JP3486525B2 - Magnetic toner and image forming method - 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 in electrophotography, electrostatic recording and the like, and more particularly to an insulating magnetic toner and an image forming method using the magnetic toner.

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic method, U.S. Pat. No. 2,297,691 and JP-B-42-23910 are known.
Publication (US Pat. No. 3,666,363) and Japanese Patent Publication No. 43-24748 (US Pat. No. 4,074)
Although a large number of methods are known, as described in No. 1,361), etc., a photoconductive substance is generally used and an electric latent image is formed on a photoconductor by various means. ,
Next, the latent image is developed with toner to form a visible image, and if necessary, the toner image is transferred to a transfer material such as paper and then fixed by heating, pressure, etc. to obtain a copy.

Various methods are known for visualizing an electrostatic latent image using toner. For example, US Pat. No. 2,874,
No. 063 specification, magnetic brush method, No. 2,618,552 specification, cascade development method, and No. 2,221,776 specification, powder cloud method. A large number of developing methods are known, such as a fur brush developing method and a liquid developing method.

Among these developing methods, a magnetic brush method, a cascade method, a liquid developing method, and the like, which use a developer mainly containing toner and carrier, have been widely put into practical use.

On the other hand, various developing methods using a one-component developer consisting only of toner have been proposed, and one of them is a method using a developer consisting of magnetic toner particles.

In the developing method using the above magnetic toner,
There are instability factors related to the magnetic toner used. that is,
A considerable amount of fine powdery magnetic material is mixed and dispersed in the magnetic toner, and a part of the magnetic material is exposed on the surface of the magnetic toner particles. It also affects the triboelectrification property and, as a result, affects various properties required for the magnetic toner such as the developing property and durability of the magnetic toner.

In the conventional developing method using a magnetic toner containing a magnetic substance, if a developing process (for example, copying) is repeated for a long period of time, the fluidity of the developer containing the magnetic toner is deteriorated, and the developer is normally processed. However, it is not possible to obtain sufficient triboelectrification, uneven charging is likely to occur, and a fogging phenomenon is likely to occur in a low temperature and low humidity environment, which easily causes a problem on a toner image. When the adhesiveness between the binder resin that constitutes the magnetic toner particles and the magnetic material is weak, repeated development steps cause
There is a tendency that the magnetic substance is removed from the surface of the magnetic toner particles to give an adverse effect such as a decrease in image density.

When the dispersion of the magnetic substance in the magnetic toner particles is non-uniform, the magnetic toner particles containing a large amount of the magnetic substance accumulate on the sleeve, resulting in a decrease in image density and unevenness in density called a sleeve ghost. Occurrence may be seen.

Conventionally, proposals have been made regarding magnetic iron oxide contained in magnetic toners, but there are still some points to be improved.

For example, Japanese Patent Laid-Open No. 3-67265 proposes a method of using spherical magnetic particles having a divalent metal oxide in the surface layer of magnetic iron oxide particles. In this method, the coercive force of the magnetic particles is preferably 40 to 70 oersteds (3.2 to 5.6 kA / m), which is relatively small, in order to weaken the magnetic binding force and magnetic cohesive force of the magnetic toner. It is also stated that smaller ones are better.

However, as a result of a detailed study by the present inventors, when spherical magnetic particles are used in a magnetic toner, magnetic particles appearing on the surface of the magnetic toner particles are more spherical than spherical hexagonal or octahedral particles. It was found that the amount of abrasion on the surface of the photoconductor was large because there were many fine particles.

Magnetic particles having a small coercive force (H _c ) and a remanent magnetization (σ _r ) have a weak magnetic binding force, and therefore fog is likely to occur especially in a low humidity environment. This is considered to be due to the following reasons.

In the development using the magnetic toner, a magnet having four or more magnetic poles is usually provided inside the developer carrying member (developing sleeve). When magnetic toner flies from the developing sleeve to the photoconductor to form a visible image on the photoconductor, the propulsive force is the triboelectric charge amount of the magnetic toner, and the magnetic force of the magnetic particles suppresses it. is there. If the saturation magnetization is large, the magnetic restraining force of the magnetic toner that has come to the magnetic pole position of the magnet in the developing sleeve becomes large, and the phenomenon of fogging can be suppressed, but in the magnetic toner located between the magnetic poles of the magnet in the developing sleeve, Since the saturation magnetization is lowered, the development cannot be suppressed by the saturation magnetization. Especially in a low humidity environment, since the charge amount of the magnetic toner becomes large, the magnetic toner easily fly to the photoconductor,
Fog is likely to occur.

In the magnetic material proposed in Japanese Patent Laid-Open No. 3-67265, since Zn (OH) ₂ is gradually dropped during the oxidation reaction, a large amount of zinc-iron oxide is present inside the magnetic particles. You can do what you are doing. Furthermore, since the zinc content is high and the zinc content is also high inside the magnetic particles, the magnetic properties (particularly σ _r and H _c ) are low. Furthermore, since the content of zinc component is high, the magnetic substance tends to be reddish, and when such a magnetic substance is used as toner, image formation is performed, the halftone image becomes brownish. Cheap.

In JP-A-62-279352 and JP-A-62-278131, magnetic toners containing magnetic iron oxide containing silicon element are proposed. Such magnetic iron oxide intentionally allows the silicon element to be present inside the magnetic iron oxide, but the fluidity of the magnetic toner containing the magnetic iron oxide still has a point to be improved.

Japanese Patent Publication No. 3-9045 proposes to control the shape of magnetic iron oxide into a spherical shape by adding a silicate. Magnetic iron oxide obtained by this method, since a large amount of silicon element is distributed inside the magnetic iron oxide because a silicate is used for controlling the particle size, the amount of silicon element present on the magnetic iron oxide surface is small, The improvement of fluidity of the magnetic toner tends to be insufficient.

Japanese Patent Laid-Open No. 61-34070 proposes a method for producing ferric tetraoxide by adding a hydroxosilicate solution during the oxidation reaction to ferric trioxide. The ferrosoferric oxide particles produced by this method have Si near the surface.
Although it contains an element, the Si element forms a layer near the surface of the ferrosoferric oxide particles, and the particle surface has a problem that it is weak against mechanical impact such as friction.

In order to solve the above problems, the inventors of the present invention have disclosed that in Japanese Patent Laid-Open No. 5-72801, magnetic iron oxide contains a silicon element, and the magnetic material surface contains a total silicon element. A magnetic toner containing magnetic iron oxide in which 44 to 84% of the ratio is present is proposed.

However, in the magnetic toner containing the magnetic iron oxide, the fluidity of the toner and the adhesiveness with the binder resin have been sufficiently improved, but due to the uneven distribution of silicon element on the surface of the magnetic iron oxide, The environmental characteristics, especially the charging characteristics tend to deteriorate when left for a long time under high humidity.

Further, Japanese Patent Application Laid-Open No. 4-362954 proposes a magnetic iron oxide containing both silicon element and aluminum element, but it has a point to be improved in environmental characteristics.

Further, Japanese Patent Application Laid-Open No. 5-213620 proposes a magnetic iron oxide containing a silicon component and having the silicon component exposed on the surface. Have a point to do.

Furthermore, in recent years, it has been desired to improve the image quality of a copy image or a print image by digitizing a copying machine and making fine particles of magnetic toner.

In a photographic image containing characters, the characters of the copied image are clear, and the photographic image is required to have density gradation that is faithful to the original. In general, in copying a photo image with text, if the line density is increased to make the text clear, not only the density gradation of the photo image is impaired, but also the halftone portion tends to have a sharp image.

When the line density is increased, the amount of the magnetic toner deposited in the transfer step of the magnetic toner is large, so that the magnetic toner is pressed against the photoconductor and adheres to the photoconductor during the transfer, so that the magnetic toner in the line image comes off. In addition, a so-called hollow image phenomenon occurs, and a copy image with low image quality is likely to be obtained. On the other hand, when trying to improve the density gradation of the photographic image, the density of the character line decreases, and the sharpness tends to decrease.

In recent years, the image density has been read and the density gradation has been improved to some extent by digital conversion. However, further improvements are expected.

Further, by reducing the magnetic toner particle size, the surface area of the magnetic toner per unit weight is increased,
The width of the charge amount distribution is likely to be large and fogging is likely to occur. The increase in the surface area of the magnetic toner makes the charging characteristics of the magnetic toner more susceptible to the environment.

When the particle size of the magnetic toner is reduced as described above, the dispersion state of the magnetic substance and the colorant, the magnetic characteristics of the magnetic substance, and the surface characteristics affect the charging property of the magnetic toner.

When such a small-diameter magnetic toner is applied to a high-speed copying machine, it may cause excessive fog in a low-humidity environment, causing fog and a decrease in density.

Here, in order to solve the various problems described above, the technique disclosed in Japanese Patent Laid-Open No. 101529/1996: The surface of a magnetic material is covered with a thin film of iron-zinc oxide. The saturation magnetization (σ _s ) under a magnetic field of 58 kA / m (1 k Oersted) is 50 Am ² / kg or more, the remanent magnetization (σ _r [Am ² / kg]) and the coercive force (H
The product (σ _r × H _c ) of _c [kA / m]) is 60 to 250 [k
A ² m / kg], a magnetic toner containing a magnetic material is disclosed.

However, in JP-A-8-101529, a magnetic toner having a small particle size (especially, a toner particle size of 7.5 μm is used).
The following magnetic toner) process speed 380mm / s
When developing to a high-speed copying machine of ec or higher (high-speed copying machine of A4 copying speed 60 sheets per minute or more), the following phenomenon occurs when the image output durability is continued, especially in a low humidity environment. It often becomes.

1) Among the toner particles existing on the developing sleeve, toner particles having a small particle size are selectively developed,
As the image output durability is continued, the phenomenon of selective development in which the toner particle size on the developing sleeve becomes coarser is more likely to occur. Along with that, a phenomenon that the image quality is deteriorated easily occurs.

