JP3083034B2 - Developer for developing electrostatic image 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 an image in which a latent image is formed by using an electrophotographic photosensitive member as a latent image holding member, and the latent image is visualized using a developer and transferred to a transfer material. The present invention relates to a developer for developing an electrostatic image used in a forming method and an image forming method.

[0002]

2. Description of the Related Art Electrophotography is disclosed in U.S. Pat.
As described in, for example, US Pat. No. 691 and the like, a number of methods are known. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means, and then the latent image is formed. The image is developed using toner, and if necessary, the toner image is transferred to a transfer member such as paper, and then fixed by heating, pressure, or solvent vapor to obtain a copy. Further, as a method of developing using a toner or a method of fixing a toner image, various methods have been conventionally proposed, and a method suitable for each image forming process is adopted.

Conventionally, toners used for these purposes are generally prepared by melt-mixing a coloring agent composed of a dye and a pigment in a thermoplastic resin, uniformly dispersing the same, and then using a pulverizer or a classifier to obtain a toner having a desired particle size. Has been manufactured.

[0004] Although this process can produce fairly good toners, it does have certain limitations, namely the range of choice of toner materials. For example, the resin colorant dispersion must be sufficiently brittle and capable of being pulverized in economically feasible manufacturing equipment. However, when the resin colorant dispersion is made brittle to satisfy these requirements, the particle size range of the particles formed when actually pulverized at a high speed tends to be widened, and in particular, a relatively large proportion of the fine particles The problem of inclusion occurs. Further, such a highly brittle material is susceptible to further pulverization or pulverization when used for development in a copying machine or the like. Further, in this method, it is difficult to completely and uniformly disperse solid fine particles such as a colorant in a resin,
Depending on the degree of the dispersion, fog may be increased, the image density may be reduced, and the color mixture / transparency may be poor. Further, exposure of the coloring agent to the fracture surface may cause fluctuations in development characteristics.

On the other hand, in order to overcome the problems of the toner by these pulverization methods, production of a toner by a suspension polymerization method is disclosed in Japanese Patent Publication Nos. 36-10231, 43-10799 and 51-14895. A method has been proposed. In the suspension polymerization method, a polymerizable monomer, a colorant, a polymerization initiator and a crosslinking agent, if necessary, a charge control agent,
After the other additives are uniformly dissolved or dispersed into a monomer composition, the monomer composition is dispersed in a continuous phase containing a dispersion stabilizer, for example, an aqueous phase using a suitable stirrer. Simultaneously, a polymerization reaction is carried out to obtain toner particles having a desired particle size.

This method does not include a pulverizing step at all, so that the toner does not need to be brittle, and a soft material can be used. There is an advantage of having a triboelectric charging property. Further, since the classification step can be omitted, the cost reduction effect is large, such as saving energy, shortening the time, and improving the process yield. And, at present, further improvement in the dispersibility of the colorant, further improvement in the granulation property for realizing the omission of the classification step, etc. are greatly expected in connection with the uniform triboelectric charging property. Much research has been done on all materials constituting the developer, such as improvements in binders.

As described above, the polymerization method toner has many advantages, but from the viewpoint of further improving the image quality and durability of electrophotography in recent years, sufficient toner has not yet been obtained.

[0008] Polymerized toner is characterized by its manufacturing method.
Among the various additives added to the monomer composition, those having polarity tend to be unevenly distributed on the toner surface and in the vicinity thereof. This feature can reduce the amount of additives used to impart various toner properties, but on the other hand, when considered from the viewpoint of improving image quality, especially maintaining high image quality, it can be used with sleeves, carriers, etc. There is a problem that the deterioration of the toner surface due to the rubbing of the toner greatly affects the toner characteristics.

Further, the polymerized toner has such characteristics, so that it is generally susceptible to the effects of temperature and humidity, causing problems such as excessive charge under low humidity and insufficient charge under high humidity. There is an urgent need to develop a toner having a stable charge amount even in the environment.

Further, in recent years, low-temperature fixing properties have been desired for toners used in electrophotography from the viewpoint of energy saving.

To meet this requirement, a toner binder material having good wettability and adhesion to paper is selected as the toner formulation, and the melt viscosity characteristics of the toner are designed to exhibit low viscosity at lower temperatures. .

However, when such a toner is used, although low-temperature fixability is achieved, the adhesion of the toner to the photoreceptor is increased, the transferability is deteriorated, and the toner is fused to the drum. It causes deterioration.

In order to further improve the image quality, attempts have been made in the art to reduce the particle size of the toner to increase the fidelity to an image. This tends to increase the surface area per contact and increase the amount of charged electricity of the toner. In addition, since the charged amount of the toner is large, the adhesion between the toners is strong, the fluidity is reduced, and problems occur in the stability of toner supply and in the application of tribo to the supplied toner.

Therefore, the charging is more stable than before.
Although a toner having good fluidity has been demanded, a sufficient toner has not yet been obtained.

In general, a carrier constituting a two-component developer is mainly classified into a conductive carrier represented by iron powder and a so-called insulating carrier in which the surface of iron powder, nickel, ferrite or the like is coated with an insulating resin. Separated. When an alternating electric field is applied to improve the image quality, if the resistance of the developer carrier is low, the carrier leaks the latent image potential and a good image cannot be obtained. When the carrier core is conductive, it is preferable to use the carrier core after coating, and ferrite having a relatively high resistance is preferably used as the core material.

Further, since iron powder has a high magnetic force, in a developing area where the developer toner is developed, the developer brush is hardened, so that nicks are easily formed and roughness is easily generated. Is difficult to obtain. Therefore,
Ferrite is also preferably used to reduce the magnetic force of the carrier to achieve high image quality.

