against the photoconductor 801 by pressing force, and the photoconductor 801 is pressed.
It rotates following the rotation of.

When the bias V ₂ is applied to the charging roller 802, 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 from a developing bias applying unit 813 to the developing sleeve constituting the developing unit 805. The transfer roller 806 (conductive elasticity) as a contact transfer unit that presses the transfer material 808 to which the transfer bias V ₃ is applied by the transfer bias power supply 807 against the photoconductor 801 is applied to the toner image formed on the photoconductor 801 by the development. The toner image on the transfer material is electrostatically transferred to the transfer material 808 by the layer 806a and the core metal 806b).
Heating and pressing means 81 having 1a and pressing roller 811b
Heat and pressure fixation is carried out by 1. After the transfer of the toner image, the surface of the photoconductor 801 is exposed to contaminants such as transfer residual toner.
The surface of the photoconductor 801 is cleaned by a cleaning device 809 having an elastic cleaning blade pressed against the photoconductor 801 in the counter direction.
It is repeatedly imaged.

As described above, the primary charging means is described using the charging roller 802 as the contact charging means, but may be a contact charging means such as a charging blade or a charging brush, or a non-contact corona charging means. The contact charging means generates less ozone in the charging step.
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 blade or a transfer belt, or a non-contact corona transfer unit. The contact transfer unit generates less ozone in the transfer process.

Further, another fixing method applicable to the image forming method of the present invention will be described with reference to fixing means shown in FIG. FIG. 5 shows a recording material 519 on which a toner image is formed.
And a heating member 511 fixedly supported by the heating member 511 and a pressing member 518 which is in pressure contact with the heating member and makes the recording material adhere to the heating member via the film 515.

In the fixing device shown in FIG.
Has a smaller heat capacity than a conventional heat roll and has a linear heating part, and the maximum temperature of the heating part is 100
It is preferable that it is -300 degreeC.

The fixing film 515 located between the heating element 511 and the pressing roller 518 as a pressing member is preferably a heat-resistant sheet having a thickness of 1 to 100 μm. Polyester, PET (polyethylene terephthalate), PF
A (tetrafluoroethylene-perfluoroalkylvinyl ether copolymer), PTFE (polytetrafluoroethylene), polyimide, polyamide, and other polymer sheets, metal sheets such as aluminum, and laminates composed of metal sheets and polymer sheets Sheets are used.

A more preferable constitution of the fixing film is that these heat-resistant sheets have a release layer and / or a low-resistance layer.

Reference numeral 511 denotes a low-heat-capacity linear heating element fixedly supported by the apparatus.
The resistive material 513 is applied to an alumina substrate 512 having a length of 0 mm and a length of 240 mm to a width of 1.0 mm. Energization is DC100V cycle 20m
A pulse corresponding to a desired temperature and energy release amount controlled by the temperature detecting element 514 is given by changing the pulse width in a pulse-like waveform of sec. The approximate pulse width is 0.5 msec to 5 msec. The fixing film 515 moves in the direction of the arrow in the figure by contacting the heating element 511 whose energy and temperature are controlled in this manner.

An example of the fixing film has a thickness of 20 μm.
m heat-resistant film (for example, polyimide, polyetherimide, PES, PFA
It is an endless film in which a release layer obtained by adding a conductive agent to a fluororesin such as TFE or PAF) is coated at 10 μm.
Generally, the total thickness is less than 100 μm, more preferably 40 μm.
Less than m is good. The drive of the film is performed by the drive roller 516 and the driven roller 517 and the tension without being wrinkled in the direction of the arrow due to the tension.

Reference numeral 518 denotes a pressure roller having a rubber elastic layer having good releasability such as silicone rubber.
The heating element is pressurized through the film with the pressure of kg, and is rotated by pressing against the film. The unfixed toner 520 on the recording material 519 is
The image is guided to a fixing unit by an entrance guide 521, and a fixed image is obtained by the above-described heating.

Although the fixing film 515 has been described as an endless belt, a sheet feeding shaft and a winding shaft may be used, and the fixing film may be an edged film.

The methods for measuring the physical properties of the toner of the present invention are listed below.

(1) Binder resin contained in toner
Measurement of chloroform-insoluble content of 2 g of toner_A) To cylindrical filter paper (for example, Toyo
No. manufactured by Filter Paper Co., Ltd. 86R) into a Soxhlet extractor
Apply 200 ml of chloroform. About 120 ° C
Reflux for 10 hours using a temperature controlled oil bath.
Components soluble in chloroform (T_B) Concentrated chloroform
After shrinking and drying, vacuum drying at 60 ° C for 24 hours
More quantitative. Chloroform insolubility of binder resin in toner
Component (T_C) To determine the colorant (magnetic material)
THF-insoluble components (T_D ) From the following formula
Is calculated.

[0233]

(Equation 1)

Alternatively, the extraction residue (T _E ) can be weighed, and the chloroform-insoluble content (T _C ) can be determined from the following formula.

[0235]

(Equation 2)

(2) Measurement of Acid Value of Binder Resin, Binder Resin and Wax Contained in Toner The measurement is performed according to the measuring method described in JIS K0070. Measurement device: Automatic potentiometric titrator AT-400 (manufactured by Kyoto Electronics) Calibration of the device: 120 ml of toluene and 30 ml of ethanol
Is used. Measurement temperature: 25 ° C. Sample preparation: 1.0 g of toner is added to 120 ml of toluene and dissolved by stirring with a magnetic stirrer at room temperature (about 25 ° C.) for about 10 hours. Further, 30 ml of ethanol is added to make a sample solution.

Measurement operation: 1) The sample is used after removing additives other than the binder resin (polymer component) in advance, or the acid value and content of components other than the binder resin and the cross-linked binder resin are used. Is obtained in advance. 0.5 to 2.0 (g) of the crushed sample is precisely weighed, and the weight of the polymer component is defined as W (g). For example, when measuring the acid value of the binder resin from the toner, the acid value and the content of the colorant or the magnetic material are separately measured, and the acid value of the binder resin is obtained by calculation. 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 × 5.61｝ / W

Incidentally, the acid value (Av.
G) is the acid value (Av) of the binder resin contained in the toner.
・ B), acid value (Av ·
It can be calculated by the following equation using S).

[0240]

(Equation 3)

(3) Measurement of THF Insoluble Content of Binder Resin and Binder Resin Contained in Toner 0.5 to 1.0 g of a toner sample was weighed (W ₁ g),
A cylindrical filter paper (for example, No. 86R manufactured by Toyo Roshi Kabushiki Kaisha) is put into a Soxhlet extractor, and THF 200 m
After extracting with a solvent for 10 hours, evaporating the soluble component solution extracted with the solvent, vacuum drying at 100 ° C. for several hours, and weighing the amount of the THF soluble resin component (W
₂ g). Find the weight other than the resin component in the toner (W
₃ g). The THF-insoluble content of the binder resin contained in the toner is determined by the following equation.

[0242]

(Equation 4)

Alternatively, the extraction residue (W ₄ g) is weighed,
The THF-insoluble matter may be determined from the following equation.

[0244]

(Equation 5)

The measurement of the THF-insoluble content of the binder resin before the formation of the toner is performed in the same manner as described above using the binder resin as a sample, and the weight (W) of the sample before the extraction is measured.
₅ g) and the weight of the extraction residue after extraction (W ₆ g) can be obtained from the following equation.

[0246]

(Equation 6)

(4) Measurement of melting point of wax ASTM D3418-8 using a differential scanning calorimeter (DSC measuring apparatus) and DSC-7 (manufactured by PerkinElmer).
Measure according to 2.

The measurement sample is 2 to 10 mg, preferably 5 m
Weigh g precisely.

This was put in an aluminum pan, and an empty aluminum pan was used as a reference.
The measurement is performed at a temperature rising rate of 10 ° C./min and at normal temperature and normal humidity between 0 ° C.

In this heating process, an endothermic peak of the main peak of the DSC curve in the temperature range of 30 to 200 ° C. is obtained. The temperature of the endothermic main peak is defined as the melting point of the wax.

(5) Measurement of DSC Curve of Toner The DSC curve in the process of raising the temperature of the toner is measured in the same manner as the measurement of the melting point of the wax.

(6) Glass transition temperature (Tg) of binder resin
ASTM D3418-8 using a differential scanning calorimeter (DSC measuring device) and DSC-7 (manufactured by PerkinElmer).
Measure according to 2.

The measurement sample is 5 to 20 mg, preferably 10
Weigh the mg precisely.

This was put in an aluminum pan, and an empty aluminum pan was used as a reference.
The measurement is performed at a temperature rising rate of 10 ° C./min and at normal temperature and normal humidity between 0 ° C. In this heating process, an endothermic peak of a main peak in a temperature range of 40 to 100 ° C. is obtained.

The intersection between the line of the midpoint of the baseline before and after the endothermic peak appears and the differential heat curve is defined as the glass transition temperature Tg in the present invention.

(7) Measurement of molecular weight distribution of wax GPC measuring device: GPC-150C (Waters) Column: GMH-HT 30 cm double (manufactured by Tosoh Corporation) Temperature: 135 ° C. Solvent: o-dichlorobenzene (0.1% ionol) Addition) Flow rate: 1.0 ml / min Sample: Inject 0.4 ml of 0.15% sample

Measurement is performed under the above conditions, and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used for calculating the molecular weight of the sample. In addition, Mark-Hou
It is calculated by converting to polyethylene using a conversion formula derived from the wink viscosity formula.

(8) Measurement of Molecular Weight Distribution by GPC of THF Soluble Content of Binder Resin Raw Material or Toner In the present invention, the molecular weight distribution by GPC using tetrahydrofuran (THF) as a solvent was measured under the following conditions.
The molecular weight is 800 or more.