2) When the cleaning blade is turned over or a cleaning failure occurs, the waste toner that is not removed by the cleaning blade slips through the cleaning blade and enters the developing area, resulting in image deterioration and exposure of the waste toner. Occurrence of fusion to the body drum (these phenomena are thought to be due to the unstable behavior of the waste toner in the cleaner).

3) A non-uniform phenomenon of the sleeve coat state (especially the sleeve coat state may become wavy) may occur when the image is continuously produced and durable in a low humidity environment. This phenomenon is considered to be caused by the destabilization of the toner chargeability in a low humidity environment.

Particularly in the future, since the toner particle size tends to be further reduced and the speed of copying machines is increasing, it is an important issue to solve the above problems 1) to 3). .

[0035]

SUMMARY OF THE INVENTION An object of the present invention is to provide a magnetic toner and an image forming method using the toner, which solves the above problems.

Still another object is to provide a magnetic toner capable of obtaining a good image even in a high speed copying machine and an image forming method using the toner.

Still another object is to provide a magnetic toner which has stable triboelectric charge amounts between toner particles and between a toner and a toner carrier such as a sleeve and which can be controlled to a charge amount suitable for a developing system to be used. It is to provide an image forming method using the same.

Still another object is to provide a magnetic toner capable of faithfully developing a digital latent image and sharply reproducing the edge portion of a dot, and an image forming method using the toner. Especially.

Still another object is to provide a magnetic toner that maintains the initial performance even when the toner is continuously used for a long period of time, and an image forming method using the toner.

Still another object is to provide a magnetic toner having less fog and reversal fog even in an image forming process including post-charging, and an image forming method using the toner.

Still another object is to provide a magnetic toner that reproduces a stable image that is not affected by changes in temperature and humidity, and an image forming method using the toner.

Still another object of the present invention is to provide a magnetic toner having excellent storage stability which maintains initial characteristics even after long-term storage, and an image forming method using the toner.

Still another object is to provide a magnetic toner which gives a good image even when the toner particle size is made small and even under low humidity, and an image forming method using the toner.

[0044]

The present invention relates to a magnetic toner containing at least a binder resin, a magnetic material and a charge control agent, wherein the magnetic material is at least one kind selected from Zn, Mn and Ti. Including element A and silicon element,
In the element distribution analysis in the magnetic material, the dissolution rate of iron element is 1
The content of the element A that elutes by 0 mass% is 60 mass% or more of the total content of the element A, and the content of the silicon element that elutes by the iron element dissolution rate of 10 mass% is the total content of the silicon element. 70 mass% or more of the amount, and the content of elemental silicon that elutes up to an iron element dissolution rate of 10 mass% is larger than the content of element A that elutes up to an iron element dissolution rate of 10 mass%, The present invention relates to a magnetic toner containing at least one calixarene compound represented by the following general formula (1) as a control agent.

[0045]

[Chemical formula 3] [In the formula, R ₁ and R ₅ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ₁ and R ₅ may be the same or different, and R ₂ and R ₆ are represents hydrogen atom, R ₃ and R ₄ represents a hydrogen atom, R ₇ is a alkyl group, a Lee <br/> group, shows the a recycler click radical, n is an integer from 4 to 8 And m represents an integer of 0 to n, which is n or less. In the present invention, the electrostatic latent image on the electrostatic image carrier is developed by the developing means in the developing section to form a toner image on the electrostatic latent image carrier, and the toner image is recorded on the recording material. In an image forming method for transferring and fixing the transferred toner image on the recording material, the developing means has a toner, and the magnetic toner having the above-mentioned configuration is used as the toner. Regarding

By adopting the toner constitution of the present invention, a toner having a small particle diameter can be processed at a process speed of 380 mm / se.
Even when applied to a high-speed copying machine of c or higher (high-speed copying machine of A4 copying speed 60 sheets per minute or more), a good image can be provided for a long time.

By applying the toner of the present invention to the image forming method of the present invention, a high quality image can be provided for a long period of time.

[0048]

BEST MODE FOR CARRYING OUT THE INVENTION The magnetic substance of the present invention is such that the magnetic characteristics of the magnetic substance are changed by the silicon element existing in the vicinity of the surface of the magnetic substance and at least one element A selected from Zn, Mn and Ti. In addition, the electric resistance of the magnetic material can be controlled, and the charge amount distribution of the magnetic toner can be controlled.

The magnetic substance used in the magnetic toner of the present invention contains at least one element A selected from Zn, Mn and Ti and a silicon element, and in the element distribution in the magnetic substance, the iron element dissolution rate is 10% by mass. The content of the element A that elutes up to 60 mass% or more of the total content of the element A, and the content of the silicon element that elutes up to 10 mass% of the iron element dissolution rate is 70 mass% of the total content of the silicon element. The magnetic property, which is not less than mass% and more than the content of element A eluted at an iron element dissolution rate of 10 mass% is higher than the content of element A eluted at an iron element dissolution rate of 10 mass%. It is the body.

Furthermore, the content of at least one element A selected from Zn, Mn, and Ti must be 0.05 to 3 mass% based on the total iron element. By adjusting the content, it is possible to control the electric resistance of the magnetic material and control the distribution of the charge amount of the magnetic toner.

The content of at least one element A selected from Zn, Mn and Ti is 3% by mass based on the total iron element.
If it exceeds, the blackness of the magnetic material may change and the blackness of the copy image may change.

Further, the magnetic characteristics of the magnetic material (especially H _c ,
σ _r ) and electric resistance are liable to change, and as a result, when such a magnetic material is used in toner, fog occurs in low humidity, and image density decreases and initial image density decreases after being left in high humidity. It may occur.

The content of at least one element A selected from Zn, Mn and Ti is 0.05 based on the total iron element.
If it is less than 10% by mass, it becomes difficult to control the electric resistance of the magnetic substance, and when such a magnetic substance is used for the toner, the toner charge-up phenomenon is likely to occur particularly in a low humidity environment. Image density is likely to decrease.

Further, the content of at least one element A selected from Zn, Mn, and Ti present in the iron element dissolution rate up to 10 mass% is 60 mass% or more of the total content of the element A. is necessary.

Here, the content rate of at least one element A selected from Zn, Mn, and Ti present in the iron element dissolution rate up to 10 mass% is less than 60 mass% of the total content of the element A. In such a case, it becomes difficult to control the electric resistance of the magnetic substance, and when such a magnetic substance is used for the toner, the toner charge-up phenomenon is likely to occur particularly in a low humidity environment, and the image is accompanied by the phenomenon. The concentration tends to decrease. The presence of a layer containing at least one element A selected from Zn, Mn and Ti in the vicinity of the surface of the magnetic material plays a role in controlling the electric resistance of the magnetic material and is important for charging the magnetic toner. By playing a role.

Further, it is necessary that the total silicon element content is 0.05 to 2 mass% based on the total iron elements constituting the magnetic body, and the total silicon element content is the above content. As a result, it is possible to provide a magnetic material that is effective in controlling the fluidity of the magnetic toner and improving the charging characteristics in a high humidity environment.

When the total silicon element content is less than 0.05% by mass based on the total iron elements constituting the magnetic material,
The fluidity of the magnetic toner is lowered, and if it exceeds 2% by mass, the charging property is lowered when the magnetic toner is left for a long time in a high humidity environment.

The surface of the magnetic material has a two-layer structure of a layer containing a large amount of silicon element and a layer containing a large amount of at least one element A selected from Zn, Mn and Ti. It is preferable that the layer that is included in a large amount forms the surface layer.

By the outermost surface layer containing a large amount of silicon element, the magnetic material partially present on the surface of the magnetic toner particles improves the fluidity of the magnetic toner, and the chargeability of the magnetic toner becomes good.

If the content of the silicon element existing up to the iron element dissolution rate of 10 mass% is not more than 70 mass% of the total silicon element content, the above effect is small.

Further, the layer containing a large amount of at least one element A selected from Zn, Mn and Ti makes it possible to control the electric resistance of the magnetic material and to reduce the density and fog due to excessive charging in a low humidity environment. To suppress the decrease of the toner charge amount in a high humidity environment.

The above is due to the fact that the surface layer containing the silicon element is easily charged, and the difference in electrical resistance between the surface layer containing the silicon element and the next layer containing the element A. It is considered that the movement of the electric charge easily occurs between the surface layer and the inside of the magnetic substance, and as a result, the stable charging property of the magnetic toner is exhibited.

Further, the content of the elemental silicon that elutes up to the iron element dissolution rate of 10% by mass is at least 1 selected from Zn, Mn, and Ti that elutes up to the iron element dissolution rate of 10% by mass.
When the content of the element A of the seed is smaller than the content of the seed A, the two-layer structure of the layer containing a large amount of silicon element and the layer containing a large amount of element A may be reversed.

When this two-layer structure is reversed, the effect of improving the fluidity of the toner by the layer containing the silicon element is reduced, and the layer containing a large amount of the silicon element on the surface of the magnetic material becomes the inner layer.
The control effect of the charge amount and electric resistance of the magnetic toner decreases, and the charge-up phenomenon of the magnetic toner easily occurs, especially in a low humidity environment, and the image density may decrease.

When the element A is inside the layer containing a large amount of silicon element and the layer is not formed, the initial image density after being left for a long time in a high temperature and high humidity environment is likely to be slightly low and the density gradation is deteriorated. It's easy to do.

The shape of the magnetic material used in the present invention is preferably a hexahedral shape or an octahedral shape. This is because the hexahedral or octahedral magnetic material is less likely to appear on the surface of the magnetic toner particles, and the photoconductor is less likely to be scraped or scratched.

Further, the number average particle diameter of the magnetic material used in the present invention is preferably 0.05 to 0.35 μm.

This is because the number average particle diameter of the magnetic substance is 0.0
If it is less than 5 μm, the magnetic substance becomes reddish, and if it is more than 0.35 μm, the magnetic substance is not uniformly dispersed in the magnetic toner particles, and the charge amount distribution of the magnetic toner is broad. And the image quality easily deteriorates due to fogging.

