JP3230044B2 - Electrostatic image developing toner, image forming method, and process cartridge - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used as a developer for developing an electrostatic image such as electrophotography and electrostatic printing, and more particularly to a negatively chargeable toner. Further, the present invention provides
The present invention relates to an image forming method using the toner and a process cartridge having the toner.

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
JP-A (U.S. Pat. No. 3,666,363) and JP-B-43-24748 (U.S. Pat.
Many methods are known, for example, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means, and then the latent image is developed. (Hereinafter referred to as "toner"), transfer the toner image to a transfer material such as paper if necessary, and fix it with a heat, pressure, pressure heat fixing roller or solvent vapor, etc. to make a copy or print. Is what you get.

In the case where a step of transferring a toner image is provided, a step for removing residual toner on the photoconductor is usually provided.

As a developing method for visualizing an electric latent image using toner, for example, US Pat. No. 2,874,06
No. 3,618,552, and the cascade developing method described in U.S. Pat. No. 2,618,552, and U.S. Pat. No. 2,221,776. Powder cloud method, US Patent 3,909,2
A method using a conductive magnetic toner described in Japanese Patent No. 58-58 is known.

Various methods and techniques have been developed for the final step of fixing a toner image on a sheet such as paper. Currently, the most common method is a pressure heating method using a heating roller. The pressure heating method using a heating roller performs fixing by allowing the toner image surface of the sheet to be fixed to pass through the surface of the heating roller having a surface formed of a material having releasability with respect to the toner while pressing the surface under pressure. It is. According to this method, since the surface of the heating roller and the toner image of 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 is quickly performed. be able to.

In recent years, a fixing device has been put into practical use, which has a pressing member which is opposed to a heating member and which is in contact with a heating member instead of a heat roller, and which makes a recording material adhere to the heating member via a film.

Further, in recent years, with the spread of printers, digitalization of copiers, and finer toner particles, higher image quality of copy images has been desired.

In particular, in a photographic image containing characters, it is required that the characters of the copy image be clear, and that the photographic image have a density gradation characteristic faithful to the original. In general, in copying a photographic image containing characters, if the line density is increased in order to make the characters clear, not only the density gradation of the photographic image is impaired, but also the halftone portion tends to be very rough.

Further, as described above, the line image is crushed or jumped at the time of fixing, and the image quality of the copy image is liable to be deteriorated.

Further, when the line density is increased, the toner is pressed against the photoconductor at the time of transfer and adheres to the photoconductor due to a large amount of toner applied in the toner transfer process. A hollow image may occur, resulting in a low-quality copy image. Conversely, when trying to improve the density gradation of a photographic image, the density of the character lines is reduced, and the sharpness is likely to be reduced.

In recent years, density gradation has been improved to some extent by reading image density and converting it into digital data. However, further improvements are desired.

This is largely due to the developing characteristics of the developer. In other words, the development potential (difference between the photoconductor potential and the developer carrier potential) and the image density do not have a linear relationship. In the halftone region, the image density becomes very small due to a slight change in the development potential. Greatly change. Therefore, it is difficult to obtain a sufficiently satisfactory density gradation.

Normally, in order to copy a line image and maintain its sharpness, the amount of toner increases due to the influence of the edge effect. Therefore, the maximum image density in a solid image portion which is not easily affected by the edge effect is obtained. Is about 1.30, and a sufficient line image can be obtained.

However, in a photographic image, the maximum density of the photograph itself largely depends on its surface glossiness, which is 1.9.
It is very high, from 0 to 2.00. Therefore, in copying a photographic image, even if the glossiness of the surface is suppressed, since the image area is large, there is substantially no increase in density due to the edge effect. Therefore, the maximum image density in the solid image portion is 1. 4
About 1.5 is required.

Therefore, the developing potential and the image density are set to a first-order (linear) relationship, and the maximum image density is set to 1.4 to
A value of 1.5 is very important in copying a photo image containing text.

Further, the density gradation is greatly affected by the saturation charge amount and charging speed of the toner. If the saturation charge amount is appropriate for the development conditions, and the frictional charging speed of the toner is further low, in the initial toner image,
The maximum image density is low and tends to be thin and blurry as a whole.

As described above, if the maximum image density is about 1.3, there is no problem in the case of a line image, and there is little problem even if the toner charging speed is low.

Even when the charging speed is low, the initial copy image density increases when the saturation charge amount of the toner is increased. However, when continuous copying is performed, the charge amount of the toner gradually increases, and may eventually exceed the development proper charge amount, resulting in a decrease in copy image density. In this case as well, as described above, if the maximum image density is about 1.3, there is no problem or there is little problem with the line image.

In other words, these factors are more influenced by the saturation charge amount and charging speed of the toner in the photographic image than in the line image.

On the other hand, when the particle size of the toner is reduced, it is apparent that the dispersion state of the charge control agent and the colorant greatly affects the chargeability of the toner.

As a method of controlling the charge of the toner used in the toner for developing an electrostatic image, there is a method of adding a dye or a pigment, which is generally called a charge control agent, to the toner. The compound has been used.

According to Japanese Patent Application Laid-Open No. 60-170864, among the chromium complex salt compounds, those having good compatibility with the binder resin exhibit a uniform negative charging property and can provide a clear copy image. Those that are liable to cause residual toner to be wiped on the photoreceptor due to poor cleaning and filming phenomenon, and that are insoluble in a binder resin (especially polyester resin) have good chargeability and good filming. Has been described.

However, a toner using a metal complex compound insoluble in a binder resin has poor dispersibility in a binder resin. Therefore, when the toner is made into fine particles using such a metal complex salt compound, the toner tends to be excessively charged particularly under low humidity, and fog and a decrease in density are likely to occur. This is because, in the fine pulverization step in the production of toner, a large difference occurs between the charge control agent amount ratio (weight ratio) of the generated fine powder having a small particle size and the charge control agent amount ratio (weight ratio) of the coarse powder having a large particle size ( The so-called segregation of the charge control agent), which causes a difference in the charge amount between the toner particles.

When the classified fine powder and the classified coarse powder generated in the classifying step for classifying the toner particles are reused, the segregation of the charge control agent becomes more remarkable. For this reason, the toner produced by reusing fine powder and coarse powder is liable to reduce the image density due to poor chargeability of the toner under low humidity and fog is likely to occur. Was difficult to reuse together. JP-A-3-2092
As proposed in Japanese Patent Publication No. 66, only the reuse of the classified coarse powder has been limited. JP-A-61-15546
No. 4, JP-A-62-177561 proposes a charge control agent for an azo-based iron complex with improved dispersibility. However, a rapid rise in the charge of the toner cannot be obtained. Under wet conditions, the image density was easily reduced. When the toner is made finer (9 μm or less in weight average diameter) for higher image quality, the charge amount of the toner is significantly increased under low humidity, the line image becomes thinner, the image density is reduced, and the toner is excessively charged. In addition, reverse charging toner is generated due to poor charging of the toner on the developer carrying member, and reverse potential fog is likely to occur.

To improve the chargeability of a toner using such an azo-based iron complex, JP-A-1-3066862 proposes a developer using a silicone resin-coated carrier having a high charge-imparting property. Japanese Unexamined Patent Publication No. 2-153362 proposes a developing device in which a toner layer thickness regulating member and a toner replenishment auxiliary member are improved. These are intended to improve the developability of the toner by using a charging member other than the toner, and are not sufficient as the intrinsic performance of the toner itself. It is difficult to maintain good images across.

[0026]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide a toner for developing an electrostatic image capable of maintaining high quality image quality for a long period of time.

It is an object of the present invention to provide a toner for developing an electrostatic charge image which has a good dispersibility of a charge control agent, a uniform charge of the toner, maintains a high image density for a long period of time, and has a high resolution without fog. Aim.

It is an object of the present invention to provide a toner for developing an electrostatic image, in which the toner is rapidly charged, and a good image equivalent to that before the standing can be obtained even when the toner is left for a long time or under high humidity.

An object of the present invention is to provide a toner for developing an electrostatic charge image which can obtain a high quality image without using a special charging auxiliary member.

An object of the present invention is to provide a toner for developing an electrostatic image capable of obtaining a satisfactory image over a long period of time even in various environments, even in a fine particle toner corresponding to high-definition image development.

An object of the present invention is to provide a toner for developing an electrostatic charge image, which can reuse classified fine powder and classified coarse powder generated in toner production.

It is an object of the present invention to provide a toner for developing an electrostatic image, which is highly adaptable to an electrophotographic process which does not adversely affect a photosensitive member or a developer carrier.

An object of the present invention is to provide an image forming method and a process cartridge using these toners.