The column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) was passed through the column at this temperature as a solvent at a flow rate of 1 ml per minute.
When the sample is a binder resin material, a material obtained by passing the binder resin material through a roll mill (130 ° C., 15 minutes) is used. If the sample is a toner, dissolve the toner in THF
m, and the filtrate is used as a sample.
The measurement is performed by injecting 50 to 200 μl of a THF sample solution of a resin adjusted to a sample concentration of 0.05 to 0.6% by weight. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number. As standard polystyrene samples for creating calibration curves,
For example, Pressure Chemical Co.
Or Toyo Soda Kogyo Co., Ltd. has a molecular weight of 6 × 1
0 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 1
0 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10
⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and at least about 10 standard polystyrene samples are suitable. An RI (refractive index) detector is used as the detector.

In order to accurately measure a molecular weight region of 10 ³ to 2 × 10 ^6, a plurality of commercially available polystyrene gel columns may be used in combination.
rs Co., Ltd. μ-styragel 500, 10 ³ , 1
0 ⁴ 10 ⁵ of combinations and, shodex of Showa Denko Co., Ltd.
KA-801, 802, 803, 804, 805, 8
06,807 are preferred.

From the molecular weight distribution obtained by GPC obtained by the above method, the ratio of the integrated molecular weight of 10,000 to 100,000 to the integrated molecular weight of 800 or more is calculated, whereby the component having a molecular weight of 10,000 to 100,000 is calculated. Is determined.

The 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 allowed to stand 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.

(9) Measurement of contact angle of toner Measurement device: FACE contact angle measurement device (manufactured by Kyowa Interface Chemical Co., Ltd.) Measurement temperature: 23 to 25 ° C. Measurement humidity: 40 to 60% relative humidity Sample preparation: about 10 g of toner Is compression molded at a pressure of 200 kgf / cm ² for 2 minutes to have a diameter of 25 mm and a thickness of about 10 mm.
A disc-shaped sample of mm is prepared. This is about 27mm inside diameter
Glass sample bottle (for example, Snap Cup N
o. 30) and apply a pressure of 5 to 10 kgf / cm ² for about 5 to 10 minutes on a hot plate heated to 100 to 120 ° C. through a Teflon sheet. When the toner is softened and melted, it is cooled to room temperature, the glass sample bottle is broken, and the melted and molded product of the toner is taken out.
This is sequentially polished using an abrasive of # 280 → # 800 → # 1500 to obtain a disk-shaped sample having a diameter of 25 mm and a thickness of 5 mm. The surface for measuring the contact angle is finished so as not to be visually damaged. In addition, ion-exchanged water or commercially available purified water is used for the measurement, the contact angle is measured five times for each sample, and the average value is defined as the toner contact angle.

(10) Measurement of Particle Size Distribution of Toner The particle size distribution of the toner of the present invention is measured using a Coulter Counter TA-II or a Coulter Multisizer (manufactured by Coulter). As the electrolytic solution, a 1% NaCl aqueous solution is prepared using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter Scientific Japan) can be used. As a measurement method,
To 100 to 150 ml of the electrolytic aqueous solution, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant, and 2 to 20 mg of a measurement sample is further added. The electrolyte in which the sample is suspended is approximately 1 to
The dispersion treatment was performed for 3 minutes, and the measurement apparatus used a 100 μm aperture as a 2 μm aperture.
The volume and number distribution of the toner were measured to calculate a volume distribution and a number distribution. Then, a weight-average particle diameter (D ₄ ) on a weight basis (the representative value of each channel is regarded as a representative value of each channel) determined from the volume distribution according to the present invention was determined.

As the channels, 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.

(11) Measurement of Content of Different Elements in Magnetic Iron Oxide The amount of elements in the magnetic iron oxide was determined by using a fluorescent X-ray analyzer SYSTE.
M3080 (manufactured by Rigaku Denki Kogyo Co., Ltd.) using JI
It can be measured by performing X-ray fluorescence analysis according to the general rules of SK0119 X-ray fluorescence analysis.

(12) Measurement of Content Distribution of Different Elements in Magnetic Iron Oxide Regarding the content distribution of different elements in magnetic iron oxide, the amount of elements dissolved in hydrochloric acid or hydrofluoric acid was determined by plasma emission spectroscopy (I
CP) to obtain the dissolution rate from the concentration of each element at the time of dissolution with respect to the concentration of each element at the time of total dissolution.

(13) Measurement of Number Average Particle Diameter of Magnetic Body The number average diameter of the magnetic body was determined by a transmission electron microscope at a magnification of 4.
It can be obtained by randomly selecting 300 magnetic materials using a photograph taken at a magnification of 10,000 times and measuring with a digitizer.

(14) Measurement of Magnetic Properties of Magnetic Body The magnetic properties of the magnetic body are described in “Vibration sample type magnetometer VSM-3S
-15 "(manufactured by Toei Kogyo KK) using an external magnetic field 795.8.
Measured under kA / m.

(15) BET of magnetic substance and external additive fine powder
Of Specific Surface Area by Nitrogen Adsorption Measured by Magnetic Field Method The specific surface area of the magnetic material and the fine powder of the external additive can be measured by using a specific surface area measuring device Autosoap 1 (manufactured by Yuasa Ionics) according to the BET method. And BE
The specific surface area is calculated using the T multipoint method.

(16) Measurement of Methanol Wettability of Inorganic Fine Powder 0.2 g of inorganic fine powder is added to 50 ml of water in a 250 ml Erlenmeyer flask. Methanol is titrated from the burette until all of the silica is wetted. At this time, the solution in the flask is constantly stirred with a magneck stirrer. The end point is observed by the suspension of the entire amount of the fine silica powder in the liquid, and the methanol wettability is expressed as the percentage of methanol in the liquid mixture of methanol and water at the end point.

(17) Determination of Zirconium Element Contained in Chloroform-Insoluble Content (Gel) in Toner The zirconium element can be measured and quantified using an X-ray fluorescence analyzer 3080 (manufactured by Rigaku Corporation). it can.

The amount of the organic zirconium compound to be quantified is 0.0, 0.5, 1.0, 2..
Five kinds of toner samples, each containing 0 and 5.0% by weight, are manufactured and press-molded using a sample press-molding machine.

The X of each toner sample was measured under the following conditions.
Measure the line intensity. Measurement potential and voltage 50 kV, 50 mA Kα peak angle of zirconium element 22.5 ° Crystal plate LiF Measurement time 60 seconds

The measured X-ray intensity of each toner and the content of the organic zirconium compound in the toner, that is, the Z
A calibration curve based on the r element content is created, and the Zr element content (Z ₁ ) is determined from the calibration curve created from the actually measured X-ray intensity of the toner.

Next, the chloroform-soluble matter obtained by performing Soxhlet extraction of the toner with chloroform is evaporated to dryness, and the chloroform-soluble matter obtained is subjected to the same method as the determination of the zirconium element in the toner. Using a fluorescent X-ray analyzer, the Zr element content (Z ₂ ) of the chloroform-soluble portion is determined.

From the difference between the zirconium element content (Z ₁ ) in the toner and the zirconium element content (Z ₂ ) contained in the chloroform-soluble component, the toner gel (chloroform-insoluble component) was obtained using the following formula. The content (Z ₃ ) of the contained zirconium element is determined.

[0279]

(Equation 7)

[0280]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Production of the Polymer of the Present Invention: (Production Example 1) 200 parts by weight of xylene was charged into a reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introduction tube, a dropping device, and a decompression device. 67 parts by weight of styrene, 17 parts by weight of butyl acrylate, 16 parts by weight of monobutyl maleate, and 5 parts by weight of di-t-butyl peroxide as a polymerization initiator were added, and the mixture was heated to the reflux temperature for 12 hours while passing nitrogen gas through. Held. Then, xylene was distilled off under reduced pressure to obtain a polymer (1).

The polymer (1) obtained had Mw = 7000
0, Mw / Mn = 2.3, Tg = 59.4 ° C., acid value 3
It was 8.1 mgKOH / g.

(Preparation Example 2) Except that in Preparation Example 1, 78 parts by weight of styrene, 20 parts by weight of butyl acrylate, 3 parts by weight of monobutyl maleate and 4 parts by weight of a polymerization initiator (di-t-butyl peroxide) were used. In the same manner, a polymer (2) was obtained.

The polymer (2) obtained had Mw = 900
0, Mw / Mn = 2.3, Tg = 60.2 ° C., the acid value was 8.2 mg KOH / g.

(Production Example 3) Except that in Production Example 1, 75 parts by weight of styrene, 20 parts by weight of butyl acrylate, 6 parts by weight of monobutyl maleate and 4 parts by weight of a polymerization initiator (di-t-butyl peroxide) were used. In the same manner, a polymer (3) was obtained.

The polymer (3) obtained had Mw = 8,000
0, Mw / Mn = 2.2, Tg = 60.4 ° C., acid value is 1.
It was 7.7 mgKOH / g.

(Production Example 4) In Production Example 1, 75 parts by weight of styrene, 20 parts by weight of butyl acrylate, 5 parts by weight of monobutyl maleate and 3.2 parts by weight of a polymerization initiator (di-t-butyl peroxide) were used. A polymer (4) was obtained in the same manner except that

The polymer (4) obtained had Mw = 14,0
00, Mw / Mn = 2.3, Tg = 58.8 ° C., and the acid value was 27.3 mgKOH / g.

(Preparation Example 5) Except that in Preparation Example 1, 73 parts by weight of styrene, 24 parts by weight of butyl acrylate, 3 parts by weight of monobutyl maleate and 3 parts by weight of a polymerization initiator (di-t-butyl peroxide) were used. In the same manner, a polymer (5) was obtained.

The polymer (5) obtained had Mw = 14,0
00, Mw / Mn = 2.5, Tg = 59.2 ° C., and the acid value was 8.7 mgKOH / g.

(Production Example 6) In Production Example 1, 72 parts by weight of styrene, 25 parts by weight of butyl acrylate, 3 parts by weight of monobutyl maleate, and 2.5 parts by weight of a polymerization initiator (di-t-butyl peroxide) were used. A polymer (6) was obtained in the same manner except that the above procedure was repeated.

The polymer (6) obtained had Mw = 20,0
00, Mw / Mn = 2.3, Tg = 59.1 ° C., and the acid value was 9.4 mgKOH / g.