An example of the method for producing the magnetic body used in the present invention is shown below, but the magnetic body used in the present invention is not limited to the magnetic body obtained by the following production method.

[Example of Manufacturing Method of Magnetic Material Used in Present Invention]
An aqueous solution containing a ferrous salt as a main component was mixed with an alkaline aqueous solution in an amount equal to or more than iron, and then the free hydroxyl group concentration was 1
The oxidation reaction is carried out at 70 to 90 ° C. while maintaining 3 g / liter.

After the completion of the oxidation reaction, a ferrous salt containing at least one element A selected from Zn, Mn and Ti is added to adjust the pH to 6.0 to 9.0, and the oxidation reaction is performed again to carry out the reaction. To end.

After completion of the oxidation reaction, a ferrous salt containing silicate is added to adjust the pH to 6.0 to 9.0, and the oxidation reaction is carried out again to complete the reaction. After completion of the reaction, the product is filtered and dried to obtain a magnetic substance.

The amount of the magnetic substance used in the present invention added to the toner is 10 to 200 parts by mass, preferably 20 to 150 parts by mass, based on 100 parts by mass of the binder resin.

The embodiments of the magnetic material of the present invention have been described above.

Further, in the present invention, it is necessary to contain at least one calixarene compound represented by the following general formula (1) as a charge control agent.

[0076]

[Chemical formula 4] [In the formula, R ₁ and R ₅ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ₁ and R ₅ may be the same or different, and R ₂ and R ₆ are represents hydrogen atom, R ₃ and R ₄ represents a hydrogen atom, R ₇ is a alkyl group, a Lee <br/> group, shows the a recycler click radical, n is an integer from 4 to 8 And m represents an integer of 0 to n, which is n or less. Here, the calixarene compound used in the present invention includes: 1) J. Am. Chem. Soc. 103 3782
3792 (1981) 2) Pure & Appl. Chem, Vol. 58, N
o11 1523-1528 (1985) 3) Tetrahedron Letters, Vo.
l. 26, No28 3343-3344 (1985) 4) Hyundai Kagaku, 182 14-23 (1986) and the like.

Examples of the calixarene compound of the present invention are shown below, but the invention is not limited thereto.

[0078]

[Chemical 5]

[0079]

[Chemical 6]

Here, as described in JP-A-7-295299, since the calixarene compound does not contain heavy metals, there is no need to worry about the influence of heavy metals on the human body as in the conventional case.

Further, it has a characteristic of being substantially colorless, and may be applicable as a charge control agent to a wide range of toners including color toners.

In the cyclic structure which is a characteristic of the calixarene compound, the performance as a charge control agent can be improved by changing the number of rings and the structure of R _{1 to} R _{7 in} the structural formula (1) of the calixarene compound. May be controlled.

However, if only the calixarene compound is used, it is difficult to obtain a stable and appropriate charge amount in a wide range of environments, and if the image output durability is continued, the image density may decrease.

The present inventors have made a toner containing at least one kind of the calixarene compound represented by the general formula (1) and the above-mentioned specific magnetic material, and thereby a magnetic toner having a particularly small particle diameter (particularly a toner particle diameter). Magnetic toner of 7.5 μm or less) to a high-speed copying machine with a process speed of 380 mm / sec or more (high-speed copying machine with A4 copying speed of 60 sheets per minute or more), 1) selective development 2) Bleed phenomenon of cleaning blade, occurrence of cleaning failure, and occurrence of drum fusion 3) Coat uneven phenomenon of sleeve that occurs during image forming durability under low humidity environment is solved, and during image forming durability, It was possible to obtain a good image in which the image density was stable and the image density did not decrease and the image density did not change.

In addition to the above, the effect of improving the image quality such as halftone image quality, resolution and fine line resolution could be obtained.

The details of the above reason are not clear at present, but by using a toner containing at least one kind of the specific magnetic substance and the calixarene compound represented by the general formula (1), 1) the toner The overall balance of charge accumulation and discharge is improved, and the toner charge amount distribution can be controlled. 2) By the above action, the chargeability of the waste toner in the cleaner is stabilized, and the rubbing action (rubbing action) of the waste toner on the photosensitive drum in the cleaner becomes more uniform. 3) During the production of the toner, the dispersion state of the magnetic substance and the calixarene compound in the binder resin becomes more uniform,
The distribution state of the calixarene compound existing on the toner surface becomes more uniform. It is considered that this phenomenon occurs.

Further, by applying the magnetic toner of the present invention to the image forming method of the present invention, a higher quality image (particularly the effect of further improving halftone image quality, fine line reproducibility and resolution in terms of image quality) is obtained. It became clear that it can be provided for a long time.

With respect to the above reason, when the magnetic toner of the present invention is applied to the image forming method of the present invention, the distribution of the charge amount of the magnetic toner becomes sharper, and the individual particles of the magnetic toner are more uniformly charged. It is thought to be to do so.

The addition amount of the calixarene compound used in the present invention in the toner is preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the binder resin. When the amount of the calixarene compound added to the binder resin is less than 0.1 parts by mass, the dispersibility of the calixarene compound in the toner is insufficient, and when it exceeds 15 parts by mass, a proper charge amount as a toner is stabilized. Difficult to maintain.

In the present invention, the binder resin for the toner is not particularly limited, but polyester resin and styrene-acrylic resin are preferable.

The polyester resin is not particularly limited, and conventionally known polyester resins can be used. As the monomer constituting the polyester resin, the following conventionally known substances can be used, but the present invention is not limited thereto.

As the alcohol component, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, dipropylene glycol,
Triethylene glycol, 1,5-pentanediol,
1,6-hexanediol, neopentyl glycol,
Pentaerythritol diallyl ether, trimethylene glycol, 2-ethyl-1,3-hexanediol,
Hydrogenated bisphenol A, or a bisphenol derivative represented by the following formula:

[0093]

[Chemical 7] (In the formula, R is an ethylene or propylene group, and x, y
Are each an integer of 1 or more, and the average value of x + y is 2 to 10. ) And other diols.

As the acid component, unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid and itaconic acid or acid anhydrides thereof, dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or these And aromatic dicarboxylic acids such as phthalic acid and terephthalic acid.

Examples of trihydric or higher alcohols include glycerin, sorbit, sorbitan, and the like, and trivalent or higher trivalent acids include trimellitic acid, pyromellitic acid, and acid anhydrides thereof.

The method for producing the polyester resin used in the present invention is not particularly limited, and a conventionally known production method can be applied.

The styrene-acrylic resin is not particularly limited, and a conventionally known styrene-acrylic resin can be used. As the monomer constituting the styrene-acrylic resin, the following conventionally known substances can be used, but the present invention is not limited thereto.

For example, styrene, o-methylstyrene,
m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, p- n-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o -Nitrostyrene, p-
Styrene derivatives such as nitrostyrene; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate,
Α-Methylene aliphatic monocarboxylic acid esters such as phenyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate,
Acrylic esters such as propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate and phenyl acrylate; acrylics such as acrylonitrile, methacrylonitrile and acrylamide Acid or methacrylic acid derivatives; acroleins;
Acrylic acid, methacrylic acid, crotonic acid, itaconic acid,
Examples thereof include carboxyl group-containing vinyl monomers such as maleic anhydride, fumaric acid, maleic acid and their monoesters such as methyl, ethyl, butyl and 2-ethylhexyl.

In the present invention, a combination of a styrene monomer, methacryl or an acrylic monomer and a carboxyl group-containing monomer is preferable.

As the binder resin of the toner, in addition to polyester resin and styrene-acrylic resin, styrene-vinyl methyl ether copolymer, styrene-butadiene copolymer, styrene-vinyl methyl ketone copolymer, styrene-acrylonitrile. A styrene-based copolymer of styrene such as an indene copolymer and another vinyl-based monomer;
Polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyamide, epoxy resin, polyvinyl butyral, polyacrylic acid, phenol resin,
Aliphatic or alicyclic hydrocarbon resins, petroleum resins, chlorinated paraffins and the like can be used.

In the present invention, other charge control agents may be used in combination, if necessary, and conventionally known charge control agents are used.

The following are examples of charge control agents known in the art today.

For example, an organometallic complex and a chelate compound are effective, and the above-mentioned monoazo metal complex, acetylacetone metal complex, aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid type metal complex can be used.

In addition, aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides,
Esters; phenol derivatives such as bisphenol.

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

The silica fine powder used in the present invention is BE.
Specific surface area due to nitrogen adsorption measured by T method is 30 m ² / g
Those in the above range (particularly 50 to 400 m ² / g) give good results. The fine silica powder is used in an amount of 0.01 to 8 parts by mass, preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the toner.

The silica fine powder used in the present invention may contain silicone varnish, various modified silicone varnish,
It is also preferable that they are used in combination with a treating agent such as silicone oil, various modified silicone oils, silane coupling agents, silane coupling agents having a functional group, and other organosilicon compounds.

Further, as other additives, for example, lubricants such as Teflon, zinc stearate, polyvinylidene fluoride, etc., or polishing agents such as cerium oxide, silicon carbide, strontium titanate, etc., among which strontium titanate is preferable. Alternatively, for example, a fluidity-imparting agent such as titanium oxide or aluminum oxide, among which a hydrophobic agent is particularly preferable. A small amount of an anti-caking agent or a conductivity-imparting agent such as carbon black, zinc oxide, antimony oxide, tin oxide, or white and black fine particles having opposite polarities can be used as a developing property improver.

Further, a wax-like substance may be added to the toner of the present invention for the purpose of improving offset resistance at the time of heat roll fixing.

The wax-like substance used in the present invention includes the following. Low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax,
Aliphatic hydrocarbon wax such as paraffin wax may be used.