[0034]

That is, the present invention provides a binder resin having the following formula (1), (2) or (3):

[0035]

Embedded image [Where x represents an average value and is from 35 to 150]. ]

[0036]

Embedded image [In the formula, x represents an average value, from 35 to 150, z represents an average value, from 1 to 5, and R represents hydrogen or 1 carbon atom.
Represents from 10 to 10 alkyl groups. ]

[0037]

Embedded image [In the formula, y represents an average value and is 35 to 150. ], And an azo-based iron complex compound represented by the following formula (4):

[0038]

Embedded image [Wherein X ₁ and X ₂ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a halogen atom, and X ₁ and X ₂ may be the same or different;
And m 'represents an integer of 1 to 3, R ₁ and R ₃ is a hydrogen atom, an alkyl of C ₁ ~ _18, alkenyl, sulfonamide, mesyl, sulfonic acid, carboxy ester, hydroxy, alkoxy of C ₁ ~ _18, R ₁ and R ₃ represent an acetylamino, benzoylamino group or a halogen atom;
May be the same or different; n and n ′ represent an integer of 1 to 3; R ₂ and R ₄ represent a hydrogen atom or a nitro group; A ⁺ represents a cation ion;
It has ９８98 mol% of ammonium ions, and additionally has hydrogen ions, sodium ions, potassium ions or mixed ions thereof. ]

Further, the present invention provides a charging step of applying a voltage to the charging means while bringing the charging means into contact with the member to be charged to charge the member to be charged, and forming an electrostatic image on the charged member to be charged. And developing the electrostatic image with toner to form a toner image on the member to be charged, and transferring the toner image on the member to be transferred to the transfer material with or without the intermediate transfer member. An image forming method including a transfer step of transferring and a fixing step of heating and fixing a toner image on a transfer material, wherein the toner is a binder resin, the following formula (1), (2) or (3):

[0040]

Embedded image [Where x represents an average value and is from 35 to 150]. ]

[0041]

Embedded image [In the formula, x represents an average value, from 35 to 150, z represents an average value, from 1 to 5, and R represents hydrogen or 1 carbon atom.
Represents from 10 to 10 alkyl groups. ]

[0042]

Embedded image [In the formula, y represents an average value and is 35 to 150. And a azo-based iron complex compound represented by the following formula (4):

[0043]

Embedded image [Wherein X ₁ and X ₂ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a halogen atom, and X ₁ and X ₂ may be the same or different;
And m 'represents an integer of 1 to 3, R ₁ and R ₃ is a hydrogen atom, an alkyl of C ₁ ~ _18, alkenyl, sulfonamide, mesyl, sulfonic acid, carboxy ester, hydroxy, alkoxy of C ₁ ~ _18, R ₁ and R ₃ represent an acetylamino, benzoylamino group or a halogen atom;
May be the same or different; n and n ′ represent an integer of 1 to 3; R ₂ and R ₄ represent a hydrogen atom or a nitro group; A ⁺ represents a cation ion;
It has ９８98 mol% of ammonium ions, and additionally has hydrogen ions, sodium ions, potassium ions or mixed ions thereof. ]

Further, the present invention is a process cartridge having at least a developing means and a photoreceptor, wherein the developing means and the photoreceptor are integrally formed as a cartridge.
The process cartridge is detachable from the image forming apparatus main body, and the developing means is a binder resin, the following formula (1), (2) or (3)

[0045]

Embedded image [Where x represents an average value and is from 35 to 150]. ]

[0046]

Embedded image [In the formula, x represents an average value, from 35 to 150, z represents an average value, from 1 to 5, and R represents hydrogen or 1 carbon atom.
Represents from 10 to 10 alkyl groups. ]

[0047]

Embedded image [In the formula, y represents an average value and is 35 to 150. ] And a long-chain alkyl compound represented by the following formula (4):

[0048]

Embedded image [Wherein X ₁ and X ₂ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a halogen atom, and X ₁ and X ₂ may be the same or different;
And m 'represents an integer of 1 to 3, R ₁ and R ₃ is a hydrogen atom, an alkyl of C ₁ ~ _18, alkenyl, sulfonamide, mesyl, sulfonic acid, carboxy ester, hydroxy, alkoxy of C ₁ ~ _18, R ₁ and R ₃ represent an acetylamino, benzoylamino group or a halogen atom;
May be the same or different; n and n ′ represent an integer of 1 to 3; R ₂ and R ₄ represent a hydrogen atom or a nitro group; A ⁺ represents a cation ion;
It has ９８98 mol% of ammonium ions, and additionally has hydrogen ions, sodium ions, potassium ions or mixed ions thereof. A toner containing the azo-based iron complex compound represented by the formula (1).

The present inventors have conducted intensive studies and as a result, by combining a certain type of charge control agent and a long-chain alkyl compound, it was possible to maintain a stable image for a long period without being affected by the environment while maintaining high developability. It has been found that a toner that can be maintained can be provided.

That is, in the toner for developing an electrostatic image of the present invention, a metal complex compound represented by the following general formula (4)

[0051]

Embedded image [Wherein X ₁ and X ₂ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a halogen atom, and X ₁ and X ₂ may be the same or different;
And m 'represents an integer of 1 to 3, R ₁ and R ₃ is a hydrogen atom, an alkyl of C ₁ ~ _18, alkenyl, sulfonamide, mesyl, sulfonic acid, carboxy ester, hydroxy, alkoxy of C ₁ ~ _18, R ₁ and R ₃ represent an acetylamino, benzoylamino group or a halogen atom;
May be the same or different; n and n ′ represent an integer of 1 to 3; R ₂ and R ₄ represent a hydrogen atom or a nitro group; A ⁺ represents a cation ion;
It has ９８98 mol% of ammonium ions, and additionally has hydrogen ions, sodium ions, potassium ions or mixed ions thereof. ] Is a major feature.

In general, when an azo-based iron complex compound is used as a charge control agent for an electrophotographic developer (toner), the rise of charging under high humidity is insufficient, and the initial state under high humidity or long-term storage It is difficult to obtain a satisfactory image density for the test. Also, for continuous long-term use under low humidity,
An excessive amount of charge is accumulated (charge-up), the image density is low, and fogging is conspicuous.

On the other hand, chromium and aluminum complex compounds which are insoluble in the binder resin have been widely used because the above-mentioned problems are reduced, but toners using such chromium and aluminum complex compounds are not widely used. There is a problem that it is difficult to reuse the classified fine powder and the classified coarse powder generated in the toner manufacturing process. This is because the chromium complex compound or the aluminum complex compound is segregated in the classified fine powder, the classified medium powder (used as a toner), and the classified coarse powder, and the toner manufactured by recycling the classified fine powder and the classified coarse powder is used in a low humidity environment. This is because a continuous long-term use tends to cause a decrease in image density and fog.

The present inventors have found that the segregation property of the azo-based iron complex compound in the classified powder is small and that the toner using the azo-based chromium complex compound insoluble in the binder resin having high segregation property has good developability. Considering that, by forming microdomains of the azo-based iron complex compound in the toner particles, the charge controllability of the azo-based iron complex compound can be improved and the non-segregation property of the azo-based iron complex compound can be maintained. It is a thing.

The formation of the microdomain of the azo-based iron complex compound is performed by the presence of the long-chain alkyl compound in the toner particles. This is presumed that the OH group or the carboxyl group of the long-chain alkyl compound forms an associated state, and the azo-based iron complex compound forms a microdomain under the influence of the aggregate. This makes it possible to improve the charge controllability while maintaining the non-segregation property of the azo-based iron complex compound.

The segregation property of the azo-based iron complex compound in the classified fine powder, the classified medium powder (used as toner), and the classified coarse powder generated in the production process of the toner using the azo-based iron complex compound was examined by the following method. 1.0 g to 3.0 g of each classified powder
Is weighed and placed in 200 ml of ethyl alcohol.
After dispersion with stirring for a time, the mixture was filtered, and the visible absorption spectrum of the filtrate was measured.
The relative absorbance at 480 nm was compared, and the segregation was evaluated based on the following index.

Absorbance O of the filtrate obtained from the classified fine powder
D _F , the absorbance OD _M of the filtrate obtained from the classified medium powder, the absorbance OD _G of the filtrate obtained from the classified coarse powder,

[0058] was used as an index of the segregation of the value of the OD value of _F / OD _M and OD _G / OD _M classification fines and classified coarse powder.

Further, it is preferable that A ^{+ of} the azo-based iron complex compound represented by the general formula contains 75 to 98 mol% of ammonium ions in order to obtain a stable toner image. When the azo-based iron complex compound has only an ammonium ion as a cation, there is a tendency that the image density after standing under high humidity has a slow rise. On the other hand, when only a proton or an alkali metal is contained as a cation, the image density under high humidity changes slightly.

The present inventors have studied and found that a compound having good long-term storage characteristics can be obtained by coexisting ammonium ions and alkali metal ions and / or protons as cation components. In particular, when the ammonium ion content is 75 to 98 mol%, the image density rises,
And the rising density level becomes better.

If the ammonium ion content is less than 75%, the image density tends to be low, and if it exceeds 98%, the rise of the image density tends to be slow.

Further, the present inventors have studied and found that the solubility of the azo-based iron complex compound used in the toner of the present invention in methanol is 0.1 g / 100 ml to 8 g / m.
100 ml, preferably 0.3 g / 100 ml to 4 g /
100 ml (more preferably 0.4 g / 100 ml to 2
g / 100 ml).

When the solubility is less than 0.1 g / 100 ml, the dispersibility of the charge control agent in the toner is low even if a long-chain alkyl compound is used, and the toner tribo becomes unstable, causing image fogging and scattering. Easily occur.

On the other hand, when the solubility is more than 8 g / 100 ml, long-term storage in a high-temperature, high-humidity environment
The toner is easily affected by temperature and humidity, and the chargeability of the toner is easily deteriorated, and it is difficult to obtain a sufficient image density.

These charge control agents are preferably used in an amount of 0.2 to 5 parts by weight based on 100 parts by weight of the binder resin.

In the present invention, the solubility of the charge control agent is measured as follows.

<Method of Measuring Solubility of Charge Control Agent> 2 g of the charge control agent is weighed and charged into a 300 ml Erlenmeyer flask. 100 ml of methanol is added thereto, the temperature is raised to 50 ° C. with stirring, and stirring is continued for 1 hour (when all the charge control agents are dissolved, further 2 g of the charge control agents are added and stirring is continued).

Next, the mixture is cooled to room temperature, and the insoluble charge control agent is filtered through a 0.1 μm filter to obtain a sample solution.
The absorbance at the maximum absorption wavelength is measured using a spectrophotometer. At this time, when the concentration of the charge control agent in the filtered solution is high, the measurement is performed by diluting with methanol as necessary.

On the other hand, the absorbance at the maximum absorption wavelength of a separately prepared standard solution (20 ppm concentration methanol solution) of the charge control agent was measured, and the difference between the absorbance of the standard solution and the absorbance of the sample solution was used. The solubility of the charge control agent in the sample solution is measured according to the law.