(Production Example 7) 200 parts by weight of xylene was charged into a reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen inlet tube, and a dropping device, and then 107 parts of the reactor were fed with nitrogen.
C., and as a first stage polymerization reaction, 32 parts by weight of styrene, 13 parts by weight of butyl acrylate, 5 parts by weight of monobutyl maleate and 1,1-bis (t-butylperoxy) cyclohexane 3 as a polymerization initiator Parts by weight were added dropwise and the temperature was maintained at that temperature for 8 hours. Next, as a second stage polymerization reaction, the reaction vessel is heated to 120 ° C., and a second monomer composition comprising 32 parts by weight of styrene, 13 parts by weight of butyl acrylate, 5 parts by weight of monobutyl maleate and 50 parts by weight of xylene Was added dropwise over 1 hour, and the temperature was maintained for 8 hours to terminate the polymerization reaction. Xylene was distilled off under reduced pressure to obtain a polymer (7).

The polymer (7) obtained had Mw = 15,0
00, Mw / Mn = 2.1, Tg = 60.8 ° C., and the acid value was 31.0 mgKOH / g.

(Production Example 8) In Production Example 7, 35 parts by weight of styrene, 13 parts by weight of butyl acrylate, and 2 parts by weight of monobutyl maleate were used as monomers for the first stage polymerization reaction, 35 parts by weight of styrene and butyl acrylate 13 as monomers used in the reaction
A polymer (8) was obtained in the same manner except that 2 parts by weight of monobutyl maleate and 2 parts by weight of monobutyl maleate were used.

The polymer (8) obtained had Mw = 15,0
00, Mw / Mn = 2.1, Tg = 59.8 ° C., and the acid value was 14.2 mgKOH / g.

(Production Example 9) In Production Example 7, 35 parts by weight of styrene, 14 parts by weight of butyl acrylate, and 1 part by weight of monobutyl maleate were used as monomers for the first-stage polymerization reaction. Styrene 35 parts by weight, butyl acrylate 14
A polymer (9) was obtained in the same manner except that 1 part by weight of monobutyl maleate was used.

The polymer (9) obtained had Mw = 14,0
00, Mw / Mn = 2.1, Tg = 59.1 ° C., and the acid value was 6.7 mgKOH / g.

(Production Example 10) In Production Example 7, 70 parts by weight of styrene and 2 parts by weight of monobutyl maleate were used at 100 ° C. as monomers used in the first stage polymerization reaction.
In the same manner as above except that 26 parts by weight of butyl acrylate and 1 part by weight of monobutyl maleate were used as monomers used in the second stage polymerization reaction.
0) was obtained.

The polymer (10) obtained had Mw = 21,
000, Mw / Mn = 2.3, Tg = 58.8 ° C., and the acid value was 11.2 mgKOH / g.

(Production Example 11) A polymer (11) was obtained in the same manner as in Production Example 8, except that the first-stage polymerization reaction was carried out at 100 ° C.

The obtained polymer (11) had Mw = 19,
000, Mw / Mn = 2.3, Tg = 59.1 ° C., and the acid value was 7.2 mgKOH / g.

(Production Example 12) ・ 69 parts by weight of styrene ・ 29 parts by weight of butyl acrylate ・ 2 parts by weight of monobutyl maleate ・ 2,2′-bis (4,4-di-t-butylperoxycyclohexyl) propane 0.2 parts by weight The above monomer mixture is charged and suspended in a reaction vessel equipped with a reflux tube, a stirrer, a thermometer and a nitrogen inlet tube containing 2 parts by weight of polyvinyl alcohol and 200 parts by weight of degassed ion-exchanged water. I do. Heat to 77 ° C. while passing nitrogen through, hold at that temperature for 20 hours, then add 0.5 parts by weight of benzoyl peroxide and hold for another 4 hours at 95 ° C.
And kept at that temperature for 2 hours to complete the polymerization reaction.

After the completion of the reaction, the suspension was filtered, washed with water and dried to obtain Mw = 1435,600 and Mw / Mn =
3.3, Tg = 56.3 ° C., acid value 6.2 mgKOH /
g of polymer (12) containing 3.4% by weight of a THF-insoluble matter.

(Production Example 13) 69 parts by weight of styrene 29 parts by weight of butyl acrylate 2 parts by weight of monobutyl maleate 0.2 part by weight of t-amyl peroxy 2-ethylhexanoate The above monomer mixture was used. The polymerization reaction temperature to 75 ° C
A polymer (13) was obtained in the same manner as in Production Example 12 except that the above was used.

The polymer (13) obtained had Mw = 83.
5,100, Mw / Mn = 2.3, Tg = 58.9 ° C.,
The acid value was 6.9 mgKOH / g.

(Production Example 14) 64 parts by weight of styrene 28 parts by weight of butyl acrylate 8 parts by weight of monobutyl maleate A polymer (14) was obtained in the same manner as in Production Example 12 except that the above monomer composition was used. Was.

The polymer (14) obtained had Mw = 78.
7,000, Mw / Mn = 2.3, Tg = 58.7 ° C.,
The acid value was 22.2 mg KOH / g.

(Production Example 15) • 75.5 parts by weight of styrene • 20 parts by weight of butyl acrylate • 4 parts by weight of monobutyl maleate • 0.5 parts by weight of divinylbenzene The same as in Production Example 5 except that the above monomer composition was used. Similarly, a polymer (15) was obtained.

The polymer (15) obtained had Mw = 16
5,000, Mw / Mn = 24.4, Tg = 60.3
C., the acid value was 13.2 mg KOH / g.

Production Example 16 78.5 parts by weight of styrene 20.0 parts by weight of n-butyl acrylate 1.0 part by weight of mono-n-butyl malate 0.5 part by weight of divinylbenzene The above monomer composition was used. A polymer (16) was obtained in the same manner as in Production Example 5 except for the above.

The polymer (16) obtained had Mw = 18
6,000, Mw / Mn = 22.7, Tg = 60.7
C., the acid value was 3.8 mg KOH / g.

(Comparative Production Example 1) ・ Styrene 80 parts by weight ・ Butyl acrylate 20 parts by weight ・ t-butyl peroxide 10 parts by weight The polymerization reaction was carried out in the same manner as in Production Example 1 except that the above monomer mixture was used. As a result, a comparative polymer (1) was obtained.

The obtained comparative polymer (1) had Mw =
4,000, Mw / Mn = 2.2, Tg = 59.6 ° C.,
The acid value was 0.6 mg KOH / g.

(Comparative Production Example 2) ・ 58 parts by weight of styrene ・ 20 parts by weight of butyl acrylate ・ 22 parts by weight of monobutyl maleate ・ 8 parts by weight of t-butyl peroxide Same as Production Example 1 except that the above monomer mixture was used. And a polymerization reaction was carried out to obtain a comparative polymer (2).

The comparative polymer (2) thus obtained had Mw =
4,000, Mw / Mn = 2.5, Tg = 59.3 ° C.,
The acid value was 46.1 mg KOH / g.

(Comparative Production Example 3) ・ Styrene 80 parts by weight ・ Butyl acrylate 20 parts by weight ・ t-butyl peroxide 5 parts by weight The polymerization reaction was carried out in the same manner as in Production Example 1 except that the above monomer mixture was used. As a result, a comparative polymer (3) was obtained.

The obtained comparative polymer (3) had Mw = 3
6,000, Mw / Mn = 3.2, Tg = 60.2 ° C.
The acid value was 0.4 mg KOH / g.

Comparative Production Example 4 52 parts by weight of styrene 28 parts by weight of butyl acrylate 20 parts by weight of monobutyl maleate 5 parts by weight of benzoyl peroxide Except for using the above monomer mixture, the same procedure as in Production Example 12 was carried out. By performing a polymerization reaction, a comparative polymer (4) was obtained.

The obtained comparative polymer (4) had Mw = 3
4,000, Mw / Mn = 3.3, Tg = 58.7 ° C.,
The acid value was 43.3 mg KOH / g.

(Comparative Production Example 5) ・ Styrene 80 parts by weight ・ Butyl acrylate 20 parts by weight ・ t-butyl peroxide 3 parts by weight The polymerization reaction was carried out in the same manner as in Production Example 1 except that the above monomer mixture was used. As a result, a comparative polymer (5) was obtained.

The obtained comparative polymer (5) had Mw = 9.
2,000, Mw / Mn = 4.3, Tg = 60.2 ° C.,
The acid value was 0.5 mg KOH / g.

(Comparative Production Example 6) 52 parts by weight of styrene 28 parts by weight of butyl acrylate 20 parts by weight of monobutyl maleate 3 parts by weight of benzoyl peroxide Except for using the above monomer mixture, the same procedure as in Production Example 12 was carried out. The polymer for comparison (6) was obtained by performing a polymerization reaction.

The obtained comparative polymer (6) had Mw = 8
8,000, Mw / Mn = 3.6, Tg = 59.4 ° C.,
The acid value was 41.8 mgKOH / g.

Physical Properties of Polymers (1) to (16) Obtained in Production Examples 1 to 16 and Comparative Polymers (1) to (6) Obtained in Comparative Production Examples (1) to (6) Are shown in Table 2 below.

[0326]

[Table 2]

(Production Example 1 of Binder Resin) A reflux tube, a stirrer,
Polymer (1) 7 was placed in a reaction vessel equipped with a thermometer and a decompression device.
5 parts by weight and 25 parts by weight of polymer (14)
0 parts by weight. While stirring, the mixture was heated to the reflux temperature and stirred and mixed for 2 hours. Next, xylene was distilled off under reduced pressure to obtain a binder resin 1 of the present invention.

The obtained binder resin 1 has a main peak at a molecular weight of 8,000, a sub-peak (Msp) at a molecular weight of 639,000, Mw = 215,000, and Mw / M
n = 48.0 and the acid value was 33.3 mgKOH / g.

(Production Examples 2 to 26 of Binder Resin) Tables 2 and 3
The polymers and waxes shown in Table 1 were combined and added to xylene, and binder resins 2 to 26 of the present invention shown in Tables 4 and 5 were obtained in the same manner as in Production Example 1 of the binder resin.

(Reference Binder Resin Production Examples 1 and 2) Reference polymers 1 and 2 shown in Table 5 were prepared using only the polymers shown in Table 2 without using wax.