As the aliphatic hydrocarbon wax, for example, a low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or by a Ziegler catalyst under low pressure, an alkylene polymer obtained by thermally decomposing a high molecular weight alkylene polymer, A wax such as a synthetic hydrocarbon obtained from a distillation residue of a hydrocarbon obtained by the Arge method from a synthesis gas composed of carbon monoxide / hydrogen, or obtained by hydrogenating these can be used.

Further, it is possible to use the one in which the hydrocarbon wax is fractionated by the use of a press sweating method, a solvent method, vacuum distillation or a fractional crystallization method. As an example of the aliphatic hydrocarbon wax, in the DSC curve measured by a differential scanning calorimeter, regarding the endothermic peak at the time of temperature rise and the exothermic peak at the time of temperature decrease, the endothermic onset temperature is 50 to
Aliphatic hydrocarbon system in the range of 110 ° C., having at least one endothermic peak in the temperature range of 70 to 130 ° C., and having the maximum exothermic peak during cooling within the peak temperature of the endothermic peak ± 9 ° C. Waxes can be mentioned.

The hydrocarbon as a base is synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (often two or more multi-component system), for example, the gintol method, the hydrocol method ( A fluidized catalyst bed is used), or an Arge process (using a fixed catalyst bed) that produces a large amount of waxy hydrocarbons is used to polymerize hydrocarbons having up to several hundred carbon atoms and alkylenes such as ethylene with a Ziegler catalyst. Hydrocarbons can be used.

Further, a wax synthesized by a method which does not depend on the polymerization of alkylene can be used.

Further, examples of the wax-like substance used in the present invention include oxides of aliphatic hydrocarbon wax such as oxidized polyethylene wax or block copolymers thereof; fatty acid ester such as carnauba wax and montanic acid ester wax. It is possible to use waxes containing as a main component and fatty acid esters such as deoxidized carnauba wax in which some or all are deoxidized.

Further, saturated straight-chain fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as blancinic acid, eleostearic acid and varinaric acid;
Saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubayl alcohol, ceryl alcohol and melysyl alcohol; polyhydric alcohols such as sorbitol, linoleic acid amides,
Fatty acid amides such as oleic acid amide and lauric acid amide, saturated fatty acid bisamides such as methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, hexamethylenebisstearic acid amide; ethylenebisoleic acid amide, hexamethylene Unsaturated fatty acid amides such as bisoleic acid amide, N, N'-dioleyl adipamide, N, N'-dioleyl sebacic acid amide; m-xylene bisstearic acid amide, N, N'-distearyl isophthalic acid Aromatic bisamides such as amides; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (generally referred to as metallic soap); aliphatic hydrocarbon waxes such as styrene and acrylic acid. Graft waxes grafted with vinyl monomers; partial esterification products of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; methyl ester compounds having hydroxyl groups obtained by hydrogenating vegetable oils and fats You can

Further, examples of the wax-like substance used in the present invention include aliphatic alcohol wax and alkyl monocarboxylic acid wax.

The aliphatic alcohol wax is represented by the following formula (A).

CH ₃ (CH ₂ ) _X CH ₂ OH (A) (X represents an average value and is from 20 to 250) The alkyl monocarboxylic acid wax is represented by the following formula (B).

CH ₃ (CH ₂ ) _Y CH ₂ COOH (B) (Y represents an average value and is 20 to 250)

The wax-like substance used in the present invention may be added to the binder resin in an amount of 0.1 to 20 parts by mass per 100 parts by mass of the binder resin.

In the toner of the present invention, in addition to the magnetic material of the present invention, metals such as iron, cobalt and nickel or aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony of these metals, Magnetic materials such as alloys of metals such as beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof may be used in combination.

These magnetic materials which may be used in combination have an average particle size of 0.1 to 2 μm, preferably 0.1 to 0.5 μm.
It is preferable that the amount is about 20 to 200 parts by mass with respect to 100 parts by mass of the binder resin component.

Further, as the colorant which may be used in the toner of the present invention, any suitable pigment or dye may be mentioned.

Toner colorants are well known, and examples of pigments include carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizanin lake, red iron oxide, phthalocyanine blue and indanthrene blue.

These can be used in an amount necessary and sufficient for maintaining the optical density of the fixed image, and can be 0. The amount added is 1 to 20 parts by mass, preferably 2 to 10 parts by mass. Further, a dye can be further used for the same purpose.

For example, there are azo dyes, anthraquinone dyes, xanthene dyes, methine dyes, etc., and 0.1 to 20 parts by weight, preferably 0.3 to 3 parts by weight, relative to 100 parts by weight of the binder resin. The addition amount is good.

The toner of the present invention can be mixed with a carrier and used as a two-component developer composed of the toner and the carrier.

As the above carrier, all known carriers can be used. For example, iron powder, ferrite powder, magnetic powder such as nickel powder, glass beads and the like, and the surface thereof with a fluorine resin or vinyl resin. Alternatively, those treated with a silicone resin or the like can be mentioned.

To prepare the toner according to the present invention, a binder resin, a metal salt or a metal complex, a pigment or a dye as a colorant, a magnetic substance of the present invention, a calixarene compound of the present invention, and optionally other A charge control agent, other magnetic substance, other additives, etc. are thoroughly mixed by a mixer such as a Henschel mixer or a ball mill, and then melted, kneaded and kneaded by using a heat kneader such as a heating roll, kneader or extruder. Metal compounds in the meat and the resins made compatible with each other,
The toner according to the present invention can be obtained by dispersing or dissolving a pigment, a dye, and a magnetic substance, cooling and solidifying, and then pulverizing and classifying.

Further, if desired, desired additives can be sufficiently mixed with a mixer such as a Henschel mixer to obtain the toner according to the present invention.

Further, an image forming apparatus using the toner of the present invention will be described with reference to FIG.

The surface of the photoconductor (electrostatic latent image carrier) 1 is positively charged by the primary charger (charging means) 2, and light image exposure (latent image forming means) 5 (slit exposure or laser beam scanning exposure). To form a latent image (analog or digital) by image scanning with a negatively charged magnetic toner 10 held in a developing device (developing means) 9 having a developing sleeve 4 containing a magnetic blade 11 and a magnet. Develop the latent image.

In the developing section, the bias applying means 12 applies an alternating bias, a pulse bias and / or a DC bias between the conductive substrate of the photosensitive drum (photoconductor) 1 and the developing sleeve 4.

When the transfer material P is conveyed and reaches the transfer portion, the secondary charging device (transfer means) 3 charges from the back surface (the surface opposite to the photosensitive drum side) of the transfer material P, so that the surface of the photosensitive drum is transferred. The developed image (toner image) is electrostatically transferred onto the transfer material P. The transfer material P separated from the photosensitive drum 1 is fixed by a heating and pressure roller fixing device (fixing means) 7 to fix the toner image on the transfer material P.

The toner remaining on the photosensitive drum after the transfer process is removed by a cleaning device (cleaning means) 8 having a cleaning blade. After cleaning, the photosensitive drum 1 is erased by erase exposure 6 and again
The process starting from the charging process by the primary charger 2 is repeated.

The electrostatic latent image carrier (photosensitive drum) 1 has a photosensitive layer and a conductive substrate, and moves in the arrow direction. The cylindrical developing sleeve 4, which is a toner carrier, rotates so as to move in the same direction as the surface of the electrostatic latent image carrier in the developing section. Inside the cylindrical sleeve 4, a multi-pole permanent magnet (magnet roll) that is a magnetic field generating means is arranged so as not to rotate. The magnetic toner 10 in the developing device (developing means) 9 is supplied by the toner supply roller 13 and applied onto the cylindrical surface,
And due to the friction between the surface of the sleeve 4 and the toner particles,
Toner particles are given a negative triboelectric charge, for example. Further, a magnetic doctor blade (developer layer thickness regulating member) 11 made of iron is placed close to the cylindrical surface (interval 50 μm to 5 μm).
(00 μm), the toner layer is made thin (30 μm by arranging it so as to face one magnetic pole position of the multi-pole permanent magnet).
.About.300 .mu.m) and regulated uniformly so that a developer layer thinner than the gap between the electrostatic latent image carrier 1 and the toner carrier (developing sleeve) 4 in the developing section is formed so as not to contact.

Instead of iron as the magnetic doctor blade 11, permanent magnets may be used to form the opposing magnetic poles. In the developing unit, an AC bias or a pulse bias is applied between the toner carrier 4 and the surface of the electrostatic latent image carrier to bias means 12.
May be applied.

Upon transfer of the toner particles in the developing portion, the toner particles are transferred to the electrostatic latent image side by the action of the electrostatic force of the electrostatic latent image bearing surface and the AC bias or the pulse bias.

Instead of the magnetic doctor blade 11, an elastic blade made of an elastic material such as silicone rubber may be used to regulate the layer thickness of the toner layer by pressing, and the developer may be coated on the toner carrier. .

When the image forming apparatus is used as a copying machine or a printer, the optical image exposure 5 is reflected light or transmitted light from an original, or an original is read out and converted into a signal, and scanning of a laser beam or LED is performed by this signal. It is performed by driving the array or the liquid crystal shutter array.

Further, as a material for coating the sleeve surface of the coated developing sleeve of the present invention, a polymer material forming a coating layer, conductive fine particles, etc. are used.

As the conductive fine particles used in the coated developing sleeve of the present invention, carbon fine particles are preferable, and graphite (more preferably crystalline graphite) or the like can be used in combination.

The crystalline graphite used in the present invention is roughly classified into natural graphite and artificial graphite. Artificial graphite is made by solidifying pitch coke with tar pitch or the like, firing it once at about 1200 ° C, and then putting it in a graphitization furnace.
By treating at a high temperature of about 300 ° C., carbon crystals grow and change into graphite. Natural graphite is completely graphitized from the ground by natural geothermal heat and underground high pressure for a long time. These graphites have a wide range of industrial uses because they have various excellent properties. Graphite is a very soft and smooth crystalline mineral with a dark gray or black luster, and has heat resistance, chemical stability, and excellent lubricity. The crystal structure includes hexagonal crystal and others belonging to the rhombohedral system, and has a completely layered structure. Regarding the electrical characteristics, free electrons are present between carbon-carbon bonds, making it a good conductor of electricity. The graphite used in the present invention may be natural or artificial.