[0070] Solubility = charge control agent dissolved amount (g) / methanol (100ml) Lambert - veil _{law: log e (I 0 / I} ) = ε 0 cd [ wherein, I is indicated the intensity of the transmitted light solution , I ₀ indicates the intensity of the transmitted light of methanol, ε ₀ indicates the extinction coefficient, c
Represents the concentration of the charge control agent, and d represents the thickness of the measurement solution. ]

The azo iron complex compound according to the present invention includes those represented by the following general formula (4).

[0072]

Embedded image [Wherein X ₁ and X ₂ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a halogen atom, and X ₁ and X ₂ may be the same or different;
And m 'represents an integer of 1 to 3, R ₁ and R ₃ is a hydrogen atom, an alkyl of C ₁ ~ _18, alkenyl, sulfonamide, mesyl, sulfonic acid, carboxy ester, hydroxy, alkoxy of C ₁ ~ _18, R ₁ and R ₃ represent an acetylamino, benzoylamino group or a halogen atom;
May be the same or different; n and n ′ represent an integer of 1 to 3; R ₂ and R ₄ represent a hydrogen atom or a nitro group; A ⁺ represents a cation ion;
It has ９８98 mol% of ammonium ions, and additionally has hydrogen ions, sodium ions, potassium ions or mixed ions thereof. ]

The azo type iron complex compound is used as a negative charge control agent. The azo-based iron complex compound can be synthesized by known means.

These negative charge control agents may be used alone or in combination of two or more, and may be used together with other negative charge control agents.

Typical specific examples of the azo-based iron complex compound of the above general formula include the following compounds.

[0076]

Embedded image

[0077]

Embedded image

The toner for developing an electrostatic image of the present invention comprises the azo iron complex compound in an amount of 0.1 to 100 parts by weight of the binder resin.
It is preferable to use 10 to 10 parts by weight, preferably 0.1 to 5 parts by weight.

The long-chain alkyl compound used in the present invention is represented by the following formula (1), (2) or (3).

[0080]

Embedded image [X indicates an average value, indicates a real number of 35 to 150, z
Represents an average value, indicates the real 1 to 5, R represents an alkyl group of H or C ₁ -C _10. ]

For example, ethylene is polymerized using a Ziegler catalyst, and after completion of the polymerization, it is oxidized to form an alkoxide of the catalyst metal and polyethylene. Thereafter, hydrolysis is performed to obtain a long-chain alkyl alcohol represented by the formula (1). The long-chain alkyl alcohol is reacted with a substance having an epoxy group to obtain a long-chain alkoxy alcohol represented by the formula (2). The long-chain alkyl alcohols obtained in this way both have few branches and have a sharp molecular weight distribution in accordance with the object of the present invention.

[0082]

Embedded image [Y represents an average value and represents a real number of 35 to 150. ]

The long-chain hydrocarbon compound of the formula (3) is obtained by oxidizing the long-chain hydrocarbon compound of the formula (1).

The long-chain alkyl alcohol or long-chain alkyl carboxylic acid used in the present invention is less than 30% by weight (more preferably, 2%) by weight of a hydrocarbon compound having no functional group.
5% by weight or less).

In the compounds represented by the formulas (1), (2) and (3), the average values x and y are preferably from 35 to 150. When x and y are less than 35, both the photoconductors are fused and the storage stability of the toner is reduced. x and y
Is larger than 150, the above-mentioned contribution to the charging characteristics of the toner (the formation of microdomains of the azo-based iron complex compound) is small, which does not meet the purpose of the present invention. The average value z is preferably 5 or less. z is 5
If it is larger, fusion of the photoconductor is likely to occur.
For the same reason R is a hydrocarbon group of H or C ₁ -C ₁₀ are preferred.

Further, the long-chain alkyl compound used in the present invention preferably has a number average molecular weight Mn of 150 to 2500, a weight average molecular weight Mw of 250 to 5000, and Mw / Mn of 3 or less.

If Mn is less than 150 or Mw is less than 250, fusion of the photoreceptor occurs or the storage stability of the toner is reduced. Moreover, Mn exceeds 2500 or Mw
Exceeds 5,000, the effect on the charging characteristics of the toner is small and problems such as fogging are likely to occur.

The OH value of the long-chain alkyl compound (1) or (2) used in the present invention is 2 mgKOH / mg to 1 mgKOH / mg.
50 mgKOH / mg, preferably 10 mgKOH / m
g to 120 mgKOH / mg. OH value of long-chain alkyl compound (1) or (2) is 2 mgK
If it is less than OH / mg, the dispersibility in the binder resin is reduced, and the toner is liable to be non-uniformly charged. Easy to lower. Further, when the OH value of the long-chain alkyl compound is larger than 150 mgKOH / mg, the bias of the charge density of the OH group becomes large and becomes larger than the bias of the charge density of the OH group in the binder resin. In this case, a phenomenon in which the density is low from the beginning and the density is low, or even if the initial density is high, the density gradually decreases as copying continues. Further, when the OH value is larger than 150 mgKOH / mg, many long-chain alkyl alcohols having a low molecular weight are contained, so that the toner is easily fused to the photoconductor,
Storage stability decreases.

The acid value of the long-chain alkyl compound (3) used in the present invention is from 2 mgKOH / mg to 150 mgKO.
H / mg, preferably 5 mg KOH / mg to 120 mg
It is preferably KOH / mg. Acid value is 2mgKO
If it is less than H / mg, the dispersibility in the binder resin is reduced, and the image quality of the copied image is liable to be reduced. Further, since the carboxyl group does not sufficiently form an aggregate, the charging speed of the toner is reduced, the initial copy density is reduced, and the environmental stability is also reduced. Further, the acid value is 150 mgKOH / mg.
Even when it is larger, since many low molecular weight compounds are included, the toner is easily fused to the photoreceptor, and storage stability is reduced.

When these long-chain alkyl compounds are used alone, they are preferably used in an amount of 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, per 100 parts by weight of the binder resin.

When a long-chain alkyl compound is used in combination, the total amount used is 0.1 parts by weight per 100 parts by weight of the binder resin.
It is preferred to use up to 30 parts by weight, preferably 0.5 to 20 parts by weight.

In the toner of the present invention, the content of toner particles having a particle diameter of 5 μm or less is preferably 3 to 90% by number. Conventionally, toner particles having a particle size of 5 μm or less have a difficulty in controlling the charge or impair the fluidity of the toner, a component that causes contamination of the carrier and the developing sleeve, a component that causes cleaning failure and a problem of filming on the drum, Further, it has been considered that it is necessary to positively remove or reduce as a component that scatters toner and stains the inside of the image forming apparatus.

However, the present inventors have used a specific long-chain alkyl compound, and the toner containing the azo-based iron complex compound of the above formula has high definition toner particles having a particle size of 5 μm or less.
It has been found to be very effective in forming high-resolution images.

Further, in the toner of the present invention, the particle diameter is 6.
It is preferable that the toner particles in the range of 35 to 10.08 μm are 1 to 80% by number. The toner has a weight average particle size of 4.0 to 10 μm, preferably 4.5 to 9.0 μm.
It is preferred that

The toner particles having a particle size of 5 μm or less strictly cover the electrostatic charge image and have a capability of faithfully reproducing the electrostatic charge image. However, in the electrostatic charge image itself, the electrolytic strength of the peripheral edge portion is higher than that of the central portion. In some cases, the toner particles are thinner inside the charge image than at the edge portions, and the image density may appear to be lighter.

However, the present inventors have determined that the particle size is 6.35.
1 to 80% by number of toner particles in the range of
It has been found that this problem can be solved and the content can be further sharpened. This is 6.35 to 10.08 μm on the inner side where the electric field intensity is smaller than the edge of the electrostatic charge image.
Is supplied, and a uniform image is formed by compensating for the small number of toner particles inside the edge portion.
As a result, a sharp image having excellent resolution and gradation is formed at a high density.

Further, for toner particles of 5 μm or less, the following formula N / V = −0.05N + k (where 3 ≦ k ≦ 12; 5 ≦) N ≦ 90) is most preferably satisfied. A toner containing a toner particle group having a particle size distribution satisfying this range can achieve excellent developability even for a digital latent image formed from minute spots. The present inventors have studied the particle size distribution of toner particles having a particle size of 5 μm or less, and have found that there is a condition for the existence of fine toner particles that is most suitable for achieving the object represented by the above formula. The fact that N / V is large with respect to a certain value of N indicates that toner particles of 5 μm or less are widely included, and the fact that N / V is small means that the abundance ratio of toner particles near 5 μm. Is high, indicating that the amount of other toner particles is small.
The value of N / V is in the range of 1.0 to 5.0 and N is 5
The fine line reproducibility and the high resolution can be attained even when a large amount of toner is in the range of 90 to 90 and satisfies the above relational expression for a long time.

For toner particles having a particle diameter of 12.7 μm or more, the content is preferably 2.0% by volume or less, and it is preferable that the amount is as small as possible.

The particle size distribution of the toner particles in the present invention will be described in more detail.

The number of toner particles having a particle diameter of 5 μm or less is preferably 5 to 90% by number of the total number of particles, and more preferably 9 to 75% by number. When the number of toner particles having a particle diameter of 5 μm or less is less than 5% by number, the amount of toner particles effective for high image quality is small. In particular, by continuing copying, a toner particle component necessary for achieving high image quality is reduced. The distribution deteriorates and the image quality gradually decreases. When the number of toner particles having a particle size of 5 μm or less exceeds 90% by number, aggregation and charge-up of the toner particles are liable to occur, resulting in poor cleaning and a decrease in image density, and further, a difference in density between the edge portion and the inside of the latent image. And the image tends to be a so-called hollow image. The number of toner particles having a particle diameter of 6.35 to 10.08 μm is preferably 1 to 80% by number, and more preferably 5 to 80% by number.
70% by number is good. If the number of toner particles having a particle diameter of 6.35 to 10.08 μm is more than 80% by number, the image is deteriorated, and unnecessary development (that is, too much toner) occurs, thin line reproducibility is reduced, and toner consumption is increased. Invite. on the other hand,
5% by number of toner particles having a particle diameter of 6.35 to 10.08 μm
If it is lower than this, it is difficult to obtain a high image density.