(Production Examples 1 to 6 of Comparative Binder Resins) Comparative resins 1 to 6 shown in Table 5 were prepared in the same manner except that comparative polymers and / or comparative waxes shown in Tables 2 and 3 were used.
6 was obtained.

Table 3 shows the waxes used in the above examples of the production of the binder resin and the production examples of the comparative binder resin. The obtained binder resins 1 to 26, reference binder resins 1 to 3 and comparative examples were used. Tables 4 and 5 show the formulations and physical properties of binder resins 1 to 6 for use.

[0333]

[Table 3]

[0334]

[Table 4]

[0335]

[Table 5] Example 1 100 parts by weight of binder resin (1) 2 parts by weight of zirconium compound represented by formula (164) 7 parts by weight of wax (3) 90 parts by weight of magnetic iron oxide (average particle size 0.18 μm, The coercive force is 10.7 KA / m, the residual magnetization is 11.2 Am ² / kg, and the saturation magnetization is 81.5 Am ² / kg. The above mixture is melt-kneaded with a biaxial extruder heated to 130 ° C., and the cooled mixture is hammered. It was coarsely ground in a mill. The coarsely pulverized product is finely pulverized by a jet mill, and the obtained finely pulverized product is classified by an air classifier to have a weight average diameter of 6.9 μm.
m of magnetic toner was obtained.

With respect to 100 parts by weight of the magnetic toner, hydrophobic dry silica (BET specific surface area: 200 m ² / g) was used.
0 parts by weight was externally added using a Henschel mixer to obtain a toner (1).

The toner (1) had an acid value of 15.1 mg KOH
/ G, the difference between the acid value (Av · S) of the chloroform-soluble portion and the acid value (Av · G) of the chloroform-insoluble portion (Av · G).
G-Av.S) is 53.3 mgKOH / g, and the binder resin of the toner is 46.2% by weight of chloroform-insoluble matter.
And contained 54.5% by weight of a THF-insoluble matter.
The THF-soluble component has a main peak (M
p) and a subpeak (Ms
p). The zirconium element in the toner was 0.2%.
It contained 2% by weight. The contact angle of the toner was 107 degrees.

The wax dispersibility of the obtained toner was evaluated by the following evaluation method. Table 9 shows the evaluation results.

(Evaluation Method of Wax Dispersibility in Toner) The toner was observed at a low magnification (for example, 30 to 100 times) using an optical microscope equipped with a polarizing plate, and about 500 toner particles were removed from the toner. The number of bright spots indicating the presence of free wax particles was determined. Rank 5: No bright spot through the polarizing plate Rank 4: 1 to 10 bright spots (to the extent that there is no practical problem) Rank 3: 11 to 20 bright spots (to the extent that the fog density of the image becomes high) Rank 2:21 Up to 30 bright spots (to the extent that wax adheres to the photosensitive drum) Rank 1: 31 or more bright spots (to the extent that wax and toner adhere to the photosensitive drum)

Using this toner, a digital copying machine GP-215 manufactured by Canon (process speed: 105 mm /
5, film heating fixing shown in FIG. 5), Canon copier NP-6650 (process speed 320 mm / sec, hot roll fixing) and Canon copier NP-6085 (process speed 513 mm / sec, shown at 811 in FIG. 4). In addition to the modification to remove the toner cleaning member from the fixing device (heat roll fixing), a continuous image output test of 50,000 sheets was performed to evaluate the initial and endurance image density and the cleaning property on the photoconductor. As a result, good results were obtained as shown in Table 8.

(Evaluation Method of Toner Cleaning Property on Photoconductor) "Cleaning property" of the photoconductor after durability was evaluated according to the following criteria. A: No filming on photoreceptor surface B: Slight filming on non-paper passing area on photoreceptor surface C: Minor filming on paper passing area on photoreceptor surface D: Filming that causes image fogging occurs on the surface of the photoreceptor. E: Toner fusion that causes image spots occurs on the surface of the photoreceptor.

Further, the fixing devices of GP-215, NP-6650 and NP-6085 were removed, and an external drive device and a temperature control device were attached. The fixing speed is set to the same as each copier, and the fixing temperature is changed and the fixing test is performed. The low-temperature fixing property, the high-temperature offset resistance, and the heating member of the fixing device (heat-resistant film, heating roller and pressure roller)
When the state of adhesion of the toner was evaluated, good results were obtained as shown in Table 9.

The "image density" was measured by measuring reflection density using a Macbeth densitometer (manufactured by Macbeth) using an SPI filter, and measuring a circular image having a diameter of 5 mm.

(Evaluation Criteria for Low-Temperature Fixing Property According to GP-215) An image density of 1.3 to 1.
The image was fixed by passing a solid black image of No. 4 and then rubbing with a Dasper (manufactured by Ozu Sangyo Co., Ltd.) under a load of 50 g / cm ² to determine the density reduction rate. Rank 5: Density reduction rate due to rubbing is less than 5% Rank 4: Density reduction rate due to rubbing is less than 10% Rank 3: Density reduction rate due to rubbing is less than 15% Rank 2: Density reduction rate due to rubbing is 20 Less than% Rank 1: Density reduction rate by rubbing is 20% or more

(Evaluation Criteria for Low-Temperature Fixing Ability by NP-6650 and NP-6085) Set the temperature of the fixing unit to 180 ° C.
The test was performed under the same conditions as in the fixing test using GP-215, except that Rank 5: Density reduction rate due to rubbing is less than 5% Rank 4: Density reduction rate due to rubbing is less than 10% Rank 3: Density reduction rate due to rubbing is less than 15% Rank 2: Density reduction rate due to rubbing is 20 Less than% Rank 1: Density reduction rate by rubbing is 20% or more

(Evaluation Criteria for Hot Offset) Rank 5: Not generated at all Rank 4: Slight offset generated, but practically acceptable Rank 3: Offset generated that can be easily discriminated visually Rank 2: Notable offset Occurrence Rank 1: Paper wraps around the roller

(Evaluation Criteria for Toner Contamination of Heating Member of Fixing Unit) Rank 5: No toner contamination was found Rank 4: Slight contamination was found, but practically acceptable Rank 3: Contamination that can be easily visually discriminated Seen Rank 2: Remarkable contamination seen Rank 1: Contaminated toner adheres to the front and back surfaces of paper

Examples 2 to 23 In place of the binder resin (1) used in Example 1, binder resins (2), (7), (1
Toners (2) to (23) of the present invention were produced in the same manner as in Example 1 except that 3) and (16) to (26) were used, and that no wax (3) was used. Was evaluated in the same way as Tables 6 and 7 show the constitution and physical properties of the toner, and Tables 8 and 9 show the evaluation results.

[Reference Example 1] Reference binder resin (1) was used in place of binder resin (1) used in Example 1, and reference wax (1) was used in place of wax (3). A reference toner (1) was produced in the same manner as in Example 1 except that 2 parts by weight and 4 parts by weight of the reference wax (2) were used, and evaluated in the same manner as in Example 1. Tables 6 and 7 show the constitution and physical properties of the toner, and Tables 8 and 9 show the evaluation results.

[Reference Example 2] Reference binder resin (2) was used in place of binder resin (1) used in Example 1, and reference wax (1) was used in place of wax (3). The reference toner (2) was prepared in the same manner as in Example 1 except that 3 parts by weight and 3 parts by weight of the reference wax (3) were used, and the organic zirconium compound (67) was used instead of the organic zirconium compound (164). It was manufactured and evaluated in the same manner as in Example 1. Tables 6 and 7 show the constitution and physical properties of the toner, and Tables 8 and 9 show the evaluation results.

Comparative Example 1 100 parts by weight of a binder resin for comparison (1) 2 parts by weight of a charge control agent containing a zinc element represented by the formula (176) 7 parts by weight of wax for comparison 1 90 parts by weight of iron oxide (average particle size: 0.18 μm, coercive force: 10.7 KA / m, residual magnetization: 11.2 Am ² / kg, saturation magnetization: 81.5 Am ² / kg) Similarly, comparative toner (1) was produced. Tables 6 and 7 show the constitution and physical properties of the toner, and Tables 8 and 9 show the evaluation results.

[0352]

Embedded image

[Comparative Examples 2 to 6] In the same manner as in Example 1 except that comparative binder resins (2) to (6) were used instead of binder resin (1) used in Example 1, Comparative toner (2)
To (6). The comparative toner (2) was manufactured using 7 parts by weight of the comparative wax (2) instead of the wax (3) used in Example 1, and the comparative toners (3) to (6) ) Is the wax (3) used in Example 1.
It was manufactured without using. Tables 6 and 7 show the constitution and physical properties of the toner, and Tables 8 and 9 show the evaluation results.

[0354]

[Table 6]

[0355]

[Table 7]

[0356]

[Table 8]

[0357]

[Table 9]

[0358]

According to the present invention, a low-temperature machine which is suitable for a medium-to-high-speed machine using a hot-roll fixing device, or a medium-to-low-speed machine using a pressure-bonding heat fixing system using a fixed heating heater via a heat-resistant film. It is a toner that exhibits fixability and does not cause contamination of the heating member due to offset from low to high temperatures. The present invention also provides a colorant (particularly a magnetic substance)
Is excellent in low-temperature fixability showing good halftone fixability even when used as a binder resin for a toner having a small particle diameter in which the content of is increased.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a developer supply system developing device (using a magnetic blade as a regulating member) in which a developer carrier capable of using the toner of the present invention in a developing method is incorporated.

FIG. 2 is a schematic diagram showing an example of a developer supply system developing device (using an elastic blade as a regulating member) in which a developer carrier capable of using the toner of the present invention in a developing method is incorporated.

FIG. 3 is a schematic cross-sectional view of a part of a developer carrier that can use the toner of the present invention in a developing method.

FIG. 4 is a schematic explanatory view of an image forming method to which the toner of the present invention can be applied.

FIG. 5 is a schematic diagram of a fixing device applicable to the image forming method of the present invention.