For the purpose of forming a high quality image, Japanese Patent Application Laid-Open No.
No. 04663 discloses that the saturation magnetization value of a carrier is 50 em.
It has been proposed that a good image without nicks can be obtained by setting the ratio to u / g or less. However, when a carrier having a gradually decreased saturation magnetization value is used, the reproducibility of the fine wire becomes better, As the distance from the carrier increases, the phenomenon that the carrier adheres to the electrostatic image carrier (so-called photosensitive drum) (carrier adhesion) becomes more remarkable.

Japanese Patent Publication No. 4-3868 proposes using so-called hard ferrite having a coercive force of 300 gauss or more as a carrier. However, this is a system for using the hard ferrite having a high coercive force to make full use of the carrier. In order to realize a small high-quality color copier,
It is preferable to use a developer carrier using a fixed magnetic core. In this case, a hard carrier having a high coercive force has a problem that transportability is rather deteriorated due to its self-aggregating property.

Further, Japanese Patent Application Laid-Open No. 2-88429 proposes to use a hard ferrite composed of a spinel phase and a magnet plumbite phase containing a lanthanoid element as a carrier. In a system in which development is performed by an alternating electric field for obtaining a higher quality image because of having conductivity, it is not preferable in that the charge leaks through the carrier to disturb the development.

Therefore, in a system for performing development using an alternating electric field, the resistance of the carrier needs to be at least a certain level.

As described above, a sufficient developer carrier which satisfies high image quality, particularly, reproducibility of highlight while preventing carrier adhesion has not yet been obtained.

On the other hand, the electrophotographic photosensitive member has various structures in order to obtain required characteristics or according to the type of the applied electrophotographic process. As a typical electrophotographic photoreceptor, a photoreceptor having a photoconductive layer formed as an image holding layer on a support and a photoreceptor having a photoconductive layer and an insulating layer formed thereon as an image holding layer are provided. It has a body and is widely used. A photoreceptor composed of a support and a photoconductive layer is used for image formation by the most common electrophotographic processes, that is, charging, image exposure and development, and if necessary, transfer.

In the case of a photoreceptor having an insulating layer, the insulating layer protects the photoconductive layer, improves the mechanical strength of the photoreceptor,
It is provided for the purpose of improving the dark decay characteristic, or being applied to a specific electrophotographic process (further, for the purpose of eliminating pollution). A typical example of a photoreceptor having such an insulating layer or an electrophotographic process using a photoreceptor having an insulating layer is described in, for example, US Pat.
048, JP-B-41-16429, JP-B-38-15446, JP-B-46-3713, JP-B-42-23910, and JP-B-43-24.
748, JP-B-42-19747, JP-B-36-4121, and the like.

The electrophotographic photosensitive member is, of course,
It is required to have predetermined sensitivity, electrical characteristics, and optical characteristics according to the applied electrophotographic process.
However, not only that, the durability of the photoreceptor is also an important property. Even if the photosensitive member has excellent electrophotographic characteristics at low humidity, it is difficult to obtain a stable and clear image on a photosensitive member whose surface potential is significantly reduced at high humidity. Also, in the electrophotographic process of transferring, since the photoreceptor is usually used repeatedly, the chemical bond of the surface forming substance is broken by corona discharge, and as a result, it acts with ionized oxygen, ozone, moisture, nitric oxide, etc. As a result, the surface has a low resistance, and in particular, the electrostatic charge retention ability under high humidity is reduced, and the sharpness of an image is often impaired. In addition, adhering matter such as paper dust often lowers the charge holding ability of the photoreceptor and causes image deletion.

Since the surface of the photosensitive member is coated with a resin, the performance of the resin is particularly important, and a resin having excellent durability has been demanded. Recently, a polycarbonate resin having bisphenol A as a skeleton (hereinafter, referred to as bisphenol A type polycarbonate) has been studied as a binder for the surface layer as a resin satisfying these requirements.

First, a polycarbonate resin as an engineering plastic generally has a large surface free energy, and a developer (hereinafter abbreviated as a toner) tends to adhere to the surface. When an image is displayed in this situation, a phenomenon that many white dots appear on the entire black image (hereinafter abbreviated as solid) is likely to occur.

Secondly, when preparing a photoreceptor, a film is formed by dissolving the binder resin and the charge transport material in a solvent, coating and drying. A resin formed under such conditions has a residual strain stress in its internal structure, and a polycarbonate resin has a particularly strong tendency, and has a drawback that a so-called solvent crack is easily generated. When handling the photoreceptor thus created or mounting it on an electrophotographic device, for example,
When the photosensitive member comes into contact with various oils or the like used in the apparatus, cracks easily occur on the photosensitive member. When the cracks occur, they appear as defective images.

Third, since the coefficient of friction of the surface is large, there is a problem that the cleaning amount is increased by cleaning with urethane rubber or the like, and it is difficult to increase the number of durable sheets.

[0029]

SUMMARY OF THE INVENTION An object of the present invention is to provide a developer for developing an electrostatic image and an image forming method which solve the above problems.

That is, an object of the present invention is to provide a developer for developing an electrostatic image and an image forming method, which have good fluidity, chargeability, coloring power and granulation property.

It is a further object of the present invention to provide a developer for developing an electrostatic image and an image forming method having good fixability, fluidity, granulation property and chargeability.

Another object of the present invention is to provide a developer for developing an electrostatic image and an image forming method, which are not easily influenced by environmental fluctuations such as temperature and humidity and have a stable triboelectric charging property in each environment. I do.

It is a further object of the present invention to provide an image forming method which is excellent in transferability and cleaning properties, and which can obtain excellent images even after running many sheets without causing cleaning defects. .

[0034]

The present invention attains the above object by the following constitutions.