Further, for the same reason as the value of N, the value of V is set to 0.
It is preferably from 5 to 70% by volume.

The value of k is 3 to 12, preferably 4 to 12.
It is preferably 10.

When k is less than 3, the number of toner particles having a particle size smaller than 5.0 μm is small, and the image density, resolution and sharpness are reduced. The appropriate presence of fine toner particles, which has been considered unnecessary, contributes to the closest packing of the toner during development and contributes to forming a uniform image. In particular,
By uniformly filling the thin lines and the outline of the image, the sharpness is visually enhanced.

If k exceeds 12, the presence of unnecessarily fine powders tends to slightly lower the image density when copying or printing a large number of papers, and tends to cause problems such as filming. The content of toner particles having a particle size of 12.7 μm or more is preferably 2.0% by volume or less, more preferably 1.0% by volume or less, and further preferably 0.5% by volume or less. If it exceeds 2.0% by volume, fine line reproducibility tends to be poor. Weight average particle size of toner is 4 to 10
μm (more preferably, 4.5 to 9.0 μm), and this value cannot be considered separately from the above-described components. If the weight average particle diameter is less than 4 μm, problems such as contamination inside the apparatus due to toner scattering during long-term use, a decrease in image density in a low humidity environment, and poor cleaning of the photoconductor are likely to occur. When the weight average particle diameter exceeds 10 μm, the resolution of the minute spots of 100 μm or less is not sufficient, and the fine spots tend to scatter to non-image areas, resulting in poor image quality.

Examples of the binder resin used in the toner of the present invention include polyester resins, vinyl resins, epoxy resins and the like. Among them, a polyester-based resin or a vinyl-based resin is more preferable in terms of charging characteristics and fixability.

The preferred composition of the polyester resin is as follows.

The polyester resin contained 45 to 55 of all components.
mol% is the alcohol component, 55 to 45 mol%
Is an acid component.

Examples of the alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol; hydrogenated bisphenol A; bisphenol derivative represented by the following formula (A);

[0109]

Embedded image

Diols represented by the formula (B):

[0111]

Embedded image Is mentioned.

Examples of the divalent carboxylic acid containing 50 mol% or more of the total acid component include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride or anhydrides thereof; succinic acid, adipic acid, sebacic acid Alkyl dicarboxylic acids such as azelaic acid or anhydrides thereof; succinic acids having an alkyl group or alkenyl group having 6 to 18 carbon atoms as a substituent or anhydrides thereof; Saturated dicarboxylic acids or anhydrides thereof are exemplified.

The particularly preferred alcohol component of the polyester resin is a bisphenol derivative represented by the above formula (A), and the preferred acid component is phthalic acid, terephthalic acid, isophthalic acid or its anhydride, succinic acid, n-dodecenylsuccinic acid. Or dicarboxylic acids such as anhydrides thereof, fumaric acid, maleic acid, and maleic anhydride.

The glass transition temperature of the polyester resin is 40
-90 ° C, preferably 45-85 ° C, a number average molecular weight (Mn) of 1,000-50,000, preferably 1,500-20,000, and a weight average molecular weight (M
w) should be 3,000 to 2,000,000, preferably 4,000 to 1,500,000.

Examples of the monomer of the vinyl copolymer 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; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl bromide; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, methacrylic acid Ethyl, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate,
Α-methylene aliphatic monocarboxylic esters such as phenyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, acrylic Acid n
Acrylates such as octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl Vinyl ketones such as methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalenes; acrylonitrile, methacryloyl Acrylic acid derivatives such as nitrile and acrylamide or methacrylic acid derivatives; esters of α, β-unsaturated acids and diesters of dibasic acids.

Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenylsuccinic anhydride Unsaturated dibasic acid anhydrides such as those; methyl maleate half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, methyl itaconate Half esters of unsaturated dibasic acids such as half ester, methyl alkenyl succinate half ester, methyl fumarate half ester and methyl half mesaconic acid; unsaturated dibasic acid esters such as dimethyl maleic acid and dimethyl fumaric acid; Acid, methacrylic acid, crotonic acid, such as cinnamic acid alpha, beta-unsaturated acid; crotonic acid anhydride, such as alpha of cinnamic acid anhydride, beta-unsaturated acid anhydride, the alpha, beta
-Anhydrides of unsaturated acids and lower fatty acids; and monomers having a carboxyl group such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, acid anhydrides and monoesters thereof.

Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene; Monomers having a hydroxyl group such as (hydroxy-1-methylhexyl) styrene are exemplified.

The glass transition temperature of the vinyl binder resin is 45.
To 80 ° C, preferably 55 to 70 ° C, the number average molecular weight (Mn) is preferably 2,500 to 50,000, and the weight average molecular weight (Mw) is preferably 10,000 to 1,500,000.

In the present invention, a homopolymer or copolymer of a vinyl monomer, polyester, polyurethane,
Epoxy resin, polyvinyl butyral, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, etc. may be used by mixing with the above-mentioned binder resin if necessary. it can.

When two or more resins are mixed and used as a binder resin, as a more preferred form, those having different molecular weights are preferably mixed at an appropriate ratio.

The toner for developing an electrostatic image of the present invention may be either a magnetic toner or a non-magnetic toner. When used as a magnetic toner, the following magnetic materials are preferably used.

The magnetic material contained in the magnetic toner includes:
Iron oxides such as magnetite, maghemite, ferrite, or iron oxides containing other metal oxides; Fe, Co,
Metals such as Ni, or these metals and Al, C
o, Cu, Pb, Mg, Ni, Sn, Zn, Sb, B
Examples thereof include alloys with metals such as e, Bi, Cd, Ca, Mn, Se, Ti, W, and V, and mixtures thereof.

For example, ferric oxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ),
Yttrium iron oxide (Y ₃ Fe ₅ O ₁₂ ), cadmium iron oxide (CdFe ₂ O ₄ ), gadolinium iron oxide (Gd ₃ Fe ₅
-O _12), oxidized iron-copper (CuFe ₂ O _4), oxidation Tetsunamari (Pb
Fe ₁₂ —O ₁₉ ), nickel iron oxide (NiFe ₂ O ₄ ), neodymium iron oxide (NdFe ₂ O ₃ ), barium iron oxide (B
aFe ₁₂ -O ₁₉ ), magnesium iron oxide (MgFe
₂ O ₄ ), iron manganese oxide (MnFe ₂ O ₄ ), iron lanthanum oxide (LaFeO ₃ ), iron powder (Fe), cobalt powder (C
o) and nickel powder (Ni). The above-mentioned magnetic materials are used alone or in combination of two or more.
Particularly preferred magnetic materials for the purposes of the present invention are ferric oxide or γ.
-Fine powder of iron sesquioxide.

These magnetic materials have an average particle size of 0.1 to 2 μm.
m (preferably 0.1 to 0.3 μm), and the magnetic characteristics when a 10K Oersted is applied show a coercive force (Hc) of 20 to 150.
Oersted, saturation magnetization (σr) 5 to 200 emu / g
(Preferably 50 to 100 emu / g) residual magnetization (σ
r) Those having 2 to 20 emu / g are preferred.

With respect to 100 parts by weight of the binder resin, the magnetic material 1
It is preferable to use 0 to 200 parts by weight, preferably 20 to 150 parts by weight.

A coloring agent may be used in the toner of the present invention as needed. Colorants that can be used in the toner of the present invention include any suitable pigments or dyes.

For example, pigments include carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, bengara, phthalocyanine blue, and indanthrene blue. It is preferable to use 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight of the pigment based on 100 parts by weight of the binder resin. Similarly, a dye is used as a coloring agent. For example, there are anthraquinone dyes, xanthene dyes and methine dyes, and 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, per 100 parts by weight of the binder resin.
It is preferred to use parts by weight of the dye.

In the present invention, if necessary, one or more release agents may be further contained in the toner.

The following are examples of the release agent used in the present invention. Aliphatic hydrocarbon-based waxes such as low-molecular-weight polyethylene, low-molecular-weight polypropylene, microcrystalline wax and paraffin wax; oxides of aliphatic hydrocarbon-based waxes such as oxidized polyethylene wax, or block copolymers thereof; carnauba wax; Waxes mainly containing a fatty acid ester such as montanic acid ester wax; and those obtained by partially or entirely deoxidizing an acid component from a fatty acid ester such as deoxidized carnauba wax. Further, fatty acid amides such as linoleic acid amide, oleic acid amide and lauric acid amide; saturated fatty acid bisamides such as methylene bisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide and hexamethylenebisstearic acid amide; Unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethine bis oleic acid amide, N, N'-dioleyl adipamide, N, N'-diolein sebacic acid amide; m-xylene bis stearic acid amide; Aromatic bisamides such as N, N'-distearylisophthalamide; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (commonly referred to as metallic soaps); hydrogen Graft waxes obtained by grafting waxes with vinyl monomers such as styrene and acrylic acid; partial esterified products of fatty acids such as behenic acid monoglyceride and polyhydric alcohols; and hydroxyl groups obtained by hydrogenating vegetable oils and fats. And a methyl ester compound having the same.

As the release agent particularly preferably used in the present invention, an aliphatic hydrocarbon wax can be mentioned. This is because when the wax is applied to the resin having an acid value of 5 to 50 used in the present invention, the dispersibility thereof is extremely improved, so that not only the fixing property but also the case where an organic photoreceptor is used. In addition, the shaving amount can be further reduced.