Claims (124)

[Claims] 1. A negatively triboelectric toner containing at least a binder resin, a colorant, a wax and an organometallic compound, wherein (a) the toner has an acid value of 5 to 35 mgKOH / g.
(B) the binder resin of the toner is a vinyl polymer, (c) the binder resin of the toner has a chloroform-insoluble content of 3 to 50% by weight, and (d) tetrahydrofuran (THF) of the toner. The soluble component has a main peak in a molecular weight region of 5,000 to 30,000 and a subpeak and / or at least one shoulder in a molecular weight region of 200,000 to 1.5 million in a chromatogram obtained by gel permeation chromatography (GPC) measurement. (E) the organometallic compound comprises zirconium, an aromatic diol, an aromatic hydroxycarboxylic acid, an aromatic monocarboxylic acid, and an aromatic polycarboxylic acid. Organic zirconium compound coordinated and / or bound to an aromatic compound selected from the group consisting of carboxylic acids Triboelectric negative toner, characterized in that. 2. The toner according to claim 1, wherein said toner has an acid value of 10 to 30 mg KO.
2. The negatively triboelectrically chargeable toner according to claim 1, wherein the toner is H / g. 3. The negatively triboelectrically chargeable toner according to claim 1, wherein the binder resin of the toner contains 5 to 45% by weight of a chloroform-insoluble component. 4. The negative frictionally chargeable toner according to claim 1, wherein the binder resin of the toner contains 10 to 40% by weight of a chloroform-insoluble content. 5. The THF-soluble component of the toner has a molecular weight of 7000 to 2 in a chromatogram measured by GPC.
The negative frictionally chargeable toner according to any one of claims 1 to 4, wherein the toner has a main peak in a region of 5000. 6. The THF-soluble component of the toner has a molecular weight of 9000 to 2 in a chromatogram measured by GPC.
The negatively triboelectric toner according to any one of claims 1 to 4, wherein the toner has a main peak in an area of 10,000. 7. The toner according to claim 1, wherein the THF-soluble component of the toner contains 20 to 60% by weight of a component having a molecular weight of 10,000 to 100,000 in a chromatogram measured by GPC. 3. The negatively triboelectrically chargeable toner described in 1. above. 8. The toner according to claim 1, wherein the THF-soluble component of the toner contains 25 to 50% by weight of a component having a molecular weight of 100,000 or more in a chromatogram measured by GPC. Negatively chargeable toner. 9. The THF-soluble component of the toner has a molecular weight of from 300,000 to 12 in a chromatogram measured by GPC.
The negative frictionally chargeable toner according to any one of claims 1 to 7, wherein the toner has at least one subpeak and / or shoulder in an area of 10,000. 10. The THF-soluble component of the toner has a molecular weight of 300,000 to 1 in a chromatogram measured by GPC.
2. The composition according to claim 1, wherein the composition has at least one subpeak and / or shoulder in a region of 200,000 and contains 25 to 50% by weight of a component having a molecular weight of 100,000 or more.
8. The negative frictionally chargeable toner according to any one of items 1 to 7, 11. The negative frictionally chargeable toner according to claim 1, wherein the organic zirconium compound is added to the toner as a charge control agent. 12. The method according to claim 1, wherein the organic zirconium compound is a zirconium complex in which an aromatic diol, an aromatic hydroxycarboxylic acid or an aromatic polycarboxylic acid is coordinated. The negatively triboelectrically chargeable toner as described in the above. 13. The method according to claim 1, wherein the organic zirconium compound is a zirconium complex salt which coordinates an aromatic diol, an aromatic hydroxycarboxylic acid or an aromatic polycarboxylic acid. The negatively triboelectrically chargeable toner as described in the above. 14. The organic zirconium compound contains, as a main component, a zirconium complex or complex salt in which one molecule of an aromatic diol, aromatic hydroxycarboxylic acid or aromatic carboxylic acid is coordinated. 12. The negative frictionally chargeable toner according to any of 11. 15. The organic zirconium compound contains, as a main component, a zirconium complex or a complex salt in which an aromatic diol, an aromatic hydroxycarboxylic acid or an aromatic carboxylic acid is coordinated in two molecules. 12. The negative frictionally chargeable toner according to any of 11. 16. The organic zirconium compound contains, as a main component, a zirconium complex or complex salt in which three molecules of an aromatic diol, an aromatic hydroxycarboxylic acid or an aromatic carboxylic acid are coordinated. 12. The negative frictionally chargeable toner according to any of 11. 17. The organic zirconium compound contains a zirconium complex or complex salt in which four molecules of an aromatic diol, an aromatic hydroxycarboxylic acid or an aromatic carboxylic acid are coordinated as a main component. 12. The negative frictionally chargeable toner according to any of 11. 18. The organic zirconium compound is a zirconium aromatic carboxylate having an aromatic carboxylic acid, an aromatic hydroxycarboxylic acid or an aromatic polycarboxylic acid. The negative frictionally chargeable toner according to any one of the above. 19. The negative frictionally chargeable toner according to claim 1, wherein the organic zirconium compound has a structure represented by the following formula (1). Embedded image [Wherein, Ar represents an alkyl group, an aryl group,
Aralkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryloxy group, hydroxyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group,
X and Y represent an aromatic residue which may have an acyloxy group, a carboxyl group, a halogen, a nitro group, a cyano group, an amino group, an amide group or a carbamoyl group;
X and Y may be the same or different, L represents a neutral ligand, water, alcohol, ammonia, alkylamine or pyridine, and C ₁ represents Monovalent cation, hydrogen, monovalent metal ion,
Represents ammonium or alkylammonium and represents C ₂
Represents a divalent cation or a divalent metal ion, n represents 2, 3, or 4, m represents 0, 2, or 4, and an aromatic carboxylic acid serving as a ligand in each complex or each complex salt; The aromatic diols may be the same or different, and may be a mixture of complex compounds having different numbers of n and / or m, and the counter ions C ₁ and C ₂
May be a mixture of different complex salts. ] 20. The toner of claim 1, wherein the organic zirconium compound has a structure represented by the following formula (2). Embedded image [Wherein, Ar represents an alkyl group, an aryl group,
Aralkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryloxy group, hydroxyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group,
X and Y represent an aromatic residue which may have an acyloxy group, a carboxyl group, a halogen, a nitro group, a cyano group, an amino group, an amide group or a carbamoyl group;
X and Y may be the same or different, L represents a neutral ligand, water, alcohol, ammonia, alkylamine or pyridine, and A represents an anion. Represents a halogen, a hydroxyl ion, a carboxylate ion, a carbonate ion, a nitrate ion, a sulfate ion, a cyanide ion or a thiocyan ion, A may have different ions from each other, C ₁ is a monovalent cation,
Hydrogen, a monovalent metal ion, ammonium or alkylammonium; C ₂ represents a divalent cation or a divalent metal ion; n represents 1, 2, 3, or 4;
Represents 1, 2, 3, 4, 5 or 6, and m represents 0, 1,
2, 3, or 4, wherein the anion A, aromatic carboxylic acid and aromatic diol which are ligands in each complex or each complex salt may be the same or different, and n or / And a mixture of complex compounds having different numbers of m and m, or a mixture of complex salts having different counter ions C ₁ and C _{2. When} A is a divalent anion, the counter cation coefficient k is doubled. ] 21. The negative electrode according to claim 1, wherein the organic zirconium compound has a structure represented by the following formula (3), (4) or (5). Triboelectric charging toner. Embedded image Wherein R is hydrogen, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, Group, a halogen, a nitro group, an amino group or a carbamoyl group, which may be linked to each other to form an aliphatic ring, an aromatic ring or a heterocyclic ring, in which case the ring may have a substituent R And the substituent R is 1
You may have up to eight, even if each is the same,
C ₁ may represent a monovalent cation, hydrogen, alkali metal, ammonium or alkylammonium, 1 represents an integer of 1 to 8, and n represents 2, 3 or 4
And m represents 0, 2 or 4, and the aromatic carboxylic acid or aromatic diol serving as a ligand in each complex or complex salt may be the same or different, and n or It may be a mixture of complex compounds having different numbers of / and m, or a mixture of complex salts having different counter ions C ₁ . ] 22. The negative electrode according to claim 1, wherein the organic zirconium compound has a structure represented by the following formula (6), (7) or (8). Triboelectric charging toner. Embedded image Wherein R is hydrogen, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, Group, a halogen, a nitro group, an amino group or a carbamoyl group, which may be linked to each other to form an aliphatic ring, an aromatic ring or a heterocyclic ring, in which case the ring may have a substituent R And the substituent R is 1
You may have up to eight, even if each is the same,
A may be different, A represents an anion, a halogen, a hydroxide ion, a carboxylate ion, a carbonate ion, a nitrate ion, a sulfate ion, a cyanide ion or a thiocyan ion, and A may have mutually different ions. , C ₁
Represents a monovalent cation, hydrogen, a monovalent metal ion, ammonium or alkylammonium, and n represents 1,
Represents 2,3 or 4, k represents 1,2,3,4,5 or 6, m represents 0,1,2,3 or 4, and is a ligand in each complex or each complex salt The aromatic carboxylic acids and aromatic diols may be the same or different, and may be a mixture of complex compounds having different numbers of n and / or m, and may be a cation C ₁ or / and A mixture of two or more complex compounds having different anions A may be used. When A is a divalent anion, the coefficient k of the counter cation is doubled. ] 23. The negative triboelectrically chargeable toner according to claim 1, wherein the organic zirconium compound has a structure represented by the following formula (36) or (37). . Embedded image [Wherein, Ar represents an alkyl group, an aryl group,
Aralkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, hydroxyl, acyloxy, alkoxycarbonyl, aryloxycarbonyl, acyl, carboxyl, halogen, nitro, cyano, amino, amide A ₁ represents a monovalent anion, a halogen ion, a hydroxide ion, a nitrate ion or a carboxylate ion, A ₂ represents a divalent anion,