The present invention (first invention) can be directly obtained by a suspension polymerization method using a polymerizable monomer composition containing at least a polymerizable monomer, a colorant and a styrene-butadiene resin. And a toner having a copolymerization ratio of the styrene-butadiene resin (styrene-butadiene) of 95: 5 to 65:35. The present invention relates to a developer for developing an electrostatic image, comprising titanium oxide having an average particle size of from 0.1 to 0.2 μm and a hydrophobicity of from 20 to 98%.

The present invention (second invention) uses a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, a polyester resin and a styrene-butadiene resin, and is directly produced by a suspension polymerization method. And a toner having a copolymerization ratio of the styrene-butadiene resin (styrene: butadiene) of 95: 5 to 65:35, wherein the developer is an electrostatic charge image developing developer. And a titanium oxide having an average particle diameter of 0.01 to 0.2 μm and a hydrophobicity of 20 to 98%.

The present invention (third invention) uses a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, a vinyl resin having an acid component, and a polyester resin. A developer for developing an electrostatic charge image containing a toner obtained directly by a method, wherein the developer has an average particle diameter of 0.01 to 0.2 μm and a degree of hydrophobicity of 20 to 98%. The present invention relates to a developer for developing an electrostatic image, comprising titanium.

The present invention (the fourth invention) uses an electrophotographic photosensitive member having at least a conductive support and a photosensitive layer having a laminated structure of a charge generation layer and a charge transport layer to form a latent image. In an image forming method for forming, visualizing the latent image using a developer, and transferring and forming the latent image on a transfer material, a substance having a fluorine atom and / or a silicon atom exists in a surface layer of the electrophotographic photosensitive member. And the ratio of the fluorine atom and the silicon atom to the carbon atom by XPS measurement is as follows: fluorine atom / carbon atom (F / C) = 0.01 to 1.00 silicon atom / carbon atom (Si / C) = 0.03 to 1.00, and the developer is prepared by a suspension polymerization method using a polymerizable monomer composition containing at least a polymerizable monomer, a colorant and a styrene-butadiene resin. Directly obtained toner. Toner having a copolymerization ratio of styrene-butadiene resin (styrene: butadiene) of 95: 5 to 65:35 and titanium oxide having an average particle size of 0.01 to 0.2 μm and a hydrophobicity of 20 to 98%. It relates to an image forming method characterized by containing.

The present invention (fifth invention) uses an electrophotographic photosensitive member having at least a conductive support and a photosensitive layer having a laminated structure of a charge generation layer and a charge transport layer to form a latent image. In an image forming method for forming, visualizing the latent image using a developer, and transferring and forming the latent image on a transfer material, a substance having a fluorine atom and / or a silicon atom exists in a surface layer of the electrophotographic photosensitive member. And the ratio of the fluorine atom and the silicon atom to the carbon atom by XPS measurement is as follows: fluorine atom / carbon atom (F / C) = 0.01 to 1.00 silicon atom / carbon atom (Si / C) = 0.03 to 1.00, and the developer is suspended using a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, a polyester resin and a styrene-butadiene resin. G directly obtained by the polymerization method. Is over, the styrene - copolymerization ratio of butadiene resins (styrene: butadiene) is 95:
5 to 65:35 toner and 0.01 to 0.2
The present invention relates to an image forming method comprising titanium oxide having an average particle size of μm and a hydrophobicity of 20 to 98%.

The present invention (sixth invention) uses an electrophotographic photosensitive member having at least a conductive support and a photosensitive layer having a laminated structure of a charge generation layer and a charge transport layer to form a latent image. In an image forming method for forming, visualizing the latent image using a developer, and transferring and forming the latent image on a transfer material, a substance having a fluorine atom and / or a silicon atom exists in a surface layer of the electrophotographic photosensitive member. And the ratio of the fluorine atom and the silicon atom to the carbon atom by XPS measurement is as follows: fluorine atom / carbon atom (F / C) = 0.01 to 1.00 silicon atom / carbon atom (Si / C) = 0.03 to 1.00, and the developer is a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, a vinyl resin having an acid component, and a polyester resin. Directly obtained by the suspension polymerization method Donor and 0.01 to 0.2μ
The present invention relates to an image forming method comprising titanium oxide having an average particle diameter of m and a hydrophobicity of 20 to 98%.

Hereinafter, the present invention will be described in detail.

The carrier particles used in the present invention preferably have an average particle size of 5 to 100 μm, more preferably 20 to 80 μm. When the thickness is smaller than 5 μm, carrier adhesion to the photoreceptor is likely to occur.
If it exceeds 0 μm, the magnetic brush at the developing pole becomes coarse, and a high quality image cannot be obtained. In the present invention, the particle size of the carrier is randomly extracted by 300 or more by an optical microscope, and the image processing and analysis apparatus Luzex3 manufactured by Nireco Co., Ltd.
As a result, the carrier diameter is determined by the ferrite diameter in the horizontal direction.
It was measured.

The carrier used in the present invention can be used by coating the surface of the carrier particles with an optional resin, if necessary, for controlling the specific resistance and improving the durability. As the coating resin, a known suitable resin can be used, and examples thereof include an acrylic resin, a fluorine resin, a silicon resin, and an epoxy resin.

In the present invention (the first to third inventions), the toner contained in the developer is subjected to a surface treatment while hydrolyzing the coupling agent, for example, to a thickness of 0.01 to 0.2 μm. By mixing with titanium oxide fine particles having an average particle diameter and a hydrophobicity of 20 to 98%, it is possible to obtain a toner for developing an electrostatic charge image which is hardly influenced by the environment such as temperature and humidity.

This has not been achieved with hydrophobic silica as a generally known flow improver.

The reason is that the silica fine particles themselves have a strong negative chargeability, while the titanium fine particles have a substantially neutral chargeability, so that a constant flow without being affected by the charge of the toner particles. It is considered that the property is obtained.