Specific examples of the release agent preferably used in the present invention include, for example, a low-molecular-weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or a Ziegler catalyst under low pressure; And a wax such as a synthetic hydrocarbon obtained from a distillation residue of a hydrocarbon obtained by the Age method from a synthesis gas consisting of carbon monoxide and hydrogen, or a synthetic hydrocarbon obtained by hydrogenating these. Further, those obtained by separating a hydrocarbon wax by use of a press sweating method, a solvent method, vacuum distillation or a fractional crystallization method are more preferably used. The hydrocarbon as a base is a hydrocarbon synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide-based catalyst (often a multi-component system of two or more) (for example, the Zintol method, the Hydrochol method (fluid catalyst) Bed) or the Aige method (using a fixed catalyst bed) that yields a lot of waxy hydrocarbons (hydrocarbons with a carbon number of up to about several hundred) obtained by Ziegler catalyst polymerization of alkylenes such as ethylene. Is preferred because it is a straight-chain hydrocarbon with few branches and long saturation. Particularly, a wax synthesized by a method not based on the polymerization of alkylene is preferable in view of its molecular weight distribution.

In the molecular weight distribution, the molecular weight is 400 to 2400.
, A peak preferably exists in a region having a molecular weight of 450 to 2,000, particularly preferably 500 to 1600. By providing such a molecular weight distribution, the toner can have favorable thermal characteristics.

The amount of the release agent used in the present invention is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the binder resin.

These release agents are prepared by dissolving the binder resin in a solvent, heating the resin solution, and adding and mixing the release agent while stirring, or mixing the binder resin with the release agent during kneading. Is preferably mixed with a binder resin.

When a fluidity improver is used as an external additive in a toner, the fluidity improver used in the present invention may be increased by mixing with a toner particle, as compared with before and after mixing. Anything is fine. For example,
Fluorinated resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; fine powder silica such as wet-process silica or dry-process silica, and surface of these silicas with silane coupling agent, titanium coupling agent, silicone oil, etc. There is a treated fine silica powder.

Preferred fluidizing agents are fine powders produced by the vapor phase oxidation of silicon halide compounds.
It is what is called dry silica or fumed silica, and is manufactured by a conventionally known technique. For example, it utilizes the thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame, and the basic reaction formula is as follows.

SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

In this manufacturing process, it is also possible to obtain a composite fine powder of silica and another metal oxide by using another metal halide such as aluminum chloride or titanium chloride together with the silicon halide. The particle size is preferably in the range of 0.001 to 2 μm as an average primary particle size, particularly preferably 0.01 to 2 μm.
It is preferable to use silica fine powder in the range of 02 to 0.2 μm.

The commercially available silica fine powder produced by the vapor phase oxidation of a silicon halide used in the present invention includes, for example, those commercially available under the following trade names.

AEROSIL (Nippon Aerosil) 130 200 300 380 TT600 MOX170 MOX80 COK84 Ca-O-Sil (CABOT CO.) M-5 MS-7 MS-75 HS-5 EH-5 Wacker HDK N20 V15 WAC -CHEMIE GMBH) N20E T30 T40 DC Fine Silica (Dow Corning C
o. Fransol (Fransil)

Further, it is more preferable to use a treated silica fine powder obtained by subjecting a silica fine powder produced by vapor-phase oxidation of the silicon halide compound to a hydrophobic treatment. It is particularly preferable that the treated silica fine powder is obtained by treating the silica fine powder such that the degree of hydrophobicity measured by a methanol titration test shows a value in the range of 30 to 80.

The hydrophobicity is given by chemically treating with an organosilicon compound or the like which reacts with or physically adsorbs silica fine powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halide is treated with an organosilicon compound.

Examples of such organosilicon compounds include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyl Dimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxy Silane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyl Disiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 per molecule
There is a dimethylpolysiloxane having hydroxyl groups bonded to Si, each of which has one siloxane unit and the terminal unit is one each. These are used alone or as a mixture of two or more.

[0145] fluidizing agent used in the present invention has a specific surface area by nitrogen adsorption measured by BET method is 30 m ² / g or more, preferably not less than 50 m ² / g give good results. Fluidizer 0.01 for 100 parts by weight of toner
To 8 parts by weight, preferably 0.1 to 4 parts by weight.

When the toner of the present invention is used for a two-component developer, the toner is used in a mixture with a carrier. The carrier used in the present invention includes, for example, metal particles such as iron, nickel, copper, zinc, cobalt, manganese, chromium, and rare earths which have been oxidized or not oxidized, and those metal particles, oxide particles, and ferrite particles. Can be used.

The coated carrier obtained by coating the surface of the carrier particles with a resin is particularly preferable in the developing method in which an AC bias is applied to the developing sleeve. As a coating method, a method of dissolving or suspending a coating material such as a resin in a solvent and attaching a coating liquid prepared on the surface of the carrier core particles, a method of mixing the carrier core particles and the coating material with a powder, A conventionally known method can be applied.

Examples of the fixing material to the carrier core particle surface include polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, styrene resin, acrylic resin, polyamide, polyvinyl butyral, and amino. Examples include acrylate resins, basic dyes and lakes thereof, silica fine powder, and alumina fine powder. These may be used alone or in combination.

The processing amount of the fixing material is 0.1 to 30% by weight (preferably 0.5 to 20% by weight) based on the carrier core particles.
% By weight) is preferred. The average particle size of these carriers is 1
It preferably has a size of 0 to 100 μm, preferably 20 to 70 μm.

As a particularly preferred embodiment, Cu—Zn—
Fe ternary ferrite particles, the surface of which is coated with a resin such as a fluororesin or a styrene resin.
For example, a mixture of polyvinylidene fluoride and styrene-methyl methacrylate resin, a mixture of polytetrafluoroethylene and styrene-methyl methacrylate resin,
A mixture of a fluorine-based copolymer and a styrene-based copolymer is used. Fluorine resin and styrene resin are 90:
10-20: 80, preferably 70: 30-30-3
It is used by mixing at a weight ratio of 0:70. The coating amount on the carrier core is 0.01 to 5% by weight, preferably 0.1 to 1% by weight. 250 mesh pass, 400
An average particle size of 10 to 100 μm (preferably 20 to 70 μm) in which mesh-on carrier particles are 70% by weight or more.
A coated magnetic ferrite carrier having the following is preferred. Examples of the fluorine-based copolymer include vinylidene fluoride-tetrafluoroethylene copolymer (10:90 to 90:10), and examples of the styrene-based copolymer include styrene-2-ethylhexyl acrylate (20:80). ~ 80: 20),
Styrene-2-ethylhexyl acrylate-methyl methacrylate (20-60: 5-30: 10-50) is exemplified. The coated magnetic ferrite carrier preferably has a sharp particle size distribution, has a favorable triboelectric charging property with respect to the toner of the present invention, and can improve the electrophotographic properties of a two-component developer.

When the mixing ratio of the toner of the present invention to the carrier is 2 to 15% by weight, preferably 4 to 13% by weight as the toner concentration in the developer, generally good results can be obtained. If the toner density is less than 2%, the image density is low, making it impractical. If it exceeds 15%, fog and scattering in the machine are increased, and the useful life of the developer is shortened.

To prepare the toner for developing an electrostatic image of the present invention, a binder resin, a magnetic material, a release agent, a colorant, a charge control agent or other additives are mixed with a mixer such as a Henschel mixer or a ball mill. Thoroughly mix, melt, knead and knead using a hot kneader such as a heating roll, kneader, extruder to make the resins compatible with each other. Can be obtained to obtain the toner of the present invention.

Further, the fluidizing agent and the toner are sufficiently mixed by a mixer such as a Henschel mixer to obtain a toner having a fluidizing agent on the surface of toner particles.

In the present invention, the characteristic values of the binder resin and the long-chain alkyl compound and the particle size distribution of the toner can be measured by the following measuring methods.

(1) Glass transition temperature Tg In the present invention, the glass transition temperature is measured using a differential thermal analyzer (DSC analyzer), DSC-7 (manufactured by PerkinElmer).

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.

(2) Measurement of Molecular Weight (Binder Resin) In the present invention, the molecular weight of a chromatogram by GPC (gel permeation chromatography) is measured under the following conditions.

The column was stabilized in a heat chamber at 40 ° C., and TH was used as a solvent at this temperature.
F (teratohydrofuran) at a flow rate of 1 ml per minute,
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 the sample, the molecular weight distribution of the sample was 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 × 10 ⁴ ,
5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.
It is suitable to use 6 × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ , and to use at least about 10 standard polystyrene samples. The detector has a RI (refractive index)
Use a detector.

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

(3) Measurement of molecular weight distribution (long chain hydrocarbon compound) (GPC measurement conditions) Apparatus: GPC-150C (Waters) Column: GMH-HT 30 cm 2 columns (manufactured by Tosoh Corporation) Temperature: 135 ° C. Solvent: o- Dichlorobenzene (with 0.1% ionol) Flow rate: 1.0 ml / min Sample: 0.4 ml of 0.15% sample injected

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.

(4) Measurement of acid value and OH value a) Regarding acid value A sample is precisely weighed, dissolved in a mixed solvent and added with water. This solution is subjected to potentiometric titration with 0.1 N-NaOH using a glass electrode to determine an acid value. (According to JIS K1557-1970.)

B) Regarding the hydroxyl value The sample was precisely weighed in a 100 ml eggplant flask, and 5 ml of the acetylating reagent was correctly added thereto. Then 100 ℃ ± 5
Heat by immersing in a bath at ° C. After 1-2 hours, the flask is taken out of the bath, left to cool, water is added and shaken to decompose acetic anhydride. Further, in order to complete the decomposition, the flask is again heated in a bath for 10 minutes or more and allowed to cool, and then the flask wall is thoroughly washed with an organic solvent. This solution is subjected to potentiometric titration with an N / 2 potassium hydroxide ethyl alcohol solution using a glass electrode to determine a hydroxyl value (according to JIS K0070-1966).