The graphite used in the coated developing sleeve of the present invention preferably has a particle size of 0.5 μm to 10 μm.

Further, amorphous carbon is an example of the conductive fine particles.

Amorphous carbon is generally "an aggregate of crystallites formed by burning or pyrolyzing a hydrocarbon or a compound containing carbon in a state where the air supply is insufficient".
Is defined as In particular, it is widely used because it has excellent electric conductivity, and it can be filled with a polymer material to give conductivity, or it can obtain an arbitrary conductivity to some extent by controlling the amount added. The particle size of the conductive amorphous carbon used in the present invention is preferably 5 to 100 μm, more preferably 10 to 80 μm, and further preferably 15 to 40 μm.

The conductive fine particles are preferably added in an amount of 3 to 20 parts by mass per 10 parts by mass of the resin component.

When carbon particles and graphite particles are used in combination, it is preferable to use 1 to 50 parts by mass of carbon particles per 10 parts by mass of graphite.

In addition to the conductive fine particles as described above, auxiliary components may be added to the surface coating layer of the coated developing sleeve of the present invention.

Examples of such auxiliary components include nigrosine, azine dyes containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 42-1627), and basic dyes [eg C.I.
I. Basic Yellow 2 (C.I. 4100)
0), C.I. I. Basic Yellow 3, C.I.
I. Basic Red 1 (C.I. 45160),
C. I. Basic Red 9 (C.I. 4250
0), C.I. I. Basic Violet 1 (C.
I. 42535), C.I. I. Basic Violet
3 (C.I. 42555), C.I. I. Basic Vi
olet 10 (C.I. 45170), C.I. I. Ba
sic Violet 14 (C.I. 42510),
C. I. Basic Blue 1 (C.I. 4202
5), C.I. I. Basic Blue 3 (C.I. 5
1005), C.I. I. Basic Blue 5 (C.
I. 42140), C.I. I. Basic Blue 7
(C.I. 42595), C.I. I. Basic Blu
e 9 (C.I. 52015), C.I. I. Basic
Blue 24 (C.I. 52030), C.I. I. Ba
sic Blue 25 (C.I. 52025), C.I.
I. Basic Blue 26 (C.I. 4402)
5), C.I. I. Basic Green 1 (C.I.
42040), C.I. I. Basic Green 4
(C.I. 42000)], etc., and lake pigments of these basic dyes (as a laking agent, phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide) , Ferrocyanide), C.I. I. Solven
t Black 3 (C.I. 26150), Hansa Yellow G (C.I. 11680), C.I. I. Mordl
ant Black 11, C.I. I. Pigment
Black 1, etc., or, for example, benzolmethyl-hexadecylammonium chloride, decyl-trimethylammonium chloride or dialkyltyl compounds such as dibutyl and dioctyl, metal salts of higher fatty acids,
Inorganic fine powders such as glass, mica, zinc oxide, EDTA, metal complexes of acetylacetone, vinyl polymers containing amino groups, polyamine resins such as condensation polymers containing amino groups, etc. Examples include substances that can be easily applied.

Of these, nigrosine, metal salts of higher fatty acids, and vinyl-based polymers having amino groups are particularly preferable from the viewpoint of dispersibility.

Examples of the resin component which is a polymer material forming the coat layer of the coat developing sleeve of the present invention include:
Styrene resin, vinyl resin, polyether sulfone resin, polycarbonate resin, polyphenylene oxide resin, polyamide resin, fluororesin, fibrin resin,
Thermoplastic resin such as acrylic resin, epoxy resin, polyester resin, alkyd resin, phenol resin, melamine resin, polyurethane resin, urea resin, silicone resin, polyimide resin or other thermosetting resin or photocurable resin is used. be able to. Among them, those having releasability such as silicone resin and fluororesin, or those having excellent mechanical properties such as polyether sulfone, polycarbonate, polyphenylene oxide, polyamide, phenol, polyester, polyurethane and styrene resin are more preferable. . Particularly, phenol resin is preferable.

The method for producing the coated developing sleeve used in the present invention is not particularly limited, but as an example, a blank tube after aluminum drawing (surface roughness 2
S) A method of coating the surface with a prepared liquid as in the following formulation example to a thickness of about 0.5 to 30 μm by a spraying method, and then performing a coating treatment in a step such as heat curing in a drying oven (150 ° C.). be able to.

[0155]   (Prescription example 1) Resin: Phenolic resin (solid content) 30 parts by mass ・ Carbon: 5 parts by mass of amorphous carbon   (CONDUCTEX 975 UB made by Columbia Carbon Co., Ltd.) ・ Conductive lubricant ... Artificial graphite (2 μm) 25 parts by mass ・ Nigrosine dye 5 parts by mass Diluent: methyl alcohol methyl cellosolve 200 parts by mass

[0156]   (Prescription example 2) Resin: Phenolic resin (solid content) 15 parts by mass ・ Conductive lubricant ... Artificial graphite (1 μm) 15 parts by mass ・ Nigrosine dye 7 parts by mass Diluent: methyl alcohol methyl cellosolve 225 parts by mass

Further, as a method for producing the coated developing sleeve of the present invention, after the above coating treatment, the surface of the resin coating layer of the sleeve may be polished.

As an example of this surface polishing process, while rotating the coated sleeve after the drying step at about 13S ⁻¹ , the felt is 9.8 × 10 ⁻² to 9.8 × 10 ⁻¹ M.
Contact at a pressure of about Pa.

This felt is arranged in the longitudinal direction of the sleeve 10 to 10.
There is a method of moving from one end to the other end at a speed of 50 mm / sec.

The polishing method is not limited to this, and it is also possible to use a paper waste cloth, a cloth waste cloth, or the like, and it is also possible to directly polish by hand without rotating the sleeve.

[0161]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.

Production Example 1 of Magnetic Material 100 liters of ferrous sulfate aqueous solution containing Fe ²⁺ 1.7 mol / liter and 100 liters of 3.55N caustic soda aqueous solution
The liters were mixed and stirred.

4.2 g of residual caustic soda in the mixed aqueous solution
After adjusting the temperature to 80 liters / liter, 35 liters / min of air was blown in while maintaining the temperature at 80 ° C. to once terminate the reaction.

Next, 2.25 liters of an aqueous solution prepared by adding zinc sulfate to Zn ²⁺ 0.5 mol / liter in an aqueous ferrous sulfate solution containing Fe ²⁺ 1.3 mol / liter was prepared. In addition to the reaction slurry,
The reaction was terminated by blowing air at liter / min.

Then, in an aqueous ferrous sulfate solution containing Fe ²⁺ 1.01 mol / liter, Si ⁴⁺ 0.44 mol / liter was added.
2.3 L of an aqueous solution containing sodium silicate (No. 3) was separately prepared so as to be liter, added to the reaction slurry, and air of 20 L / min was blown again to terminate the reaction.

The obtained magnetic substance was treated by the usual washing, filtration, drying and crushing steps.

The characteristics of the magnetic material are shown in Table 1.

Manufacturing Examples 2 to 4 of Magnetic Material A magnetic material having the characteristics shown in Table 1 was obtained in the same manner as in Manufacturing Example 1 except that Zn was changed to Mn and Ti.

Further, a magnetic material having the characteristics shown in Table 1 was obtained in the same manner as in Production Example 1 except that Zn and Ti were used in combination.

Production Example 1 of Comparative Magnetic Material A magnetic material having the characteristics shown in Table 1 was obtained in the same manner as in Production Example 1 except that Zn and silicon were not added.

Preparation Examples 2 to 3 of Comparative Magnetic Material By changing the amount of Zn and silicon added, the method of addition, the pH of the reaction system, the reaction time, the reaction temperature, etc., magnetic materials having the characteristics shown in Table 1 were obtained.

The measuring method of each characteristic of the magnetic material is shown below.

(1) One element A selected from Zn, Mn, and Ti If the content sample of silicon is a magnetic toner, a good solvent is selected for the binder resin, and the magnetic substance is
Separate using a magnet. By repeating this operation several times, the binder resin adhering to the surface of the magnetic material is washed away and used as a sample.

In the present invention, the contents of silicon element and element A in the magnetic material used can be determined by the following method. For example, about 3 liters of deionized water is put into a 5 liter beaker and heated in a water bath at 50 to 60 ° C.

About 25 g of a magnetic substance made into a slurry with about 400 ml of deionized water is added to a 5 liter beaker together with the deionized water while being washed with about 300 ml of deionized water.

Next, the temperature is 50 ° C. and the stirring speed is 2
While maintaining at 00 rpm, special grade hydrochloric acid is added to start dissolution.

Approximately 20 ml was sampled several times during the period from the start of dissolution to the time when everything became transparent and became
Filter with a membrane filter and collect the filtrate. The filtrate is quantified for iron element, silicon element and element A by plasma emission spectroscopy (ICP).

The iron element dissolution rate for each sample is calculated by the following equation.

[0179]

[Equation 1]

Similarly, silicon element and element A for each sample
The content of is determined by the formula shown below.

[0181]

[Equation 2]

[0182]

[Equation 3]

As shown in FIG. 1, the iron element dissolution rate-silicon element content rate and the iron element dissolution rate-element A content are plotted to obtain a curve. From this figure, the silicon content and the element A content at an iron element dissolution rate of 10% by mass are read and used as the respective contents in the present invention.

The content of total silicon element and total element A based on the total iron element is determined by the following formula.

[0185]

[Equation 4]

[0186]

[Equation 5]

(2) When the sample of average particle diameter of magnetic material is a magnetic toner, it is treated in the same manner as the content (1) and used.