The titanium oxide of the present invention is also suitable when the toner has a small particle size. When the particle size of the toner is reduced, the surface area per weight increases, and excessive charging due to rubbing is likely to occur. On the other hand, titanium oxide fine particles which can control charging and impart fluidity have a great effect.

The titanium oxide used in the present invention preferably has a hydrophobicity of 20 to 98%, preferably 30 to 90%, more preferably 40 to 80%.

If the degree of hydrophobicity is less than 20%, the amount of charge is greatly reduced due to long-term storage under high humidity, and a mechanism for accelerating the charge on the hard side is required, which complicates the apparatus and increases the degree of hydrophobicity. If it exceeds 98%, it is difficult to control the charging of titanium oxide itself, and as a result, the toner is charged up under low humidity.

In the present invention, a treatment amount of preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight with respect to 100 parts by weight of titanium oxide,
What is necessary is just to make it the above-mentioned degree of hydrophobicity.

The average particle size of the titanium oxide is preferably 0.01 to 0.2 μm from the viewpoint of imparting fluidity. If the average particle size is larger than 0.2 μm, toner charging due to poor fluidity becomes non-uniform, resulting in toner scattering and fogging. On the other hand, when the average particle size is smaller than 0.01 μm, the toner is easily embedded on the toner surface, the toner is quickly deteriorated, and the durability is reduced. As a means for hydrophobizing titanium oxide, it is preferable to perform treatment using a coupling agent.

Examples of the coupling agent usable in the present invention include a silane coupling agent and a titanium coupling agent.
All that can be subjected to a hydrophobic treatment can be used. Particularly preferably used is a silane coupling agent,
R _m SiY _n R: alkoxy group m: an integer of 1 to 3 Y: alkyl group Hydrocarbon group containing vinyl group, glycidoxy group, methacryl group n: an integer of 1 to 3 For example, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethyl Methoxysilane, hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane and the like can be mentioned.

[0053] More preferably, the following formula _{CaH 2a + 1 -Si (OC b} H 2b + 1) 3 a: 4~12 integer b: those represented by good an integer from 1 to 3.

When a in the above general formula is smaller than 4,
Although the treatment is easy, it is difficult to sufficiently achieve the hydrophobicity. If a is larger than 12, the hydrophobicity is sufficient, but coalescence between the titanium oxide particles increases, and the ability to impart fluidity is reduced. .

If b in the above general formula is larger than 3, the reactivity is lowered and the hydrophobic treatment is not sufficiently performed.

Therefore, in the above general formula, a is 4-1.
2, preferably 4 to 8, and b is 1 to 3, preferably 1 to 2.

The method for measuring the degree of hydrophobicity in the present invention is described below.

Method for Measuring Hydrophobicity The methanol titration test is an experimental test for confirming the hydrophobicity of fine titanium oxide powder having a hydrophobized surface.

The "methanol titration test" defined herein for evaluating the degree of hydrophobicity of the treated fine titanium oxide powder is carried out as follows. 0.2 g of the test titanium oxide fine powder was added to 50 m of water in a 250 ml Erlenmeyer flask.
Add to l. Methanol is titrated from the burette until all of the titanium oxide is wetted. At this time, the solution in the flask is constantly stirred with a magnetic stirrer. The end point is observed as the entire amount of titanium oxide fine powder is suspended in the liquid, and the degree of hydrophobicity is expressed as the percentage of methanol in the liquid mixture of methanol and water when the end point is reached.

Further, in the present invention, the treated titanium oxide has a light transmittance of 40% or more at a light length of 400 nm when dispersed in an ethanol solvent at a solid concentration of 0.1%. Is another feature.

That is, the titanium oxide used in the present invention has a very small primary particle size of 0.01 to 0.2 μm. However, in the state where the titanium oxide is actually mixed with the toner particles, it is not always the primary particle size. , And may exist in the form of secondary particles. Therefore, even if the primary particle diameter is small, it is difficult to sufficiently obtain the effects of the present invention if the effective diameter acting as secondary particles is large. However, 400 mm which is the lower limit wavelength in the visible region when dispersed in the liquid phase
The higher the light transmittance is, the smaller the secondary particle diameter is, and good results such as the sharpness of the projected image of the fluidity imparting ability OHP can be expected.

The method for measuring the transmittance according to the present invention will be described below.

-Transmission measurement method Sample 0.10 g Alkyd resin 13.20 * 1 Melamine resin 3.30 * 2 Thinner 3.50 * 3 Glass media 50.00 * 1 Bekkosol 1323-60- manufactured by Dainippon Ink and Chemicals, Inc.
EL * 2 Super Beckamine J-820 manufactured by Dainippon Ink and Chemicals, Inc.
-60 * 3 Amirac thinner manufactured by Kansai Paint Co. The above formulation is collected in a 150 cc mayonnaise bottle, and dispersed for 1 hour by a paint conditioner manufactured by Red Devil. 2. After the dispersion, the PET film is coated with a 2 mil doctor blade. 3.2. Is heated at 120 ° C. for 10 minutes to perform baking. 4.3. The transmittance of the sheet is measured by U-BEST 50 manufactured by JASCO Corporation in the range of 320 to 800 nm and compared.

In the present invention, the above-mentioned object of the present invention can be achieved by having the following constitution as a toner used in combination with the above-mentioned titanium oxide.

That is, in the present invention (first invention),
The toner is a toner directly obtained by a suspension polymerization method using a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, and a styrene-butadiene resin. When the copolymerization ratio (styrene: butadiene) of the resin is from 95: 5 to 65:35, the coloring power and the granulation property during toner production are improved.

In the present invention (second invention), the toner is suspended by using a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, a polyester resin and a styrene-butadiene resin. The styrene-butadiene resin has a copolymerization ratio (styrene: butadiene) of 95: 5 to 65:35.
By doing so, the fluidity, the chargeability, the coloring power, and the granulation during toner production are excellent.