Represents a sulfate ion, a hydrogen phosphate ion or a carbonate ion, and n represents 1, 2, 3 or 4, and in each metal salt, an anion A ₁ , an anion A ₂ , an aromatic carboxylic acid and an aromatic hydroxy carboxylic acid which become an acid ion. The acids may be the same or different, and may be a mixture of salts with different numbers of n. ] 24. The negatively triboelectrically chargeable toner according to claim 1, wherein the organic zirconium compound has a structure represented by the following formula (38) or (39). . Embedded image Wherein R is hydrogen, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, Group, a halogen, a nitro group, an amino group, an amide group or a carbamoyl group, which may be connected to each other to form an aliphatic ring, an aromatic ring or a heterocyclic ring. May have 1 to 8 substituents R, which may be the same or different, and A ₁ is a monovalent anion, a halogen ion, a hydroxyl ion, a nitrate ion or A ₂ represents a divalent anion, a sulfate ion, a hydrogen phosphate ion or a carbonate ion, and 1 represents 1
Represents an integer of ８8, n represents 1, 2, 3, or 4;
In each metal salt, the anion A ₁ , the anion A ₂ and the aromatic carboxylic acid serving as the acid ion may be the same or different, or may be a mixture of salts having different numbers of n. . ] 25. The negatively triboelectrically chargeable toner according to claim 1, wherein the organic zirconium compound has a structure represented by the following formula (40) or (41). . Embedded image Wherein R is hydrogen, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, Group, a halogen, a nitro group, an amino group, an amide group or a carbamoyl group, which may be connected to each other to form an aliphatic ring, an aromatic ring or a heterocyclic ring. May have 1 to 8 substituents R, which may be the same or different, and A1 is a monovalent anion, a halogen ion, a hydroxyl ion, a nitrate ion or a carboxylic acid. A2 represents an acid ion, A2 represents a divalent anion, a sulfate ion, a hydrogen phosphate ion or a carbonate ion;
And n represents 1, 2, 3, and 4. In each metal salt, the anion A1, the anion A2, and the aromatic carboxylic acid serving as an acid ion may be the same or different. Alternatively, a mixture of salts having different numbers of n may be used. ] 26. The toner according to claim 1, wherein the vinyl polymer has a carboxyl group and / or an anhydrous carboxyl group. 27. The organic zirconium compound can form a chloroform-insoluble component by interacting with a carboxyl group and / or an anhydrous carboxyl group contained as a substituent of a vinyl polymer as a binder resin. The negative frictionally chargeable toner according to claim 26. 28. The organic zirconium compound as a zirconium element in chloroform-insoluble matter in a total amount of 3%.
2. The composition of claim 1, wherein the content is 0% by weight or more.
29. The negatively triboelectrically-chargeable toner according to any one of the above-described items. 29. The organic zirconium compound as a zirconium element in chloroform-insoluble matter in a total amount of 4%.
2. The composition of claim 1, wherein the content is 0% by weight or more.
29. The negatively triboelectrically-chargeable toner according to any one of the above-described items. 30. The method according to claim 1, wherein the zirconium compound contained in the toner is contained in a chloroform-insoluble content as a zirconium element in an amount of 50% by weight or more based on the total amount of the zirconium element. Negatively chargeable toner. 31. A difference (Av · G−Av · S) between the acid value (Av · S) of the chloroform-soluble portion of the toner and the acid value (Av · G) of the chloroform-insoluble portion of the toner is from 10 to 10. 2. The amount is 150 mgKOH / g.
31. The negatively triboelectrically-chargeable toner according to any one of items 30 to 30. 32. The difference (Av · G−Av · S) between the acid value (Av · S) of the chloroform-soluble portion of the toner and the acid value (Av · G) of the chloroform-insoluble portion of the toner is 20 to 40. The amount is 130 mgKOH / g.
31. The negatively triboelectrically-chargeable toner according to any one of items 30 to 30. 33. A difference (Av · G−Av · S) between the acid value (Av · S) of the chloroform-soluble portion of the toner and the acid value (Av · G) of the chloroform-insoluble portion of the toner is from 30 to 30. The amount is 100 mgKOH / g.
31. The negatively triboelectrically-chargeable toner according to any one of items 30 to 30. 34. The toner, wherein (A) the toner has a contact angle with water of 105 to 130 degrees,
(B) the binder resin has a vinyl polymer having an acid value of 5 to 40 mgKOH / g, and (C) the resin component of the toner has a tetrahydrofuran (THF) insoluble content of 5 to 60% by weight. %, And the wax has a molecular weight of 300 to 5,000 in a chromatogram measured by gel permeation chromatography (GPC).
Has a main peak (Mp) and a weight average molecular weight (Mp).
The ratio (Mw / Mn) of w) to the number average molecular weight (Mn) is from 1.2 to 15, 4.
3. The negative frictionally chargeable toner according to any one of 3. 35. The toner has a contact angle of 107 with water.
35. The method of claim 34, wherein the angle is between about 127 degrees and about 127 degrees.
3. The negatively triboelectrically chargeable toner described in 1. above. 36. The toner has a contact angle of 110 with water.
35. The method of claim 34, wherein the angle is between 125 and 125 degrees.
3. The negatively triboelectrically chargeable toner described in 1. above. 37. The binder resin contains 7 to 35 mg KOH.
The negatively triboelectrically chargeable toner according to any one of claims 34 to 36, comprising a vinyl polymer having an acid value of / g. 38. The binder resin is 10 to 30 mg KO.
37. The negative frictionally chargeable toner according to claim 34, comprising a vinyl polymer having an acid value of H / g. 39. The toner according to claim 3, wherein the binder resin of the toner contains 7 to 55% by weight of a THF-insoluble component.
39. The negative frictionally chargeable toner according to any one of items 4 to 38. 40. The negative frictionally chargeable toner according to claim 34, wherein the binder resin of the toner contains 10 to 50% by weight of a THF-insoluble component. 41. The wax according to claim 34, wherein the wax has a main peak at a molecular weight of 600 to 4500 and a ratio (Mw / Mn) of 1.5 to 10 in a chromatogram measured by GPC. 40. The negatively triboelectrically chargeable toner according to any one of the above items 40. 42. The wax according to claim 34, wherein the wax has a main peak at a molecular weight of 700 to 4000 in a chromatogram measured by GPC and has a ratio (Mw / Mn) of 1.7 to 8. 40. The negatively triboelectrically chargeable toner according to any one of the above items 40. 43. The toner according to claim 41, wherein the wax is one of a hydrocarbon wax, a polyethylene polymer and a polypropylene polymer. 44. The negative frictionally chargeable toner according to claim 41, wherein the wax has a structure represented by the formula (a). Embedded image (In the formula, A represents a hydroxyl group or a carboxyl group, and a represents an integer of 20 to 60.) 45. The wax according to claim 1, wherein the wax is 1 to 20 mgKOH /
42. The toner of claim 41, wherein the toner is an acid-modified polypropylene having an acid value of g. 46. The method according to claim 46, wherein the wax is 1 to 20 mgKOH /
42. The toner of claim 41, wherein the toner is an acid-modified polyethylene having an acid value of g. 47. The wax may be a differential scanning calorimeter (DS)
The endothermic main peak temperature at the time of temperature rise measured in C) is 70
42. The toner of claim 41, wherein the temperature is from 140 to 140 [deg.] C. 48. The wax may be a differential scanning calorimeter (DS)
42. The negative frictionally chargeable toner according to claim 41, wherein the melting point defined by the endothermic peak temperature at the time of temperature rise measured in C) is 80 to 135 [deg.] C. 49. The wax is provided by a differential scanning calorimeter (DS).
The toner according to claim 41, wherein the melting point defined by the endothermic peak temperature at the time of temperature rise measured in C) is 85 to 130 ° C. 50. The toner contains two or more kinds of different waxes, and has a molecular weight of 50 in the chromatogram of all the waxes contained in the toner by GPC measurement.
It has a main peak at 0 to 7000 and has a ratio (Mw / M
4. The method according to claim 2, wherein n) is 1.2 to 15.
41. The negative frictionally chargeable toner according to any one of 4 to 40. 51. The toner contains two or more different waxes and has a molecular weight of 70 as determined by GPC measurement of all the waxes contained in the toner.
It has a main peak from 0 to 6000 and has a ratio (Mw / M
4. The method according to claim 3, wherein n) is 1.5 to 12.
41. The negative frictionally chargeable toner according to any one of 4 to 40. 52. The toner contains two or more different waxes and has a molecular weight of 10 based on a chromatogram of all the waxes contained in the toner as measured by GPC.
It has a main peak at 00 to 5000 and a ratio (Mw / M
41. The negative frictionally chargeable toner according to claim 34, wherein n) is 2 to 10. 53. The method according to claim 5, wherein the at least one wax is one of a hydrocarbon wax, a polyethylene polymer and a polypropylene polymer.
0. A negatively triboelectrically chargeable toner according to item 0. 54. The at least one wax of formula (a)
The negatively triboelectrically-chargeable toner according to claim 50, having a structure represented by: Embedded image (In the formula, A represents a hydroxyl group or a carboxyl group, and a represents an integer of 20 to 60.) 55. The method according to claim 55, wherein the at least one wax is 1 to 2
The negative frictionally chargeable toner according to claim 50, wherein the toner is an acid-modified polypropylene having an acid value of 0 mgKOH / g. 56. The method according to claim 56, wherein the at least one kind of wax is 1 to 2
The negative frictionally chargeable toner according to claim 50, wherein the toner is an acid-modified polyethylene having an acid value of 0 mgKOH / g. 57. The binder resin has an aromatic vinyl monomer and a (meth) acrylic acid ester monomer in a molecule having two or more peroxide groups, and halves the cleavage reaction of each peroxide group for 10 hours. The method according to claim 1, wherein a vinyl polymer synthesized by a radical polymerization method is contained in an amount of at least 10% by weight by using a radical polymerization initiator having a temperature difference of 5 ° C or more and changing the polymerization reaction by 5 ° C or more. 3