By projecting a transmission electron micrograph of the magnetic material,
Of the 40,000-fold enlargement, after arbitrarily selecting 250,
The Martin diameter in the projected diameter (the length of a line segment that bisects the projected area in the fixed direction) is measured, and this is represented by the number average diameter.

[0189]

[Table 1]

Production Example of Coat Developing Sleeve A blank tube after aluminum drawing (surface roughness 2S)
A coating solution of the following formulation A was coated on the surface by a spray method to a thickness of about 20 μm, and then heat-cured in a drying oven (150 ° C.) for coating treatment.

[0191]   <Prescription A> Resin: Phenolic resin (solid content) 30 parts by mass ・ Carbon: Amorphous carbon 10 parts by mass   (CONDUCTEX 975 UB made by Columbia Carbon Co., Ltd.) ・ Conductive lubricant ... Artificial graphite (2 μm) 20 parts by mass ・ Nigrosine dye 5 parts by mass Diluent: methyl alcohol + methyl cellosolve 200 parts by mass

Further, after performing the above-mentioned coating treatment, the felt is brought into contact with the pressure of 0.1 MPa while rotating the coating sleeve after the drying step at 12 S ^-1 . This felt was moved from one end to the other end at a speed of 30 mm / sec in the longitudinal direction of the coated sleeve to carry out surface polishing to obtain a coated developing sleeve A of the present invention.

In the examples of the present invention, the toner charge amount on the sleeve, fogging, presence / absence of sleeve coat unevenness occurring during image formation durability, selective developability, halftone image quality, resolution, and fine line reproducibility were evaluated and measured. The procedure was as follows.

1) Toner Charge Amount on Sleeve The charge amount of the toner layer per unit area on the sleeve (toner charge amount on the sleeve in the present invention) was determined by using a so-called suction type Faraday cage method. In this suction type Faraday cage method, the outer cylinder is pressed against the sleeve where the toner layer is present to suck all the toner on a certain area on the sleeve, and at the same time, it accumulates in the inner cylinder electrostatically shielded from the outside. This is a method in which the amount of charge per unit area of the toner layer existing on the sleeve (the amount of toner charge on the sleeve) can be determined by measuring the amount of charge.

2) A fogged A4 paper was used to form a solid white copy image, and the re-fogged value was evaluated by the difference in reflectance between the paper passed through the copying machine and the paper of the same lot.

The reflectance was measured at an arbitrary 9 points on the paper using a reflection densitometer TC-6MC manufactured by Tokyo Denshoku Co., Ltd., and the average value of 9 points was taken as the fog value.

The evaluation criteria for fog are shown below.

[0198]

[Table 2]

3) Regarding the occurrence of sleeve coat unevenness that occurs during image output durability, the sleeve of the developing device is observed every 1000 sheets from the start of image output durability, and the toner coated on the sleeve of the developing device is checked. When the state was non-uniform (especially, the sleeve coat state sometimes became wavy), it was determined that sleeve coat unevenness occurred.

When the toner coated on the sleeve of the developing device was in a uniformly coated state, it was determined that the sleeve coating was not uneven.

4) Selective developability The volume average particle diameter of the toner evaluated as the toner on the developing sleeve after the end of durability was measured by the Coulter counter method, and the volume average particle diameter of the toner on the developing sleeve after the end of durability was measured. The difference between the volume average particle diameters of the evaluated toners was used as an evaluation criterion.

The volume average particle diameter of the toner is Coulter Multisizer (manufactured by Coulter Co.) and the electrolyte is ISO.
It is measured using TON R-II (1% NaCl aqueous solution Coulter Scientific Japan).

The measuring method is as follows:
0.1 to 5 m of a surfactant as a dispersant in 150 ml.
1 and 2 to 20 ml as a measurement sample.

The electrolytic solution in which the sample was suspended was subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the dispersion was treated with the above-mentioned measuring device for 10
The volume average particle diameter is calculated by measuring the volume and number of particles of 2 to 60 μm using an aperture of 0 μm.

[0205]

[Table 3]

The following halftone image quality, resolution, and fine line reproducibility were evaluated and measured after the end of image development durability.

5) Halftone image quality The halftone image quality is an image obtained by arbitrarily measuring image densities at 10 points using a Macbeth reflection densitometer for an image obtained by copying an A4 0.3 halftone full surface solid original. The evaluation standard was the difference between the maximum value and the minimum value of the concentration.

The halftone image quality here means the halftone density uniformity of the halftone image obtained by copying.

Poor halftone density uniformity (poor halftone image quality) means that the halftone image obtained by copying has uneven density and there are many variations in halftone image density. Is.

The evaluation criteria for halftone image quality are shown below.

[0211]

[Table 4]

6) Resolution The evaluation of the resolving power of the copied image was performed by the following method.

A pattern composed of five thin lines having the same line width and spacing, and 2.8, 3.2, 3.6, and 6 mm intervals within 1 mm.
4.0, 4.5, 5.0, 5.6, 6.3, 7.1,
Create an original image that looks like 8.0, 9.0, 10.0 lines.

An image obtained by copying the original document having these 12 types of line images under appropriate copying conditions is observed with a magnifying glass, and the number of images in which fine lines are clearly separated (number of lines /
mm) was used as a means for evaluation.

Here, the larger the value of the number of images (lines / mm) in which fine lines are clearly separated is, the better the level of blurring of the line image of the copied image is, and the higher the resolution is. , High image quality.

The evaluation criteria for resolution are as shown in the following table.

[0217]

[Table 5]

7) Fine line reproducibility Fine line reproducibility was measured by the following method.

That is, an image obtained by copying an original of a fine line having a width of 100 μm accurately under proper copying conditions is used as a measurement sample, and a Luzex 450 particle analyzer is used as a measuring device. Measure the line width.

At this time, since the line width measurement position has unevenness in the width direction of the fine line image of the toner, the average line width of the unevenness is taken as the measurement point.

From this, the fine line reproducibility value (%) is calculated by the following formula.

[0222]

[Equation 6]

Here, the closer the fine line reproducibility value is to 100%, the more faithful the copied image becomes to the original line width.

Therefore, the closer the fine line reproducibility value is to 100%, the higher the image quality.

The evaluation standard of fine line reproducibility was the absolute value of the value (%)-100 (%) of fine line reproducibility of the copied image.

[0226]

[Table 6]

[Example 1] 100 parts by mass of polyester resin (polyester resin consisting of bisphenol A-trimellitic acid-terephthalic acid) 90 parts by mass of magnetic substance of Production Example 1 Calix allene of compound example 1 Compound 1 part by mass Aliphatic alcohol wax represented by the following formula (A) 3 parts by mass CH ₃ (CH ₂ ) _X CH ₂ OH (A) (X: average value 47, Mw = 765)

After thoroughly mixing the above materials with a blender,
The mixture was kneaded by a twin-screw kneading extruder set at 110 ° C. The obtained kneaded product was cooled, coarsely pulverized by a cutter mill, and then finely pulverized by a fine pulverizer using a jet stream, and the finely pulverized powder obtained was classified to have a volume average particle diameter of 6.51 μm. Magnetic toner of

100 parts by mass of the obtained black fine powder magnetic toner was mixed with negatively charged hydrophobic dry colloidal silica (BET).
0.6 parts by mass of a specific surface area of 300 m ² / g) was added and mixed with a Henschel mixer to obtain a toner for evaluation, and a commercially available copying machine Canon NP-6085 (process speed 51
3 mm / sec, developing sleeve is coated developing sleeve A
Was used), and the images were evaluated under the environmental conditions of normal temperature and low humidity (23.5 ° C., 5%).

With respect to the above-mentioned toner for evaluation, the toner was left for 2 weeks under high temperature and high humidity (32.5 ° C., 80%) environmental conditions, and then the image formation was evaluated.

As is clear from Tables 7 and 8, the results were good images with high image density after 100,000 sheets under both environmental conditions.

[0232] The charge amount on the sleeve is stable even after 100,000 sheets have been run, and particularly high temperature and high humidity (32.5 ° C, 80%).
The amount of charge on the initial sleeve did not decrease under environmental conditions. During the image formation endurance, the cleaning blade did not turn up, the cleaning failed, and the drum fusion did not occur.

Further, no unevenness of the sleeve coat was generated during the image forming durability, and the selective developing property was also good.

Example 2 The same material as in Example 1 was used except that the charge control agent was changed to the calixarene of Compound Example 6 in Example 1, and the same method as in Example 1 was used. Thus, a magnetic toner having a volume average particle diameter of 6.55 μm was obtained.

100 parts by mass of the obtained black fine powder magnetic toner was mixed with negatively charged hydrophobic dry colloidal silica (BET).
0.6 parts by mass of a specific surface area of 300 m ² / g) was added and mixed with a Henschel mixer, and then the same evaluation as in Example 1 was performed.

As is clear from Tables 7 and 8, the results were good images with high image density after 100,000 sheets under both environmental conditions.

The charge amount on the sleeve is stable even after running 100,000 sheets, especially in high temperature and high humidity (32.5 ° C., 80%).
The amount of charge on the initial sleeve did not decrease under environmental conditions. During the image formation endurance, the cleaning blade did not turn up, the cleaning failed, and the drum fusion did not occur.

Further, no unevenness of the sleeve coat was generated during the image forming durability, and the selective developing property was also good.

Example 3 Using the evaluation toner obtained in Example 1, the commercially available copying machine Canon NP-6085 used in the evaluation of Example 1 was replaced with the commercially available copying machine Canon NP-9800 (process). Speed 503mm / se
c, the developing sleeve was made of SUS), and the same evaluation as in Example 1 was performed.

As is clear from Tables 7 and 8, the results were good images with high image densities after 100,000 sheets under both environmental conditions.

The charge amount on the sleeve is stable even after running 100,000 sheets, especially in high temperature and high humidity (32.5 ° C., 80%)
The amount of charge on the initial sleeve did not decrease under environmental conditions. During the image formation endurance, the cleaning blade did not turn up, the cleaning failed, and the drum fusion did not occur.