Furthermore, in the present invention (third invention), the toner uses a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, a vinyl resin containing an acid component, and a polyester resin. Since the toner is directly obtained by the suspension polymerization method, the fixing property, the fluidity, the granulating property and the charging property are improved.

That is, in the present invention (first invention), by adding a styrene-butadiene resin to the polymerizable monomer composition, the coloring property is excellent and the granulation step in the polymerization toner production step is carried out. Can have very good granulation properties. It is considered that the reason for this is that the additive resin improves the dispersibility of pigments and the like, and the granulation stabilizing effect is increased due to the improvement.

The composition capable of effectively producing the effect of the present invention is such that the copolymerization ratio of styrene and butadiene is 95: 5-6.
The ratio is preferably 5:35.

If the styrene ratio exceeds 95%, the elasticity in the toner decreases, and the effect of adding the resin is not exhibited. On the other hand, if it is less than 65%, the viscosity of the monomer system increases sharply, and the granulation property decreases.

The styrene-butadiene resin used in the present invention may be any copolymer such as a random copolymer, a graft copolymer and a block copolymer. As a configuration that can occur in the above, a block copolymer is preferable.

The reason why the block copolymer is more effective is that the block copolymer has a reduced molecular chain spread to the monomer and has a certain elasticity as butadiene. I think that the.

In the present invention, the content of the styrene-butadiene resin in the toner is 0.1% with respect to the toner.
It is preferable that the amount be 1 part by weight or more and 10 parts by weight or less.

When the content is less than 0.1 part by weight,
The effect is not exhibited as good granulation is obtained due to the insufficient amount of addition, and when the amount exceeds 10 parts by mass, the elastic component in the toner increases due to the excessive amount of addition, which adversely affects the granulation. Become like

In the present invention (second invention), the chargeability and the fluidity can be improved by adding a polyester resin to the polymerizable monomer composition. Although the reason for this cannot be explained in detail at present, the fact that polar components are easily localized on the toner surface by suspension polymerization in an aqueous system causes carboxy groups, hydroxyl groups, and amide groups. It is considered that the polyester resin containing many polar components such as bonds is unevenly distributed on the toner surface.

Further, when the styrene-butadiene resin is contained in the polymerizable monomer composition, the coloring property is improved, and very good granulation is performed in the granulation step of the polymerization toner production process. Property. It is considered that the reason for this is that the additive resin improves the dispersibility of pigments and the like, and the granulation stabilizing effect is increased due to the improvement.

As the polyester used in the present invention, any polyester may be used as long as it is soluble in the polymerizable monomer. From the viewpoint of charging stability, the polyester has an acid value of 30 mg KOH / g or less. It is preferred that

The acid value of the polyester is 30 mg KOH / g
If it exceeds, too much polyester is unevenly distributed on the toner surface, and the water absorption is rapidly increased, so that the environmental stability of charging is reduced.

Further, a resin obtained by modifying a polyester with a styrene monomer or the like has improved solubility in a polymerizable monomer while maintaining a polar component. This is preferable because the suspension state is further stabilized and a toner having more excellent charging characteristics can be obtained.

The polyester constituents include:
Any one can be used as long as it maintains the above-mentioned acid value.Examples of the acid component monomer include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, and glutaric acid. , Adipic acid, pimelic acid,
Suberic acid, azelaic acid, sebacic acid, succinic acid, cyclohexanedicarboxylic acid, trimellitic acid, etc. are useful, and as the alcohol component monomer, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol , 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane, alkylene glycols and polyalkylene glycols, bisphenol A, hydrogenated bisphenol, bisphenol A Ethylene oxide adducts, bisphenol A propylene oxide adducts, glycerin, trimethylolpropane, pentaerythritol and the like are useful.

The constitution which can effectively bring about the effect of the present invention is such that the copolymerization ratio of styrene and butadiene is 95: 5-6.
The ratio is preferably 5:35.

If the styrene ratio exceeds 95%, the elasticity in the toner decreases, and the effect of adding the resin is not exhibited. On the other hand, if it is less than 65%, the granulation property is reduced.

The styrene-butadiene resin used in the present invention may be any copolymer such as a random copolymer, a graft copolymer and a block copolymer. As a configuration that can occur in the above, a block copolymer is preferable.

The reason why the block copolymer is more effective is that the block copolymer has a reduced molecular chain spread to the monomer and has a certain elasticity as butadiene. I think that the.

In the present invention, the sum of the contents of the styrene-butadiene resin and the polyester resin in the toner is 0.1 part by weight or more and 10 parts by weight or more with respect to 100 parts by weight of the toner.
It is preferable that the amount is not more than part by weight. When the content is less than 0.1 part by weight, the effect on the granulation property and the charging property is hardly exhibited, and when the content exceeds 10 parts by weight, the granulation property deteriorates due to excessive addition, and the fluidity also deteriorates. Let it.

Further, in the present invention (third invention), the present inventors conducted various studies in consideration of improving the fixability to a transfer material, particularly paper, by the wettability with a toner resin. Result A toner obtained by adding a polyester resin containing many polar components such as a carboxyl group, a hydroxyl group, and an amide bond, and a vinyl resin having an acid value, to the above-described titanium oxide subjected to a surface treatment as an external additive is combined. It has been found that a toner excellent in fixing property, fluidity, granulation property, environmental stability, etc. can be obtained.

This cannot be achieved only by the conventional means disclosed in JP-A-56-116043 and JP-A-60-238846.