(5) Measurement of particle size distribution As a measuring apparatus, COULTER MULTISIZE was used.
An interface (manufactured by Nikkaki) to output the number distribution and volume distribution to R II (manufactured by Coulter) and PC980
One connected with a personal computer (manufactured by NEC) was used. The electrolyte is 1% N using 1st grade sodium chloride.
Prepare aCl aqueous solution. As a measuring method, a surfactant is used as a dispersant in 100 to 150 ml of the electrolytic aqueous solution,
Preferably alkyl benzene sulfonate 0.1 ~
Add 5 ml, and then add 2 to 20 mg of the measurement sample. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes by an ultrasonic
The particle size distribution of particles of 2 to 40 μm is measured based on the number by using a 100 μm aperture as an aperture according to II, the volume distribution and the number distribution of the particles of 2 to 40 μm are calculated, and the weight-average weight average obtained from the volume distribution is calculated. The particle size (D4: the median value of each channel is set as a representative value of the channel) is determined.

Next, the image forming method of the present invention will be described with reference to FIGS. 1, 2 and 3. As an example of an apparatus such as a copying machine or a printer for carrying out the image forming method of the present invention, there is an electrophotographic apparatus shown in FIG. 1, and a developing unit 1 contains a toner 13 of the present invention. The toner is a magnetic toner or a non-magnetic toner. In an image forming apparatus other than the apparatus shown in FIG. 1, a developing unit using a two-component developer having a toner and a carrier may be used. A charging means (for example, a charging roller, a charging brush, a charging blade or the like, which is a contact charging means) 11 to which a voltage is applied by the bias applying means 34, and a photosensitive member (for example, an OPC photosensitive drum, amorphous silicone or a polycrystalline photosensitive drum) 3) is charged, and an electrostatic charge image is formed on the photoconductor 3 by exposure (for example, laser light or light from a halogen lamp) 5. Toner coating blade (for example, elastic blade, magnetic blade, etc.) 8 and magnetic field generating means (for example, magnet) 1
The electrostatic toner image is developed with the magnetic toner 13 contained in the developing means 1 having the developing sleeve 6 containing the developing sleeve 5. For development, a regular development method or a repetitive development method is used. In the developing section, the bias applying means 12 applies alternating bias, pulse bias and / or
Alternatively, a DC bias is applied as needed. When the transfer material P is transported and reaches the transfer portion, a voltage is applied by the bias applying unit 33. The toner image on the surface of the photoconductor 3 is charged by being pressed by a transfer unit (for example, a transfer roller, a transfer belt, etc.) from the back surface (the side opposite to the photoconductor 3 side) of the transfer material P. Transfer electrostatically onto P. In some cases, the toner image on the photoconductor 3 may be transferred to an intermediate transfer member (eg, an intermediate transfer drum, an intermediate transfer belt, etc.), and the toner image may be transferred from the intermediate transfer member to the transfer material P. .

The toner image on the transfer material P separated from the photoreceptor 3 is heated and pressed by a heating device (for example, a fixing device in which a pressing roller is pressed against a fixed heating element via a heat-resistant sheet) or a heating and pressing device. The transfer material P is fixed by a roller fixing device 35). The toner remaining on the photoreceptor 3 after the transfer process is cleaned by a cleaning means (for example, a cleaning blade, a cleaning roller, a cleaning brush, or the like) 7 if necessary.
Is removed from the surface of the photoconductor 3. After the cleaning, the charging unit 11 repeats the steps starting from the charging step.

The photoreceptor 3, which is a member to be charged and is an electrostatic image holder, generally has a photosensitive layer and a conductive substrate, and rotates in the direction of the arrow. The developing sleeve 6 having a non-magnetic cylinder as a toner carrier rotates so as to advance in the same direction as the photoconductor 3 in the developing section. Inside the developing sleeve 6, a multi-pole permanent magnet (magnet roll) 15 as a magnetic field generating means is fixed and supported. The magnetic toner 13 accommodated in the developing means 1 is applied to the surface of the developing sleeve 6 by the application blade 8, and the toner particles generate triboelectric charges due to friction with the surface of the application blade 8 and / or the developing sleeve 6. Granted. The coating blade 8 uniformly applies the toner layer (for example, a thickness of 10 to 300 μm) on the surface of the developing sleeve 6. In the developing unit, for example, the AC bias f is 200 to 4,000
Hz and Vpp of 500 to 3,000 V are applied.

When transferring the toner particles in the developing section,
The toner particles transfer to an electrostatic image due to the electrostatic force of the photoconductor surface and the action of an AC bias or a pulse bias.

Next, each member of the apparatus shown in FIGS. 1 to 3 used in the embodiment will be described below. 1 to 3, reference numeral 3 denotes a photoconductor, and 11 denotes a charger (charging roll).
7 denotes a cleaning means, 5 denotes an exposure means, 2 denotes a developer accommodating container, 6 denotes a developer carrier (developing sleeve), 15 denotes a magnetic field generating means,
8 denotes an elastic layer thickness regulating member, 4 denotes a transfer means (transfer roll), 20 denotes a stay, 21 denotes a heating element, 21a denotes a heater substrate, 21b denotes a heating element, and 21c denotes a heating element. 21d shows a temperature detecting element, 22 shows a fixing film, 23 shows a pressure roller, 24 shows a coil spring, 25 shows a film end regulating flange, 26 shows a power supply connector. Show, 27
Indicates a power cutoff member, 28 indicates an entrance guide, and 29 indicates an exit guide (separation guide).

FIG. 5 is a schematic sectional view of the process cartridge taken out of the image forming apparatus main body.
The process cartridge at least integrates the developing unit 1 and the photoconductor 3 into a cartridge, and the process cartridge is formed so as to be detachable from a main body of an image forming apparatus (for example, a copying machine, a laser beam printer, or the like).

In the present embodiment, a cleaner having a developing means 1, a drum-shaped photosensitive member 3, and a cleaning blade 7,
A process cartridge in which the primary charger (charging roller) 11 is integrated is exemplified.

In this embodiment, the developing means 1 has the toner layer thickness regulating member 8 and the magnetic toner 13 in the toner container, and uses the magnetic toner 13 after the process cartridge is mounted on the image forming apparatus main body. A predetermined electric field is formed between the photosensitive drum 3 and the developing sleeve 6 by the bias from the bias applying unit, and the developing process is suitably performed.

[0176]

The present invention will be described below with reference to production examples and examples.

[Resin Production Example 1] Terephthalic acid 12 mol% Fumaric acid 18 mol% Adipic acid 10 mol% Trimellitic anhydride 12 mol% Bisphenol derivative represented by the formula (A) (R = propylene group and x + y = 2.2) 15 mol% (R = ethylene group and x + y = 2.2) 33 mol%

These are subjected to condensation polymerization to obtain Mn = 5000, M
w = 57000, Tg = 60 ° C., acid value = 20, OH value =
20 polyester resins were obtained. The polyester resin obtained here is referred to as resin A.

[Resin Production Example 2] Styrene 87 parts by weight Butyl acrylate 13 parts by weight Di-tert-butyl peroxide 3 parts by weight

The above materials were added dropwise to 200 parts by weight of xylene heated to the reflux temperature over 4 hours. Further, the polymerization was completed under xylene reflux (138 to 144 ° C.), and xylene was removed while heating to 200 ° C. under reduced pressure. The resin thus obtained is referred to as a resin B.

Styrene 75 parts by weight Butyl acrylate 25 parts by weight 2,2-bis (4,4-di-tert-butylperoxy 0.1 parts by weight cyclohexyl) propane benzoyl peroxide 0.1 parts by weight

170 parts by weight of water in which 0.12 parts by weight of a partially saponified polyvinyl alcohol was dissolved was added to the above mixture, and the mixture was vigorously stirred to obtain a suspension dispersion. The suspension dispersion was added to a reactor which was charged with 50 parts by weight of water and purged with nitrogen, and subjected to a suspension polymerization reaction at a reaction temperature of 80 ° C. for 8 hours. After the reaction was completed, the resin was washed with water, dehydrated and dried to obtain resin C.

The above resin B and resin C were mixed at a weight ratio of 70:30.
The resin obtained by dissolving in xylene at a ratio of and mixing uniformly and then removing xylene is referred to as resin D. Resin D has peaks at 12,000 and 800,000 in the molecular weight distribution, and Mn
= 7,000, Mw = 250,000, and Tg = 61 ° C.

[Resin Production Example 3] Styrene 80.0 parts by weight Butyl acrylate 10.0 parts by weight Monobutyl maleate 10.0 parts by weight Di-tert-butyl peroxide 6.0 parts by weight Perform the same procedure as for resin B,
I got

Resin E 40.0 parts by weight Styrene 45.0 parts by weight Butyl acrylate 15.0 parts by weight Divinylbenzene 0.5 parts by weight Benzoyl peroxide 0.5 parts by weight

The above mixed solution was mixed with Resin C in Resin Production Example 2
Polymerization reaction was carried out under the same conditions as described above to obtain resin F. The resin F had Tg = 60 ° C., Mn = 10000, and Mw = 100,000.

Example 1 100 parts by weight of resin A 90 parts by weight of magnetic iron oxide (average particle size 0.15 μm, Hc = 115 oersted σs = 80 emu / g, σr = 11 emu / g) Long chain represented by formula (1) alkyl alcohol 3 parts by weight (average x = 48, Mn = 440, Mw = 870, Mw / Mn = 1.98, OH number = 66) azo type iron complex compound (1) 2 parts by weight (NH ⁺ ₄ is 90 %, Other 10% is a mixture of Na ⁺ and H ⁺ )

After the above materials were premixed with a Henschel mixer, melt kneading was performed at 130 ° C. using a twin screw kneading extruder. The kneaded product was allowed to cool, then coarsely pulverized with a cutter mill, pulverized using a fine pulverizer using a jet stream, and further classified using an air classifier to obtain a weight average particle size of 6.6 μm and 5 μm.
49.3% by number, 19.6% by volume for particles of m or less
Was obtained as the magnetic toner (1).