Further, no unevenness of the sleeve coat was generated during the image forming durability, and the selective developing property was also good.

Example 4 Example 1 is the same as Example 1 except that the magnetic substance is changed to the magnetic substance of Production Example 2.
Using the same material as in Example 1 and in the same manner as in Example 1, a magnetic toner having a volume average particle size of 6.47 μm was obtained.

100 parts by weight of the obtained black fine powder magnetic toner was mixed with negatively charged hydrophobic dry colloidal silica (BET).
0.6 parts by mass of a specific surface area of 300 m ² / g) was added and mixed with a Henschel mixer, and then the same evaluation as in Example 3 was performed.

As is clear from Tables 7 and 8, the results were good images with high image density after 100,000 sheets of durability under both environmental conditions.

The charge amount on the sleeve is stable even after running 100,000 sheets, especially in high temperature and high humidity (32.5 ° C., 80%).
The amount of charge on the initial sleeve did not decrease under environmental conditions. During the image formation endurance, the cleaning blade did not turn up, the cleaning failed, and the drum fusion did not occur.

No unevenness of the sleeve coat was generated during the image forming durability, and the selective developing property was also good.

Example 5 Example 1 is the same as Example 1 except that the magnetic substance is changed to the magnetic substance of Production Example 3.
A magnetic toner having a volume average particle size of 6.59 μm was obtained by using the same material as in Example 1 and in the same manner as in Example 1.

100 parts by weight of the obtained black fine powder magnetic toner was mixed with negatively charged hydrophobic dry colloidal silica (BET).
0.6 parts by mass of a specific surface area of 300 m ² / g) was added and mixed with a Henschel mixer, and then the same evaluation as in Example 3 was performed.

As is clear from Tables 7 and 8, the results were good images with high image density after 100,000 sheets under both environmental conditions.

The charge amount on the sleeve is stable even after running 100,000 sheets, and especially high temperature and high humidity (32.5 ° C., 80%)
The amount of charge on the initial sleeve did not decrease under environmental conditions. During the image formation endurance, the cleaning blade did not turn up, the cleaning failed, and the drum fusion did not occur.

No unevenness of the sleeve coat was generated during the image forming durability, and the selective developing property was also good.

Example 6 Example 1 is the same as Example 1 except that the magnetic substance is changed to the magnetic substance of Production Example 4.
Using the same material as in Example 1 and in the same manner as in Example 1, a magnetic toner having a volume average particle size of 6.57 μm was obtained.

100 parts by mass of the obtained black fine powder magnetic toner was mixed with negatively charged hydrophobic dry colloidal silica (BET).
0.6 parts by mass of a specific surface area of 300 m ² / g) was added and mixed with a Henschel mixer, and then the same evaluation as in Example 3 was performed.

As is clear from Tables 7 and 8, the results were good images with high image density after 100,000 sheets under both environmental conditions.

The charge amount on the sleeve is stable even after running 100,000 sheets, and especially high temperature and high humidity (32.5 ° C., 80%)
The amount of charge on the initial sleeve did not decrease under environmental conditions. During the image formation endurance, the cleaning blade did not turn up, the cleaning failed, and the drum fusion did not occur.

Further, no unevenness of the sleeve coat was generated during the image forming durability, and the selective developing property was also good.

Example 7 The same materials as in Example 1 were used, except that the calixarene compound of Example 6 was used as the charge control agent in Example 1, except that the charge control agent was changed. The volume average particle size of 6.
A 41 μm magnetic toner was obtained.

100 parts by mass of the obtained black fine powder magnetic toner was mixed with negatively charged hydrophobic dry colloidal silica (BET).
0.6 parts by mass of a specific surface area of 300 m ² / g) was added and mixed with a Henschel mixer, and then the same evaluation as in Example 3 was performed.

As is clear from Tables 7 and 8, the results were good images with high image density after 100,000 sheets under both environmental conditions.

The charge amount on the sleeve is stable even after 100,000 sheets have been run, and particularly high temperature and high humidity (32.5 ° C., 80%).
The amount of charge on the initial sleeve did not decrease under environmental conditions. During the image formation endurance, the cleaning blade did not turn up, the cleaning failed, and the drum fusion did not occur.

Further, no unevenness of the sleeve coat was generated during the image forming durability, and the selective developing property was also good.

Example 8 The same material as in Example 1 was used except that the calixarene compound of Example 9 was used as the charge control agent in Example 1 except that the charge control agent was changed. The volume average particle size of 6.
A magnetic toner of 55 μm was obtained.

100 parts by mass of the obtained black fine powder magnetic toner was mixed with negatively charged hydrophobic dry colloidal silica (BET).
0.6 parts by mass of a specific surface area of 300 m ² / g) was added and mixed with a Henschel mixer, and then the same evaluation as in Example 3 was performed.

As is clear from Tables 7 and 8, the results were good images with high image density after 100,000 sheets under both environmental conditions.

The charge amount on the sleeve is stable even after running 100,000 sheets, and especially high temperature and high humidity (32.5 ° C., 80%)
The amount of charge on the initial sleeve did not decrease under environmental conditions. During the image formation endurance, the cleaning blade did not turn up, the cleaning failed, and the drum fusion did not occur.

Further, no unevenness of the sleeve coat was generated during the image forming durability, and the selective developing property was also good.

[Example 9] The same material as in Example 1 was used except that the calixarene compound of Example 4 was used as the charge control agent in Example 1 except that the charge control agent was changed. The volume average particle size of 6.
A magnetic toner of 54 μm was obtained.

100 parts by weight of the obtained black fine powder magnetic toner was mixed with negatively charged hydrophobic dry colloidal silica (BET).
0.6 parts by mass of a specific surface area of 300 m ² / g) was added and mixed with a Henschel mixer, and then the same evaluation as in Example 3 was performed.

As is clear from Tables 7 and 8, the results were good images with high image density after 100,000 sheets under both environmental conditions.

The charge amount on the sleeve is stable even after 100,000 sheets have been run, and particularly high temperature and high humidity (32.5 ° C., 80%)
The amount of charge on the initial sleeve did not decrease under environmental conditions. During the image formation endurance, the cleaning blade did not turn up, the cleaning failed, and the drum fusion did not occur.

Further, no unevenness of the sleeve coat was generated during the image forming durability, and the selective developing property was also good.

Comparative Example 1 The same material as in Example 1 was used, except that the magnetic material in Example 1 was changed to the magnetic material in Comparative Production Example 1, and the same method as in Example 1 was used. hand,
A magnetic toner having a volume average particle diameter of 6.53 μm was obtained.

100 parts by weight of the obtained black fine powder magnetic toner was mixed with negatively charged hydrophobic dry colloidal silica (BET).
0.6 parts by mass of a specific surface area of 300 m ² / g) was added and mixed with a Henschel mixer, and then the same evaluation as in Example 3 was performed.

Image development was carried out under normal conditions of room temperature and low humidity (23.5 ° C., 5%), and the image density at 100,000 sheets was 1.33.

During the image output durability test, the cleaning blade swells from around 99100 sheets,
Cleaning failure occurs from around 500 sheets, 9930
Drum fusion occurred from around 0 sheets.

Regarding the occurrence of sleeve coat unevenness during image output durability, slight sleeve coat unevenness occurred at the start and at the time of 1000 sheets after the start of the durability, but after image output durability 2000 sheets, sleeve coat unevenness occurred. The unevenness has disappeared.

The selective developability was evaluated as Δ.

When images were produced under high temperature and high humidity (32.5 ° C., 80%) environmental conditions, the initial image density was 1.25.
And the image density at 100,000 sheets was 1.35.

During the image output durability test, the cleaning blade was turned over from about 99,200 sheets.
Cleaning failure occurs from around 700 sheets, and 9960
Drum fusion occurred from around 0 sheets.

Regarding the occurrence of sleeve coat unevenness during the image output durability,
The unevenness of the sleeve coat was slightly generated, but the unevenness of the sleeve coat disappeared after the image-forming durability of 2000 sheets. The selective developability was evaluated as Δ.

Comparative Example 2 The same material as in Example 1 was used, except that the magnetic material in Example 1 was changed to the magnetic material in Comparative Production Example 2, and the same method as in Example 1 was used. hand,
A magnetic toner having a volume average particle size of 6.48 μm was obtained.

100 parts by mass of the obtained black fine powder magnetic toner was mixed with negatively charged hydrophobic dry colloidal silica (BET).
0.6 parts by mass of a specific surface area of 300 m ² / g) was added and mixed with a Henschel mixer, and then the same evaluation as in Example 3 was performed.

Image development was carried out under normal conditions of room temperature and low humidity (23.5 ° C., 5%), and the image density at 100,000 sheets was 1.34.

[0285] Further, during the image output durability test, the cleaning blade curling phenomenon occurred from around 98,700 sheets.
Although cleaning failure occurred from around 900 sheets, drum fusion did not occur.

Regarding the occurrence of sleeve coat unevenness during image output durability, slight sleeve coat unevenness occurred at the start and at the time of 1000 sheets after the start of durability, but after image output durability 2000 sheets, the sleeve coat unevenness occurred. The unevenness has disappeared.

The selective developability was evaluated as ◯ Δ as an evaluation criterion.

When image development was advanced under high temperature and high humidity (32.5 ° C., 80%) environmental conditions, the initial image density was 1.27.
And the image density at 100,000 sheets was 1.36.

During the image output durability test, the cleaning blade was turned over from about 99,300 sheets.
Cleaning failure occurred from around 800 sheets, but drum fusion did not occur.

Regarding the occurrence of sleeve coat unevenness during image output durability, at the start and at the time of 1000 sheets after the durability start,
The unevenness of the sleeve coat was slightly generated, but the unevenness of the sleeve coat disappeared after the image-forming durability of 2000 sheets. The selective developability was ◯ Δ as an evaluation criterion.