The reason for this is unknown, but
Considering the characteristic of suspension polymerization, in which polar substances tend to be unevenly distributed on the surface of oil droplets, these two resins are unevenly distributed on the toner surface. In addition to improved wettability to paper, granulation, and fluidity of the polymerized toner, the charge-imparting ability was further improved as compared with the polyester-only addition system. And the titanium oxide used in the present invention is almost neutral, whereas hydrophobic silica as a generally known flow improver is itself strongly negatively charged. It is considered that this is because the change in toner chargeability due to an insufficient environment change is suppressed by only the means described above.

The polyester used in the present invention may be any polyester as long as it is soluble in the polymerizable monomer. From the viewpoint of charging stability, the polyester has an acid value of 30 mg KOH / g or less. It is preferred that

The acid value of the polyester is 30 mg KOH / g
If it exceeds, too much polyester is unevenly distributed on the toner surface, and the water absorption is rapidly increased, so that the environmental stability of charging is reduced.

Further, a resin obtained by modifying a polyester with a styrene-based monomer or the like has improved solubility in a polymerizable monomer while maintaining a polar component. For this reason, it is preferable to use a polyester modified with a styrene-based monomer, because the suspension state can be further stabilized, and a toner having more excellent charging characteristics can be obtained.

[0092] The constituent components of the polyester include:
Any one can be used as long as it maintains the above-mentioned acid value.Examples of the acid component monomer include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, and glutaric acid. , Adipic acid, pimelic acid,
Suberic acid, azelaic acid, sebacic acid, succinic acid, cyclohexanedicarboxylic acid, trimellitic acid, etc. are useful, and as the alcohol component monomer, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol , 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane, alkylene glycols and polyalkylene glycols, bisphenol A, hydrogenated bisphenol, bisphenol A Ethylene oxide adducts, bisphenol A propylene oxide adducts, glycerin, trimethylolpropane, pentaerythritol and the like are useful.

As the vinyl resin containing an acid component used in the present invention, any polymer can be used as long as the polymer has an acid value as a whole.

Examples of the vinyl resin (polar resin) containing an acid component that can be used in the present invention include a cationic polymer and an anionic polymer as exemplified below.

1) As the cationic polymer, a polymer of a nitrogen-containing monomer such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate or styrene.
Copolymers with unsaturated carboxylic esters and the like can be mentioned.

2) Examples of the anionic polymer include nitriles such as acrylonitrile, halogen-containing monomers such as vinyl chloride, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, and other unsaturated dibasic acids and unsaturated monomers. Examples thereof include a dibasic acid anhydride, a polymer such as a nitro-based monomer, and a copolymer with a styrene-based monomer.

The vinyl resin containing these acid components preferably has an acid value of 5 to 100 mgKOH / g. When the acid value is less than 5 mgKOH / g, the influence on the chargeability is reduced, and the rise of the charge is equivalent to the effect of the polyester alone addition system.

On the other hand, the vinyl resin has an acid value of 100 mgK.
If it exceeds OH / g, emulsified particles tend to be formed during suspension polymerization, which has an adverse effect such as an increase in toner particle size distribution.

In the present invention, a method for measuring the acid value of a polyester resin or a vinyl resin containing an acid component is described below.

Oxidation measurement method A sample of 2 to 10 g was weighed with 200
The mixture is weighed in a ~ 300 ml Erlenmeyer flask, and about 50 ml of a mixed solvent of methanol: toluene = 30: 70 is added to dissolve the resin. If solubility is poor, a small amount of acetone may be added. Using a mixed indicator of 0.1% promthymol blue and phenol red, titration is carried out with a previously standardized N / 10 potassium hydroxide-alcohol solution, and the acid value is determined by the following calculation from the consumption of the alcoholic potassium solution.

Acid value = KOH (number of ml) × N × 56.1 / sample weight (where N is a factor of N / 10 KOH)

In order to exhibit the above-mentioned effects effectively, the vinyl resin and the polyester resin containing the above-mentioned acid component must satisfy the following conditions: 0.1 ≦ a + b ≦ 10 900 ≧ A × a> B × b a indicates the amount of the vinyl resin added, b indicates the amount of the polyester resin added, A indicates the acid value of the vinyl resin (mgKOH / g), and B indicates the acid value of the polyester resin (mgKOH / g). g) is satisfied.

From the viewpoint of oil droplet stability during suspension polymerization, the sum of a and b is preferably as described above. If the sum of a and b exceeds 10, the amount of the high molecular weight dissolved in the monomer system is too large, the system becomes unstable, and the content of the added resin per toner particle is not constant. This has an adverse effect on pigment dispersion, chargeability, and the like.

When the sum of a and b is less than 0.1, effects such as granulation properties, charge stability, and wettability to paper become insufficient, resulting in poor image quality and fixability.

On the other hand, if the product of A and a exceeds 900, the added vinyl resin tends to become emulsified particles during suspension polymerization, which has an adverse effect such as an increase in the particle size distribution of the toner, and causes an adverse effect on the image. A phenomenon such as fog occurs. If the product of B and b is less than 0.1, the added polyester is less likely to be unevenly distributed on the toner surface, and the charge stabilizing effect of the polyester is reduced.

When the product of A and a is smaller than the product of B and b, the amount of polyester unevenly distributed on the toner surface is extremely increased, and the effect of stabilizing toner oil droplets and leading to charging is insufficient. The distribution is wide and phenomena such as a decrease in image density and a decrease in image quality occur.

The polymerizable monomers that can be used in the polymerized toner used in the present invention (first to third inventions) include:
Styrene, o-methylstyrene, m-methylstyrene,
Styrene monomers such as p-methylstyrene, p-methoxystyrene, p-ethylstyrene, methyl acrylate
Ethyl acrylate / n-butyl acrylate / isobutyl acrylate / n-propyl acrylate / n-acrylate
Acrylic esters such as octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, etc., methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, and n-methacrylate Methacrylates such as butyl, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and other acrylonitrile and methacrylic acid Monomers such as lonitrile and acrylamide are exemplified. These monomers can be used alone or as a mixture. Among the above-mentioned monomers, it is preferable to use styrene or a styrene derivative alone or in combination with another monomer from the viewpoint of the developing characteristics and durability of the toner.