Incidentally, OD _F / which is an index of segregation property of the azo-based iron complex compound of the classified fine powder and the classified coarse powder, is used as an index.
OD _M = 1.012, was OD _G / OD _M = 0.998.

To 100 parts by weight of the magnetic toner (1), 1.0 part by weight of hydrophobic silica fine powder surface-treated with hexamethyldisilazane was mixed with a Henschel mixer. 1 was obtained. This developer No. 1 was applied to a Canon copier GP-55 under normal temperature and low humidity (23.5 ° C./5%
RH), and then under high temperature and high humidity (32.5 ° C / 8
(0% RH), 30,000 copies were printed. Further, the developer No. 1 was also applied to a Canon copier NP-9800, and after printing 200,000 sheets under normal temperature and low humidity, 10
10,000 images were printed. Tables 8 and 11 show the results of the image formation test.
Shown in

Further, a commercially available laser beam printer L
As shown in FIG. 1 (schematic diagram), a BP-SX (manufactured by Canon) was provided with an elastic blade made of urethane rubber and a charging roller on an apparatus unit (toner cartridge).
Further, a transfer roller was attached to the main body, and the heating and fixing device was further modified into the configuration shown in FIG. 2 (exploded perspective view) and FIG. 3 (cross-sectional view), and set under the following conditions.

An electrostatic latent image is formed by setting the primary charge to -600 V, and a gap (300 μm) is set without contact between the photosensitive drum 3 and the developer layer on the developer carrier 6 (including magnets). f = 1800 Hz Vpp = 1500 V) and a DC bias (V _DC = −400 V) are applied to the developing sleeve by the bias applying means 12 while _VL is −
The electrostatic image was developed by reversal development at 150 V to form a toner image on the OPC photoconductor. The obtained toner image was transferred to plain paper at a positive transfer potential, and the plain paper having the toner image was fixed on the paper through a heat fixing device. At this time, the surface temperature of the temperature measuring element 21d of the heating body 21 of the heating and fixing device is 150 ° C., the total pressure between the heating body 21 and the pressure roller 23 is 6 kg, and the nip between the pressure roller and the film is 3 m.
m, and the fixing film 22 has P
A heat-resistant polyimide film having a thickness of 50 μm and having a low-resistance release layer in which a conductive material was dispersed in TEF was used.

Under the above set conditions, room temperature and normal humidity (25 ° C., 6
In a 0% RH environment, a printout test was performed on 7,000 sheets continuously at a print speed of 8 sheets (A4) / min while replenishing the developer, and the obtained images were evaluated for the following items.

Similarly, in a high temperature and high humidity environment (32.5 ° C.,
90% RH) and under low temperature and low humidity environment (10 ° C, 15% R)
In H), an image-drawing test was performed.

In a high-temperature and high-humidity environment, 6500
After performing the image output test, under the same environment,
The sample was allowed to stand for a day, and an image printing test was further performed for 500 sheets. The results are shown in Tables 14 and 15.

Examples 2 to 21 and Comparative Examples 1 to 6 The toner was added in the same manner as in Example 1 except that the materials shown in Tables 1 to 5 were used. Was obtained. The magnetic toners of Reference Examples 1 and 2 in Table 4 are for the fine powder recycling system of Comparative Examples 3 and 5. The values of x in Tables 1, 2, 3, and 5 indicate average values. The segregation properties of these azo-based iron complex compounds are as shown in Tables 6 and 7. Using these toners in the same manner as in Example 1, Developer Nos. 2 to 21 and Comparative Example 1
~ 6.

Evaluation was performed in the same manner as in Example 1 using these developers, and the results shown in Tables 8 to 17 were obtained.

<Evaluation with Digital Copying Machine GP-55 and Analog Copying Machine NP-9800> In the present invention, the resolution of the images obtained by the copying machines GP-55 and NP-9800 was measured by the following method. . 1. A pattern consisting of five fine lines having the same line width and interval.
8; 3.2; 3.6; 4.0; 4.5; 5.0;
6; 6.3; 7.1; 8.0; 9.0 or 10.0 Create an original image drawn as if it were there. This one
An image obtained by copying an original document having two types of line images under appropriate copying conditions is observed with a magnifying glass, and the number of images (lines / mm) in which fine lines are clearly separated is defined as the value of resolution. .

The larger this number is, the higher the resolution is.

<Laser Beam Printer LBP SX>
(1) Image Density The image density was evaluated by maintaining the image density at the end of printing out 7,000 sheets on ordinary paper for copying machines (75 g / m ² ).
The image density was measured by using a "Macbeth reflection densitometer" (manufactured by Macbeth Co., Ltd.) with respect to a printout image of a white background portion having a document density of 0.00.

(2) Fog Fog was calculated from a comparison between the whiteness of the transfer paper measured by a reflectometer (manufactured by Tokyo Denshoku Co., Ltd.) and the whiteness of the transfer paper after printing solid white. If the fog value exceeds 4%, there is a practical problem.

(3) Image Quality The pattern shown in FIG. 4 was printed out and its dot reproducibility was evaluated.

◎: Very good (2 or less defects / 100) ○: Good (3 to 5/100 defects) Δ: Normal (6 to 10/100 defects) ×: Bad (11 defects) Above / 100)

(4) Fixing Property The fixing property was evaluated by applying a load of 50 g / cm ² , rubbing the fixed image with soft thin paper, and reducing the image density before and after rubbing (%).

◎ (excellent): 5% or less,
（(Good): 5% or more and less than 10% △ (normal): 10% or more and less than 20%, × (bad):
20% or more

(5) Offset Resistance The offset resistance was evaluated by printing out a sample image having an image area ratio of about 5% and evaluating the degree of stain on the image after 3000 sheets.

◎: very good (not generated), ：: good (almost no occurrence) Δ: normal, ×: bad

(6) Stain on Sleeve After completion of the printout test, the state of fixation of the residual toner on the surface of the developing sleeve and the effect on the printout image were visually evaluated.

◎: very good (no occurrence) ：: good (almost no occurrence) Δ: normal (there is sticking but little influence on the image) ×: bad (many sticking and image unevenness occurs)

At the same time, the state of the surface of the fixing film was observed to evaluate its durability.

(8) Film Staining After the printout test, the state of fixation of the residual developer on the surface of the fixing film was visually evaluated.

◎: very good (not generated), ：: good (almost no occurrence) Δ: normal, ×: bad

[0213]

[Table 1]

[0214]

[Table 2]

[0215]

[Table 3]

[0216]

[Table 4]

[0219]

[Table 5]

[0218]

[Table 6]

[0219]

[Table 7]

[0220]

[Table 8]

[0221]

[Table 9]

[0222]

[Table 10]

[0223]

[Table 11]

[0224]

[Table 12]

[0225]

[Table 13]

[0226]

[Table 14]

[0227]

[Table 15]

[0228]

[Table 16]

[0229]

[Table 17]

[0230]

As described above, the toner for developing an electrostatic image of the present invention can uniformly charge the toner particles even under severe environmental conditions of low humidity or high humidity. And high-quality images can be provided, and the performance of the electrostatic image developing toner can be improved.

[Brief description of the drawings]

FIG. 1 is a schematic explanatory view of an image forming apparatus used in an embodiment of the present invention.

FIG. 2 is an exploded perspective view of a main part of the fixing device used in the embodiment of the present invention.

FIG. 3 is an enlarged cross-sectional view of a main part showing a film state when the fixing device used in the embodiment of the present invention is not driven.

FIG. 4 is an explanatory diagram of a checker pattern for checking development characteristics of toner.

FIG. 5 is a schematic explanatory view of a process cartridge.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Developing apparatus 2 Developer container 3 Photoconductor 4 Transfer means 5 Exposure means (laser light or analog light) 6 Developing sleeve 7 Cleaning blade 8 Elastic blade 11 Charging means 12 Bias applying means 13 Magnetic developer 14 Cleaning means 15 Magnetic field generating means DESCRIPTION OF SYMBOLS 20 Stay 21 Heating body 21a Heater board 21b Heating body 21c Surface protection layer 21d Temperature measuring element 22 Fixing film 23 Pressure roller 24 Coil spring 25 Film end regulating flange 26 Power supply connector 27 Disconnecting member 28 Inlet guide 29 Outlet guide (separation guide) 33, 34 bias applying means 35 heating and pressurizing means

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Makoto Umino 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Yuji Mikuri 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inside (72) Inventor Manabu Ohno 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Nobuyuki Okubo 3-30-2, Shimomaruko 3-chome, Ota-ku, Tokyo Canon Inc. ( 72) Inventor Shunji Suzuki 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (56) References JP-A-2-134648 (JP, A) JP-A-4-204543 (JP, A) JP-A-4-97162 (JP, A) JP-A-6-123994 (JP, A) JP-A-59-67554 (JP, A) JP-A-7-36210 (JP, A) JP-A-7-36216 ( JP, A) JP-A-61-155464 (JP, A) JP-A-2-153362 (JP, A) JP-A-5-197277 (JP, A) JP-A-6-332240 (JP, A) JP-A-56-101150 (JP, A) JP, A) JP-A-3-200975 (JP, A) JP-A-3-200262 (JP, A) JP-A-63-199364 (JP, A) JP-A-2-257143 (JP, A) JP JP-A-2-284161 (JP, A) JP-A-3-121462 (JP, A) JP-A-4-143775 (JP, A) JP-A-6-83182 (JP, A) JP-A-4-220665 (JP JP-A-5-289401 (JP, A) JP-A-63-43163 (JP, A) JP-A-5-1199642 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB (Name) G03G 9/08

Claims (32)