56. The negative frictionally chargeable toner according to any one of items 4 to 56. 58. The negative frictionally chargeable toner according to claim 50, wherein at least one kind of wax is added during the production of the binder resin. 59. The toner according to claim 1, wherein the toner contains 1.0 to 8.0 parts by weight of the organic zirconium compound based on 100 parts by weight of the binder resin. Negative friction charging toner. 60. The toner according to claim 1, wherein the toner contains 0.5 to 10 parts by weight of the organic zirconium compound based on 100 parts by weight of the binder resin. Triboelectric charging toner. 61. The negative frictionally chargeable toner according to claim 1, wherein the toner is used as a one-component developer. 62. The toner of claim 1, wherein the toner is mixed with carrier particles and used as a two-component developer. 63. (I) a developing step of developing an electrostatic charge image carried on an image carrier for carrying the electrostatic charge image with a negative frictionally chargeable toner to form a toner image; (II) the image; A transfer step of transferring the toner image formed on the carrier to a recording material with or without an intermediate transfer member; and (III) heat fixing the toner image transferred to the recording material to the recording material. The negative frictionally chargeable toner contains at least a binder resin, a colorant, a wax, and an organometallic compound.
The acid value of the toner is 5 to 35 mgKOH / g,
(B) the binder resin of the toner is a vinyl polymer,
(C) The binder resin of the toner has a chloroform-insoluble content of 3 to 50% by weight, and (d) the tetrahydrofuran (THF) -soluble content of the toner in a chromatogram measured by gel permeation chromatography (GPC)
Having a main peak in the molecular weight region of 5,000 to 30,000,
(E) containing 15 to 70% of a component having a molecular weight of 10,000 to 100,000 and having at least one subpeak and / or shoulder in a region having a molecular weight of 200,000 to 1.5 million, and (e) the organometallic compound contains zirconium and An organic zirconium compound in which an aromatic compound selected from the group consisting of an aromatic diol, an aromatic hydroxycarboxylic acid, an aromatic monocarboxylic acid, and an aromatic polycarboxylic acid is coordinated and / or bonded. Image forming method. The acid value of the toner is 10 to 30 mgK.
The image forming method according to claim 63, wherein OH / g is used. 65. The image forming method according to claim 63, wherein the binder resin of the toner contains 5 to 45% by weight of a chloroform-insoluble content. 66. The image forming method according to claim 63, wherein the binder resin of the toner contains 10 to 40% by weight of a chloroform-insoluble content. 67. The image forming apparatus according to claim 63, wherein the THF-soluble component of the toner has a main peak in a molecular weight region of 7,000 to 25,000 in a chromatogram measured by GPC. Method. 68. The image according to claim 63, wherein the THF-soluble component of the toner has a main peak in a molecular weight region of 9000 to 20,000 in a chromatogram measured by GPC. Forming method. 69. The THF-soluble component of the toner was found to have a molecular weight of 10,000 to 10 in a chromatogram measured by GPC.
70. The image forming method according to claim 63, wherein the composition contains 20 to 60% by weight of the components. 70. The toner according to claim 63, wherein the THF-soluble component of the toner contains 25 to 50% by weight of a component having a molecular weight of 100,000 or more in a chromatogram measured by GPC. Image forming method. 71. The THF-soluble component of the toner has a molecular weight of 300,000 to 1 in a chromatogram measured by GPC.
64. At least one subpeak and / or shoulder in a region of 200,000.
70. The image forming method according to any one of the above items. 72. The THF-soluble component of the toner has a molecular weight of 300,000 to 1 in a chromatogram measured by GPC.
7. The composition according to claim 6, wherein the composition has at least one subpeak and / or shoulder in a region of 200,000 and contains 25 to 50% by weight of a component having a molecular weight of 100,000 or more.
70. The image forming method according to any one of items 3 to 69. 73. The image forming method according to claim 63, wherein the organic zirconium compound is added to the toner as a charge control agent. 74. The organic zirconium compound according to claim 63, wherein the organic zirconium compound is a zirconium complex in which an aromatic diol, an aromatic hydroxycarboxylic acid or an aromatic polycarboxylic acid is coordinated. The image forming method as described in the above. 75. The organic zirconium compound according to claim 63, wherein the organic zirconium compound is a zirconium complex salt which coordinates an aromatic diol, an aromatic hydroxycarboxylic acid or an aromatic polycarboxylic acid. The image forming method as described in the above. 76. The organic zirconium compound containing, as a main component, a zirconium complex or a complex salt in which one molecule of an aromatic diol, aromatic hydroxycarboxylic acid or aromatic carboxylic acid is coordinated.
74. The image forming method according to any one of the above items. 77. The organic zirconium compound contains as a main component a zirconium complex or a complex salt in which an aromatic diol, an aromatic hydroxycarboxylic acid or an aromatic carboxylic acid is coordinated in two molecules.
74. The image forming method according to any one of the above items. 78. The organic zirconium compound contains, as a main component, a zirconium complex or a complex salt in which three molecules of an aromatic diol, an aromatic hydroxycarboxylic acid or an aromatic carboxylic acid are coordinated.
74. The image forming method according to any one of the above items. 79. The organic zirconium compound containing a zirconium complex or complex salt in which four molecules of an aromatic diol, aromatic hydroxycarboxylic acid or aromatic carboxylic acid are coordinated as a main component.
74. The image forming method according to any one of the above items. 80. The organic zirconium compound is a zirconium salt of an aromatic carboxylic acid having an aromatic carboxylic acid, an aromatic hydroxycarboxylic acid or an aromatic polycarboxylic acid. The image forming method according to any one of the above. 81. The image forming method according to claim 63, wherein the organic zirconium compound has a structure represented by the following formula (1). Embedded image [Wherein, Ar represents an alkyl group, an aryl group,
Aralkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryloxy group, hydroxyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group,
X and Y represent an aromatic residue which may have an acyloxy group, a carboxyl group, a halogen, a nitro group, a cyano group, an amino group, an amide group or a carbamoyl group;
X and Y may be the same or different, L represents a neutral ligand, water, alcohol, ammonia, alkylamine or pyridine, and C ₁ represents Monovalent cation, hydrogen, monovalent metal ion,
Represents ammonium or alkylammonium and represents C ₂
Represents a divalent cation or a divalent metal ion, n represents 2, 3, or 4, m represents 0, 2, or 4, and an aromatic carboxylic acid serving as a ligand in each complex or each complex salt; The aromatic diols may be the same or different, and may be a mixture of complex compounds having different numbers of n and / or m, and the counter ions C ₁ and C ₂
May be a mixture of different complex salts. ] 82. The image forming method according to claim 63, wherein the organic zirconium compound has a structure represented by the following formula (2). Embedded image [Wherein, Ar represents an alkyl group, an aryl group,
Aralkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryloxy group, hydroxyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group,
X and Y represent an aromatic residue which may have an acyloxy group, a carboxyl group, a halogen, a nitro group, a cyano group, an amino group, an amide group or a carbamoyl group;
X and Y may be the same or different, L represents a neutral ligand, water, alcohol, ammonia, alkylamine or pyridine, and A represents an anion. Represents a halogen, a hydroxyl ion, a carboxylate ion, a carbonate ion, a nitrate ion, a sulfate ion, a cyanide ion or a thiocyan ion, A may have different ions from each other, C ₁ is a monovalent cation,
Hydrogen, a monovalent metal ion, ammonium or alkylammonium; C ₂ represents a divalent cation or a divalent metal ion; n represents 1, 2, 3, or 4;
Represents 1, 2, 3, 4, 5 or 6, and m represents 0, 1,
2, 3, or 4, wherein the anion A, aromatic carboxylic acid and aromatic diol which are ligands in each complex or each complex salt may be the same or different, and n or / And a mixture of complex compounds having different numbers of m and m, or a mixture of complex salts having different counter ions C ₁ and C _{2. When} A is a divalent anion, the counter cation coefficient k is doubled. ] 83. The image according to claim 63, wherein the organic zirconium compound has a structure represented by the following formula (3), (4) or (5). Forming method. Embedded image Wherein R is hydrogen, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, Group, a halogen, a nitro group, an amino group or a carbamoyl group, which may be linked to each other to form an aliphatic ring, an aromatic ring or a heterocyclic ring, in which case the ring may have a substituent R And the substituent R is 1
You may have up to eight, even if each is the same,
C ₁ may represent a monovalent cation, hydrogen, alkali metal, ammonium or alkylammonium, 1 represents an integer of 1 to 8, and n represents 2, 3 or 4
And m represents 0, 2 or 4, and the aromatic carboxylic acid or aromatic diol serving as a ligand in each complex or complex salt may be the same or different, and n or It may be a mixture of complex compounds having different numbers of / and m, or a mixture of complex salts having different counter ions C ₁ . ] 84. The image according to claim 63, wherein said organic zirconium compound has a structure represented by the following formula (6), (7) or (8): Forming method. Embedded image Wherein R is hydrogen, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, Group, a halogen, a nitro group, an amino group or a carbamoyl group, which may be linked to each other to form an aliphatic ring, an aromatic ring or a heterocyclic ring, in which case the ring may have a substituent R And the substituent R is 1
You may have up to eight, even if each is the same,
A may be different, A represents an anion, a halogen, a hydroxide ion, a carboxylate ion, a carbonate ion, a nitrate ion, a sulfate ion, a cyanide ion or a thiocyan ion, and A may have mutually different ions. , C ₁
Represents a monovalent cation, hydrogen, a monovalent metal ion, ammonium or alkylammonium, and n represents 1,
Represents 2,3 or 4, k represents 1,2,3,4,5 or 6, m represents 0,1,2,3 or 4, and is a ligand in each complex or each complex salt The aromatic carboxylic acids and aromatic diols may be the same or different, and may be a mixture of complex compounds having different numbers of n and / or m, and may be a cation C ₁ or / and A mixture of two or more complex compounds having different anions A may be used. When A is a divalent anion, the coefficient k of the counter cation is doubled. ] 85. The image forming method according to claim 63, wherein the organic zirconium compound has a structure represented by the following formula (36) or (37). Embedded image [Wherein, Ar represents an alkyl group, an aryl group,
Aralkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, hydroxyl, acyloxy, alkoxycarbonyl, aryloxycarbonyl, acyl, carboxyl, halogen, nitro, cyano, amino, amide A ₁ represents a monovalent anion, a halogen ion, a hydroxide ion, a nitrate ion or a carboxylate ion, A ₂ represents a divalent anion,