In the present invention (the first and second inventions), it is more preferable to polymerize the monomer system by adding a polymer / copolymer having a polar group as an additive. Since the polar polymer / copolymer gathers at the particle surface layer during granulation,
It becomes like a kind of shell, and a granulation stabilizing effect is obtained,
Further, the chargeability is improved.

The polar polymers and copolymers that can be used in the present invention are exemplified below.

Polymers of nitrogen-containing monomers such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate, copolymers with styrene / unsaturated carboxylic esters, etc., nitrile monomers such as acrylonitrile, and vinyl chloride Polymers such as halogen-containing monomers, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, and other unsaturated dibasic acids and unsaturated dibasic acid anhydrides, nitro monomers, and styrene monomers And polyesters, epoxy resins and the like.

The amount of the polar polymer / copolymer added is preferably 0.1 to 10% by weight based on the toner.

As the colorant used in the present invention, known colorants can be used. For example, carbon black, iron black, C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modant Red 30, C.I.
I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modant Blue 7, C.I. I.
Direct Green 6, C.I. I. Basic Green 4, C.I. I. Dyes such as Basic Green 6, graphite, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hanza yellow G, permanent yellow NCG, tartrazine lake, molybdenum orange, permanent orange GT
R, Benzidine Orange G, Cadmium Red, Permanent Red 4R, Watching Ledge Calcium Salt,
Brilliantamine 3B, Fast Violet B, Methyl Violet Lake, Navy Blue, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Quinacridone, Rhodamine Lake, Phthalocyanine Blue, Fast Sky Blue, Pigment Green B, Malachite Green Lake, Final Yellow Green G, etc. There are pigments. In the present invention, in order to obtain a toner using a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and the aqueous phase migration property of the colorant, preferably, surface modification, for example, hydrophobicity by a substance without polymerization inhibition It is better to have a chemical treatment. In particular, attention must be paid to the use of dyes and carbon black since many of them have polymerization inhibitory properties. As a preferable method for surface-treating the dye system, there is a method in which a polymerizable monomer is polymerized in the presence of these dyes in advance, and the obtained colored polymer is added to the monomer system. The carbon black may be treated with a substance that reacts with the surface functional group of the carbon black, such as polyorganosiloxane, in addition to the same treatment as the above-described dye.

When the toner is used as a magnetic toner, a magnetic powder may be contained. As such magnetic powder, a substance that is magnetized when placed in a magnetic field is used.
There are powders of ferromagnetic metals such as iron, cobalt and nickel, or compounds such as magnetite and ferrite. In particular, in the present invention, in order to obtain a toner using a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and aqueous phase migration property of the magnetic substance, preferably, surface modification, for example, without polymerization inhibition It is better to carry out a hydrophobic treatment with a substance.

In the present invention, for the purpose of improving the releasability during the heat roll fixing property, waxes generally used as a releasing agent such as a hydrocarbon compound may be added to the toner. Examples of the waxes used in the present invention include paraffin / polyolefin waxes and modified products thereof, for example, oxides and grafted products, higher fatty acids, metal salts thereof, and amide waxes.
These waxes have a softening point of 40 to 130 ° C, preferably 50 to 120 ° C, according to a ring and ball method (JIS K 2531).
When the softening point is 40 ° C. or less, the toner has insufficient blocking resistance and shape retention, and has a softening point of 13%.
At a temperature of 0 ° C. or higher, the effect of the releasability becomes insufficient.

These release agents may be used alone or in combination.
% By weight is preferred.

In the present invention, it is desirable to add a charge control agent to the toner material in order to control the chargeability of the toner. As these charge control agents, those having little polymerization inhibition and water phase transfer among known ones are used. For example, as positive charge control agents, nigrosine dyes, triphenylmethane dyes, quaternary ammonium salts, guanidines Derivatives, imidazole derivatives, amine-based and polyamine-based compounds, and the like, as negative charge control agents, metal-containing salicylic acid-based compounds, metal-containing monoazo-based dye compounds, urea derivatives, styrene-acrylic acid copolymers, styrene-methacrylic Acid copolymers and the like can be mentioned.

The charge control agent may be added in an amount of 0.1.
1-10% by weight is preferred.

As the polymerization initiator, any suitable polymerization initiator such as 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1'-azobis (cyclohexane-1-
Azo or diazo polymerization initiators such as carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxy carbonate, Peroxide-based polymerization initiators such as cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide and lauroyl peroxide are exemplified. These polymerization initiators are preferably added in an amount of 0.5 to 20% by weight of the polymerizable monomer, and may be used alone or in combination.

In the present invention, a known crosslinking agent or chain transfer agent may be added to control the molecular weight. The preferable addition amount is 0.001 to 15% by weight.
It is.

Further, in the first to third inventions,
The following additives can be used in combination with titanium oxide.

For the purpose of imparting various toner properties, the additive should have a particle diameter of 1/10 or less of the volume average diameter of the toner particles from the viewpoint of durability when added to the toner or when added to the toner. Is preferred. The particle size of the additive means an average particle size obtained by observing the surface of the toner particles with an electron microscope. As additives for the purpose of imparting these properties, for example, the following are used. 1) Fluidity imparting agent: metal oxide (silicon oxide, aluminum oxide, titanium oxide, etc.), carbon black, carbon fluoride, etc. Each of them has been subjected to hydrophobic treatment,
More preferred. 2) Abrasives: metal oxides (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide, etc.), nitrides (silicon nitride, etc.), carbides (silicon carbide, etc.) metal salts (calcium sulfate, barium sulfate, etc.) Calcium carbonate). 3) Lubricant: fluororesin powder (vinylidene fluoride, polytetrafluoroethylene, etc.), fatty acid metal salt (zinc stearate, calcium stearate, etc.), etc. 4) Charge controllable particles: metal oxides (tin oxide, titanium oxide, zinc oxide, silicon oxide, aluminum oxide, etc.), carbon black and the like.