(57) [Claims] 1. A binder resin, represented by the following formula (1), (2) or (3): [Where x represents an average value and is from 35 to 150]. ] [In the formula, x represents an average value, from 35 to 150, z represents an average value, from 1 to 5, and R represents hydrogen or 1 carbon atom.
Represents from 10 to 10 alkyl groups. ] [In the formula, y represents an average value and is 35 to 150. ], And an azo-based iron complex compound represented by the following formula (4): Embedded image [Wherein X ₁ and X ₂ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a halogen atom, and X ₁ and X ₂ may be the same or different;
And m 'represents an integer of 1 to 3, R ₁ and R ₃ is a hydrogen atom, an alkyl of C ₁ ~ _18, alkenyl, sulfonamide, mesyl, sulfonic acid, carboxy ester, hydroxy, alkoxy of C ₁ ~ _18, R ₁ and R ₃ represent an acetylamino, benzoylamino group or a halogen atom;
May be the same or different; n and n ′ represent an integer of 1 to 3; R ₂ and R ₄ represent a hydrogen atom or a nitro group; A ⁺ represents a cation ion;
It has ９８98 mol% of ammonium ions, and additionally has hydrogen ions, sodium ions, potassium ions or mixed ions thereof. ] 2. A binder resin, represented by the following formula (1) or (2): [Where x represents an average value and is from 35 to 150]. ] [In the formula, x represents an average value, from 35 to 150, z represents an average value, from 1 to 5, and R represents hydrogen or 1 carbon atom.
Represents from 10 to 10 alkyl groups. The electrostatic image developing toner according to claim 1, comprising a long-chain alkyl compound represented by the following formula (1) and an azo-based iron complex compound represented by the following formula (4): Embedded image [Wherein X ₁ and X ₂ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a halogen atom, and X ₁ and X ₂ may be the same or different;
And m 'represents an integer of 1 to 3, R ₁ and R ₃ is a hydrogen atom, an alkyl of C ₁ ~ _18, alkenyl, sulfonamide, mesyl, sulfonic acid, carboxy ester, hydroxy, alkoxy of C ₁ ~ _18, R ₁ and R ₃ represent an acetylamino, benzoylamino group or a halogen atom;
May be the same or different; n and n ′ represent an integer of 1 to 3; R ₂ and R ₄ represent a hydrogen atom or a nitro group; A ⁺ represents a cation ion;
It has ９８98 mol% of ammonium ions, and additionally has hydrogen ions, sodium ions, potassium ions or mixed ions thereof. ] 3. The azo-based iron complex compound has a solubility in methanol of 0.1 g / 100 ml to 8 g / 100 ml.
The electrostatic image developing toner according to claim 1, wherein: 4. The solubility of the azo type iron complex compound in methanol is from 0.3 g / 100 ml to 4 g / 100 ml.
4. The toner for developing an electrostatic image according to claim 3, wherein: 5. The solubility of the azo-based iron complex compound in methanol is from 0.4 g / 100 ml to 2 g / 100 ml.
The toner for developing an electrostatic image according to claim 4, wherein 6. The number average molecular weight M of the long-chain alkyl compound
n is 200 to 2500, and weight average molecular weight Mw is 400 to
6. The electrostatic image developing toner according to claim 1, wherein the toner has a distribution Mw / Mn of 3 or less. 7. The long-chain alkyl compound (1) or (2)
Has an OH value of 2 mgKOH / mg to 150 mgKOH /
The toner for developing an electrostatic image according to claim 1, wherein the toner is mg. 8. The long-chain alkyl compound (1) or (2)
Has an OH value of 10 mgKOH / mg to 120 mgKOH
The toner for developing an electrostatic image according to claim 7, wherein the ratio is / mg. 9. The acid value of the long-chain alkyl compound (3) is:
The toner according to any one of claims 1 to 6, wherein the toner content is 2 mgKOH / mg to 150 mgKOH / mg. 10. The toner according to claim 9, wherein the long-chain alkyl compound (3) has an acid value of 5 mgKOH / mg to 120 mgKOH / mg. 11. The toner has a weight average particle diameter of 4.0 to 1.
0 μm and for toner particles of 5 μm or less,
N / V = −0.05 N + k (5) [where N is the number% of toner having a particle size of 5 μm or less, V is 5 μm]
The following volume percentages of toner, k: 3 to 12 are shown. 11. The toner for developing an electrostatic image according to claim 1. 12. The toner has a weight average particle size of 4.5 to 9.
The following formula (6) N / V = −0.05 N + k (6) where N is the number% of toner particles having a particle size of 5 μm or less, and V is 5 μm.
The following volume percentages of toner, k: 4 to 10 are shown. The toner for developing an electrostatic image according to claim 11, which satisfies the following. 13. A charging step of applying a voltage to the charging means while bringing the charging means into contact with the member to be charged to charge the member to be charged, and a step of forming an electrostatic charge image on the charged member to be charged. A developing step of developing the electrostatic image with toner to form a toner image on the member to be charged, and a step of transferring the toner image on the member to be charged via an intermediate transfer member, or
An image forming method comprising: a transfer step of transferring the toner image on the transfer material without intervention; and a fixing step of heating and fixing the toner image on the transfer material, wherein the toner comprises a binder resin, the following formula (1), (2) or (3) [Where x represents an average value and is from 35 to 150]. ] [In the formula, x represents an average value, from 35 to 150, z represents an average value, from 1 to 5, and R represents hydrogen or 1 carbon atom.
Represents from 10 to 10 alkyl groups. ] [In the formula, y represents an average value and is 35 to 150. And a azo-based iron complex compound represented by the following formula (4): Embedded image [Wherein X ₁ and X ₂ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a halogen atom, and X ₁ and X ₂ may be the same or different;
And m 'represents an integer of 1 to 3, R ₁ and R ₃ is a hydrogen atom, an alkyl of C ₁ ~ _18, alkenyl, sulfonamide, mesyl, sulfonic acid, carboxy ester, hydroxy, alkoxy of C ₁ ~ _18, R ₁ and R ₃ represent an acetylamino, benzoylamino group or a halogen atom;
May be the same or different; n and n ′ represent an integer of 1 to 3; R ₂ and R ₄ represent a hydrogen atom or a nitro group; A ⁺ represents a cation ion;
It has ９８98 mol% of ammonium ions, and additionally has hydrogen ions, sodium ions, potassium ions or mixed ions thereof. ] 14. The image forming method according to claim 13, wherein the member to be charged is charged by charging roller means to which a voltage is applied. 15. The image forming method according to claim 13, wherein the member to be charged is charged by charging brush means to which a voltage is applied. 16. The image forming method according to claim 13, wherein the member to be charged is charged by charging blade means to which a voltage is applied. 17. The image forming method according to claim 13, wherein the toner image on the member to be charged is transferred to a transfer material by transfer roller means to which a voltage is applied. 18. The image forming method according to claim 13, wherein the toner image on the member to be charged is transferred to a transfer material by a transfer belt unit to which a voltage is applied. 19. A toner image on a member to be charged is transferred to an intermediate transfer member, and the toner image on the intermediate transfer member is transferred to a transfer material by transfer roller means to which a voltage is applied. The image forming method according to claim 13. 20. The toner image on a member to be charged is transferred to an intermediate transfer member, and the toner image on the intermediate transfer member is transferred to a transfer material by transfer belt means to which a voltage is applied. The image forming method according to claim 13. 21. The image forming method according to claim 13, wherein the long-chain alkyl compound contains a long-chain alkyl alcohol represented by the formula (1). 22. The image forming method according to claim 13, wherein the toner has a negative triboelectric charging property. 23. A process cartridge having at least a developing unit and a photoconductor, wherein the developing unit and the photoconductor are integrally formed as a cartridge, and the process cartridge is detachable from a main body of the image forming apparatus. The developing means comprises a binder resin, the following formula (1), (2) or (3): [Where x represents an average value and is from 35 to 150]. ] [In the formula, x represents an average value, from 35 to 150, z represents an average value, from 1 to 5, and R represents hydrogen or 1 carbon atom.
Represents from 10 to 10 alkyl groups. ] [In the formula, y represents an average value and is 35 to 150. And a long-chain alkyl compound represented by the following formula (4): [Wherein X ₁ and X ₂ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a halogen atom, and X ₁ and X ₂ may be the same or different;
And m 'represents an integer of 1 to 3, R ₁ and R ₃ is a hydrogen atom, an alkyl of C ₁ ~ _18, alkenyl, sulfonamide, mesyl, sulfonic acid, carboxy ester, hydroxy, alkoxy of C ₁ ~ _18, R ₁ and R ₃ represent an acetylamino, benzoylamino group or a halogen atom;
May be the same or different; n and n ′ represent an integer of 1 to 3; R ₂ and R ₄ represent a hydrogen atom or a nitro group; A ⁺ represents a cation ion;
It has ９８98 mol% of ammonium ions, and additionally has hydrogen ions, sodium ions, potassium ions or mixed ions thereof. A process cartridge comprising a toner containing the azo-based iron complex compound represented by the formula: 24. The process cartridge according to claim 23, wherein the photosensitive member is a photosensitive drum. 25. The process cartridge according to claim 24, wherein the contact charging means is provided so as to press against the photosensitive drum. 26. The process cartridge according to claim 25, wherein the contact charging means is a charging roller means. 27. The process cartridge according to claim 26, wherein the contact charging means is a charging brush means. 28. The process cartridge according to claim 26, wherein the contact charging means is a charging blade means. 29. The process cartridge according to claim 23, wherein the cleaning unit is provided in contact with the photosensitive member. 30. The process cartridge according to claim 29, wherein the cleaning means is a cleaning blade means. 31. The process cartridge according to claim 23, wherein the long-chain alkyl compound contains a long-chain alkyl alcohol represented by the formula (1). 32. The process cartridge according to claim 23, wherein the toner has a negative triboelectric charging property.