Represents a sulfate ion, a hydrogen phosphate ion or a carbonate ion, and n represents 1, 2, 3 or 4, and in each metal salt, an anion A ₁ , an anion A ₂ , an aromatic carboxylic acid and an aromatic hydroxy carboxylic acid which become an acid ion. The acids may be the same or different, and may be a mixture of salts with different numbers of n. ] 86. The image forming method according to claim 63, wherein the organic zirconium compound has a structure represented by the following formula (38) or (39). Embedded image Wherein R is hydrogen, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, Group, a halogen, a nitro group, an amino group, an amide group or a carbamoyl group, which may be connected to each other to form an aliphatic ring, an aromatic ring or a heterocyclic ring. May have 1 to 8 substituents R, which may be the same or different, and A ₁ is a monovalent anion, a halogen ion, a hydroxyl ion, a nitrate ion or A ₂ represents a divalent anion, a sulfate ion, a hydrogen phosphate ion or a carbonate ion, and 1 represents 1
Represents an integer of ８8, n represents 1, 2, 3, or 4;
In each metal salt, the anion A ₁ , the anion A ₂ and the aromatic carboxylic acid serving as the acid ion may be the same or different, or may be a mixture of salts having different numbers of n. . ] 87. The image forming method according to claim 63, wherein the organic zirconium compound has a structure represented by the following formula (40) or (41). Embedded image Wherein R is hydrogen, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, Group, a halogen, a nitro group, an amino group, an amide group or a carbamoyl group, which may be connected to each other to form an aliphatic ring, an aromatic ring or a heterocyclic ring. May have 1 to 8 substituents R, which may be the same or different, and A1 is a monovalent anion, a halogen ion, a hydroxyl ion, a nitrate ion or a carboxylic acid. A2 represents an acid ion, A2 represents a divalent anion, a sulfate ion, a hydrogen phosphate ion or a carbonate ion;
And n represents 1, 2, 3, and 4. In each metal salt, the anion A1, the anion A2, and the aromatic carboxylic acid serving as an acid ion may be the same or different. Alternatively, a mixture of salts having different numbers of n may be used. ] 88. The image forming method according to claim 63, wherein said vinyl polymer has a carboxyl group and / or an anhydrous carboxyl group. 89. The organic zirconium compound can form a chloroform-insoluble component by interacting with a carboxyl group and / or an anhydrous carboxyl group contained as a substituent of a vinyl polymer as a binder resin. The image forming method according to claim 88, wherein: 90. The organic zirconium compound as a zirconium element in a chloroform-insoluble content in a total amount of 3%.
7. The composition according to claim 6, wherein the content is 0% by weight or more.
The image forming method according to any one of Items 3 to 89. 91. The organic zirconium compound as a zirconium element in chloroform-insoluble matter in a total amount of 4%.
7. The composition according to claim 6, wherein the content is 0% by weight or more.
The image forming method according to any one of Items 3 to 89. 92. The zirconium compound contained in the toner, wherein the zirconium element is contained in chloroform-insoluble matter in an amount of 50% by weight or more based on the total amount of the zirconium element. Image forming method. 93. The difference (Av · G−Av · S) between the acid value (Av · S) of the chloroform-soluble portion of the toner and the acid value (Av · G) of the chloroform-insoluble portion of the toner is from 10 to 90. 7. The amount is 150 mgKOH / g.
The image forming method according to any one of Items 3 to 92. 94. The difference (Av · G−Av · S) between the acid value (Av · S) of the chloroform-soluble portion of the toner and the acid value (Av · G) of the chloroform-insoluble portion of the toner is 20 to 90. 7. The amount is 130 mg KOH / g.
The image forming method according to any one of Items 3 to 92. A difference (Av · G−Av · S) between the acid value (Av · S) of the chloroform-soluble portion of the toner and the acid value (Av · G) of the chloroform-insoluble portion of the toner is 30 to 90. 7. The amount is 100 mg KOH / g.
The image forming method according to any one of Items 3 to 92. 96. In the toner, (A) the toner has a contact angle of 105 to 130 degrees with water,
(B) the binder resin has a vinyl polymer having an acid value of 5 to 40 mgKOH / g, and (C) the resin component of the toner has a tetrahydrofuran (THF) insoluble content of 5 to 60% by weight. %, And the wax has a molecular weight of 300 to 5,000 in a chromatogram measured by gel permeation chromatography (GPC).
Has a main peak (Mp) and a weight average molecular weight (Mp).
The image forming method according to any one of claims 63 to 95, wherein the ratio (Mw / Mn) of w) to the number average molecular weight (Mn) is 1.2 to 15. 97. The toner has a contact angle of 107 with water.
97. The lens of claim 96, wherein the angle is between -127 degrees.
2. The image forming method according to 1., 98. The toner has a contact angle of 110 with water.
97. The device of claim 96, wherein the angle is between 125 and 125 degrees.
2. The image forming method according to 1., 99. The binder resin comprises 7 to 35 mg KOH.
The image forming method according to any one of claims 96 to 98, comprising a vinyl polymer having an acid value of / g. 100. The binder resin is 10 to 30 mgK.
The image forming method according to any one of claims 96 to 98, comprising a vinyl polymer having an acid value of OH / g. 101. The image forming method according to claim 96, wherein the binder resin of the toner contains 7 to 55% by weight of a THF-insoluble component. The image forming method according to any one of claims 96 to 100, wherein the binder resin of the toner contains 10 to 50% by weight of a THF-insoluble component. 103. The wax has a main peak at a molecular weight of 600 to 4500 in a chromatogram measured by GPC and has a ratio (Mw / Mn) of 1.5 to 10
The image forming method according to any one of claims 96 to 102, wherein: 104. The wax according to claim 96, wherein the wax has a main peak at a molecular weight of 700 to 4000 in a chromatogram measured by GPC, and has a ratio (Mw / Mn) of 1.7 to 8. 102. The image forming method according to any one of Items 102 to 102. 105. The wax is a hydrocarbon wax,
The image forming method according to claim 103, wherein the image forming method is any one of a polyethylene polymer and a polypropylene polymer. 106. The toner according to claim 103, wherein the wax has a structure represented by the formula (a). Embedded image (In the formula, A represents a hydroxyl group or a carboxyl group, and a represents an integer of 20 to 60.) 107. The wax according to claim 1, wherein the wax is 1 to 20 mg KOH.
The image forming method according to claim 103, wherein the image forming method is an acid-modified polypropylene having an acid value of / g. 108. The wax is 1 to 20 mg KOH.
104. The image forming method according to claim 103, which is an acid-modified polyethylene having an acid value of / g. 109. The wax is a differential scanning calorimeter (D)
SC), the endothermic main peak temperature at the time of temperature rise is 7
The image forming method according to claim 103, wherein the temperature is 0 to 140 ° C. 110. The wax may be a differential scanning calorimeter (D
104. The image forming method according to claim 103, wherein a melting point defined by an endothermic peak temperature at the time of temperature rise measured in SC) is 80 to 135 ° C. 111. The wax comprises a differential scanning calorimeter (D
104. The image forming method according to claim 103, wherein a melting point defined by an endothermic peak temperature at the time of temperature rise measured in SC) is 85 to 130 ° C. 112. The toner contains two or more kinds of different waxes, and has a molecular weight of 5 in the chromatogram of all the waxes contained in the toner by GPC measurement.
It has a main peak between 00 and 7000 and has a ratio (Mw / M
10. The method according to claim 9, wherein n) is 1.2 to 15.
The image forming method according to any one of Items 6 to 102. 113. The toner contains two or more kinds of different waxes, and has a molecular weight of 7 according to GPC measurement chromatogram of all waxes contained in the toner.
It has a main peak at 00 to 6000 and has a ratio (Mw / M
10. The method according to claim 9, wherein n) is 1.5 to 12.
The image forming method according to any one of Items 6 to 102. 114. The toner contains two or more kinds of different waxes, and has a molecular weight of 1 in the chromatogram of all the waxes contained in the toner by GPC measurement.
It has a main peak at 000 to 5000 and a ratio (Mw /
96. The method of claim 96, wherein Mn) is 2 to 10.
103. The image forming method according to any one of the above items. 115. The image forming method according to claim 112, wherein the at least one kind of wax is one of a hydrocarbon wax, a polyethylene polymer and a polypropylene polymer. 116. The method according to claim 1, wherein at least one kind of wax has a structure represented by the formula (a).
13. The image forming method according to item 12. Embedded image (In the formula, A represents a hydroxyl group or a carboxyl group, and a represents an integer of 20 to 60.) 117. The image forming method according to claim 112, wherein at least one kind of wax is an acid-modified polypropylene having an acid value of 1 to 20 mgKOH / g. 118. The image forming method according to claim 112, wherein at least one kind of wax is an acid-modified polyethylene having an acid value of 1 to 20 mgKOH / g. 119. The binder resin has an aromatic vinyl monomer and a (meth) acrylic acid ester monomer in a molecule having two or more peroxide groups, and halves the cleavage reaction of each peroxide group for 10 hours. Using a radical polymerization initiator having a temperature difference of 5 ° C. or more, the polymerization reaction is carried out at 5 ° C.
119. The image forming method according to claim 96, wherein the vinyl polymer synthesized by a radical polymerization method is contained in an amount of 10% by weight or more. 120. The method according to claim 11, wherein at least one kind of wax is added during the production of the binder resin.
3. The image forming method according to item 2. 121. The toner comprises the organic zirconium compound in an amount of 1.0 to 8.0 parts by weight based on 100 parts by weight of the binder resin.
125. The composition according to claim 63, wherein the content is part by weight.
The image forming method according to any one of the above. 122. The toner may contain the organic zirconium compound in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the binder resin.
125. The composition according to claim 63, wherein the content is part by weight.
The image forming method according to any one of the above. 123. An image forming method according to claim 63, wherein said toner image is formed using said toner as a one-component developer. The image forming method according to any one of claims 63 to 122, wherein the toner image is formed by mixing the toner with carrier particles and using the mixture as a two-component developer.