Comparative Example 3 The same material as in Example 1 was used, except that the magnetic material in Example 1 was changed to the magnetic material in Comparative Production Example 3, and the same method as in Example 1 was used. hand,
A magnetic toner having a volume average particle diameter of 6.56 μm was obtained.

100 parts by weight of the obtained black fine powder magnetic toner was mixed with negatively charged hydrophobic dry colloidal silica (BET).
0.6 parts by mass of a specific surface area of 300 m ² / g) was added and mixed with a Henschel mixer, and then the same evaluation as in Example 3 was performed.

Image development was carried out under normal conditions of room temperature and low humidity (23.5 ° C., 5%), and the image density at 100,000 sheets was 1.36.

Further, during the image output durability test, the phenomenon of the cleaning blade turning over occurred from around 98900 sheets,
Cleaning failure occurred from around 200 sheets, but drum fusion did not occur.

Regarding the occurrence of sleeve coat unevenness during image output durability, slight sleeve coat unevenness occurred at the start and at the time of 1000 sheets after the start of the durability, but after image output durability 2000 sheets, the sleeve coat unevenness occurred. The unevenness has disappeared.

The selective developability was ◯ Δ as an evaluation criterion.

When the image formation was advanced under high temperature and high humidity (32.5 ° C., 80%) environmental conditions, the initial image density was 1.26.
And the image density at 100,000 sheets was 1.36.

During the image output durability test, the cleaning blade swells from around 99,500 sheets.
Cleaning failure occurred from around 000 sheets, but drum fusion did not occur.

Regarding the occurrence of sleeve coat unevenness during image output durability, at the time of start and after 1000 sheets of durability start,
The unevenness of the sleeve coat was slightly generated, but the unevenness of the sleeve coat disappeared after the image-forming durability of 2000 sheets. The selective developability was ◯ Δ as an evaluation criterion.

[Comparative Example 4] In Example 1, except that the charge control agent was changed to a monoazo iron complex, the same materials as in Example 1 were used, and the volume was measured in the same manner as in Example 1. A magnetic toner having an average particle size of 6.57 μm was obtained.

100 parts by mass of the obtained black fine powder magnetic toner was mixed with negatively charged hydrophobic dry colloidal silica (BET).
0.6 parts by mass of a specific surface area of 300 m ² / g) was added and mixed with a Henschel mixer, and then the same evaluation as in Example 3 was performed.

Image development was carried out under normal conditions of room temperature and low humidity (23.5 ° C., 5%), and the image density at 100,000 sheets was 1.28.

Further, during the image output durability test, the cleaning blade swells from around 98500 sheets,
Cleaning failure occurred from around 200 sheets, but drum fusion did not occur.

Regarding the occurrence of sleeve coat unevenness during image output durability, slight sleeve coat unevenness occurred at the start and at the time of 1000 sheets after the start of durability. The unevenness has disappeared.

The selective developability was ◯ Δ as an evaluation criterion.

When images were produced under high temperature and high humidity (32.5 ° C., 80%) environmental conditions, the initial image density was 1.23.
And the image density at 100,000 sheets was 1.29.

[0307] Further, during the image output durability, the cleaning blade swells from around 98300 sheets,
Cleaning failure occurred from around 600 sheets, but drum fusion did not occur.

Regarding the occurrence of sleeve coat unevenness during the image output durability,
The unevenness of the sleeve coat was slightly generated, but the unevenness of the sleeve coat disappeared after the image-forming durability of 2000 sheets. The selective developability was ◯ Δ as an evaluation criterion.

[Comparative Example 5] The same material as in Example 1 was used, except that in Example 1, the magnetic material was changed to the magnetic material of Comparative Production Example 1 and the charge control agent was changed to a monoazo iron complex. In the same manner as in Example 1, the volume average particle size is 6.58.
A magnetic toner of μm was obtained.

100 parts by mass of the obtained black fine powder magnetic toner was mixed with negatively charged hydrophobic dry colloidal silica (BET).
0.6 parts by mass of a specific surface area of 300 m ² / g) was added and mixed with a Henschel mixer, and then the same evaluation as in Example 3 was performed.

When image development was carried out under normal conditions of room temperature and low humidity (23.5 ° C., 5%), the image density at 100,000 sheets was 1.23.

Also, during the image output durability test, the cleaning blade curling phenomenon occurred from around 98100 sheets,
Cleaning failure occurs from around 700 sheets, and 9910
Drum fusion occurred from around 0 sheets.

Regarding the occurrence of sleeve coat unevenness during image output durability, slight sleeve coat unevenness occurred at the start and at the time of 1000 sheets after the start of durability, but after image output durability 2000 sheets, sleeve coat unevenness occurred. The unevenness has disappeared.

The selective developability was evaluated as Δ.

When image formation was advanced under high temperature and high humidity (32.5 ° C., 80%) environmental conditions, the initial image density was 1. l8
The image density at 100,000 sheets was 1.25.

Also, during the image output durability test, the cleaning blade curling phenomenon occurred from around 98600 sheets.
Cleaning failure occurs from around 500 sheets, and 9890
Drum fusion occurred from around 0 sheets.

Regarding the occurrence of sleeve coat unevenness during image output durability,
The unevenness of the sleeve coat was slightly generated, but the unevenness of the sleeve coat disappeared after the image-forming durability of 2000 sheets.

The selective developability was evaluated as Δ.

[0319]

[Table 7]

[0320]

[Table 8]

[0321]

According to the present invention, the surface has at least Z.
A toner having a small particle size can be obtained by using a toner structure containing a magnetic substance formed from a layer containing a large amount of at least one element selected from n, Mn, and Ti and a layer containing a large amount of silicon element, and a calixarene compound. Even when it is applied to a high-speed copying machine with a process speed of 380 mm / sec or more, a good image can be provided for a long period of time.

Further, by applying the toner of the present invention to the image forming method of the present invention, a high quality image can be provided for a long period of time.

[Brief description of drawings]

FIG. 1 is a diagram showing the relationship between iron element dissolution rate-content of one element selected from Zn, Mn, and Ti and iron element dissolution rate-Si element content.

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

[Explanation of symbols]

1 Electrostatic latent image carrier (electrophotographic photoreceptor) 2 charging means 3 Transfer means 4 Development sleeve 5 Latent image forming means 6 erase exposure 7 fixing means 8 Cleaning means 9 Developing means 10 Developer (magnetic toner) 11 Developer layer thickness control member 12 Bias applying means 13 Developer supply roller P recording material

Continuation of the front page (56) Reference JP-A-9-134031 (JP, A) JP-A-9-59025 (JP, A) JP-A-9-59024 (JP, A) JP-A-8-278660 (JP , A) JP-A-8-272136 (JP, A) JP-A-8-146655 (JP, A) JP-A-8-101529 (JP, A) JP-A-8-50369 (JP, A) JP-A-8-150369 (JP, A) 8-30028 (JP, A) JP-A-8-15916 (JP, A) JP-A-7-295299 (JP, A) JP-A-7-152207 (JP, A) JP-A-7-77830 (JP, A) JP-A-5-341561 (JP, A) JP-A-5-119535 (JP, A) JP-A-3-237467 (JP, A) JP-A-2-201378 (JP, A) (58) Survey Fields (Int.Cl. ⁷ , DB name) G03G 9/08

Claims (3)

(57) [Claims] 1. A magnetic toner containing at least a binder resin, a magnetic material and a charge control agent, wherein the magnetic material contains at least one element A and silicon element selected from Zn, Mn and Ti, and In the element distribution analysis in the body, 1) the content of the element A eluted up to the iron element dissolution rate of 10 mass% is 60 mass% or more of the total content of the element A, 2) the iron element dissolution rate of 10 mass% %, The content of elemental silicon eluted up to 7% of the total content of elemental silicon is 7
0 mass% or more, and 3) the content of elemental silicon that elutes up to an iron element dissolution rate of 10 mass% is larger than the content of element A that elutes up to an iron element dissolution rate of 10 mass%, A magnetic toner containing at least one calixarene compound represented by the following general formula (1) as a control agent. [Chemical 1] [In the formula, R ₁ and R ₅ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ₁ and R ₅ may be the same or different, and R ₂ and R ₆ are represents hydrogen atom, R ₃ and R ₄ represents a hydrogen atom, R ₇ is a alkyl group, the aryl group, a recycler click group
The indicated, n represents an integer of 4 to 8, m is an integer of following 0 to n n. ] 2. An electrostatic latent image on the electrostatic image bearing member is developed by a developing means in a developing unit to form a toner image on the electrostatic latent image bearing member, and the toner image is transferred to a recording material, In the image forming method of fixing the transferred toner image on the recording material, the developing means has a toner, and the toner contains at least a binder resin, a magnetic material and a charge control agent, The magnetic substance contains at least one element A selected from Zn, Mn, and Ti and a silicon element, and in the element distribution in the magnetic substance, 1) the inclusion of the element A that dissolves up to an iron element dissolution rate of 10% by mass. The amount is 60 mass% of the total content of element A
And 2) the content of the elemental silicon that elutes up to the iron element dissolution rate of 10 mass% is 70 mass% or more of the total content of the silicon element, and 3) up to the iron element dissolution rate of 10 mass%. The content of the elemental silicon to be dissolved is the iron element dissolution rate 10
The content of the element A is more than the content of the element A eluting up to the mass%, and the charge control agent contains at least one kind of calixarene compound represented by the following general formula (1), and is provided in the developing unit. An image forming method, wherein the developing sleeve is a coated developing sleeve coated with a resin layer containing at least conductive fine particles. [Chemical 2] [In the formula, R ₁ and R ₅ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ₁ and R ₅ may be the same or different, and R ₂ and R ₆ are represents a hydrogen atom, R ₃ and R ₄ represents a hydrogen atom, R ₇ is a alkyl group, the aryl group, a recycler click group
The indicated, n represents an integer of 4 to 8, m is an integer of following 0 to n n. ] 3. The image forming method according to claim 2, wherein the image is formed at a process speed of 380 mm / sec or more.