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

For the dispersion medium used in the present invention, any suitable stabilizer is used. For example, as inorganic compounds, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate -Bentonite, silica, alumina and the like. As an organic compound, polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, polyacrylic acid and its salts, starch and the like can be used by dispersing them in an aqueous phase.
These stabilizers are based on 100 parts of the polymerizable monomer.
It is preferred to use 0.2 to 20 parts by weight.

When an inorganic compound is used among these stabilizers, a commercially available one may be used as it is, but in order to obtain fine particles, the inorganic compound may be formed in a dispersion medium. For example, in the case of tricalcium phosphate, it is preferable to mix an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high stirring.

For fine dispersion of these stabilizers, 0.001 to 0.1 parts by weight of a surfactant may be used. This is to promote the expected action of the dispersion stabilizer, and specific examples thereof include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, and the like.
Examples thereof include sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, and calcium oleate.

The polymerization toner used in the present invention is obtained by the following method. That is, a monomer system in which a mold release agent, a coloring agent, a charge control agent, a polymerization initiator, and other additives are added to the polymerizable monomer, and the monomer system is uniformly dissolved or dispersed by a homogenizer, an ultrasonic disperser, or the like, It is dispersed in an aqueous phase containing a dispersion stabilizer by using a conventional stirrer or a homomixer / homogenizer. Preferably, the agitation speed and time are adjusted so that the monomer droplets have a desired toner particle size, generally a particle size of 30 μm or less, and granulation is performed. After that, due to the action of the dispersion stabilizer, the particle state is maintained,
In addition, stirring may be performed to such an extent that settling of particles is prevented.
The polymerization is performed at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. In addition, the temperature may be raised in the latter half of the polymerization reaction. Later, a part of the aqueous medium may be distilled off. After completion of the reaction, the generated toner particles are collected by washing and filtration, and dried. In the suspension polymerization method, it is generally preferable to use 300 to 3000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the monomer system.

Next, the image forming method of the present invention (fourth to sixth aspects) will be described.

As a result of intensive studies, the present inventors have found that the above-described electrophotographic photoreceptor of the toner can be prepared by incorporating fluorine or silicon atoms in the surface layer of the electrophotographic photoreceptor in a specific ratio to carbon atoms. It has been found that an image forming method can be obtained in which the adhesive force to the toner is reduced, the transferability and the cleaning property are excellent, and an excellent image can be obtained satisfactorily without the occurrence of defective cleaning even after running many sheets.

That is, the present invention (the fourth to sixth inventions) uses an electrophotographic photosensitive member having at least a conductive support and a photosensitive layer having a laminated structure of a charge generation layer and a charge transport layer. And forming a latent image by using a developer to transfer the latent image to a transfer material. The developer according to any one of the first to sixth aspects of the present invention is used as the developer. Further, a substance having a fluorine atom and / or a silicon atom is present in the surface layer of the electrophotographic photoreceptor, and the ratio of the fluorine atom and the silicon atom to the carbon atom by XPS measurement is as follows. Condition By satisfying the condition of fluorine atom / carbon atom (F / C) = 0.01 to 1.00 silicon atom / carbon atom (Si / C) = 0.03 to 1.00, higher image quality can be obtained after durability. Can also be obtained.

That is, F and Si lower the surface energy of the photoreceptor and lower the transferability and adhesion. On the other hand, the presence of a carbon atom raises its surface energy. By defining this ratio, it is possible to achieve a configuration in which transferability is good and no cleaning failure occurs even in a toner configuration having a strong adhesive force as in the present invention.

Here, if the F / C and Si / C of the photoconductor surface layer are less than 0.01 and 0.03, respectively, with respect to the toner used in the present invention, the photoconductor surface energy is high,
If the F / C and Si / C each exceed 1.00, the coefficient of friction with the cleaning member decreases, and conversely, poor cleaning through the toner occurs.

A still more preferable configuration is that the surface layer in the electrophotographic photoreceptor of the present invention contains polycarbonate, and it is even more preferable that the polycarbonate is synthesized from an asymmetric diol. .

As a result, an electrophotographic photosensitive member having excellent durability and good productivity can be obtained. Further, as a preferable configuration, it is preferable that a protective layer is provided on the photosensitive layer of the electrophotosensitive member, and the protective layer contains polycarbonate.

Thus, the stability of the durability characteristic is further increased.

Further, as a more preferable constitution for achieving the object of the present invention, the ratio of fluorine atom and / or silicon atom to oxygen atom by XPS measurement of the surface layer of the electrophotographic photosensitive member of the present invention is as follows. Conditions It is preferable to satisfy fluorine atom / oxygen atom (F / O) 0.01 or more and silicon atom / oxygen atom (Si / O) 0.03 or more.

By regulating the amount of oxygen atoms to fluorine atoms and silicon atoms as described above, the adhesion to the toner containing the resin having a polar component of the present invention can be more preferably controlled.

In the present invention, X on the surface of the electrophotographic photosensitive member is
The PS measurement method is described below.

As the XPS measuring device, ESC manufactured by VG is used.
The measurement was performed using an ALAB, 200-X type, X-ray photoelectron spectrometer.

The measurement conditions were as follows: X-ray source: Mg Kα (300 W); analysis area: 2 × 3 mm.

Hereinafter, the components used in the present invention will be specifically exemplified.

The construction of the electrophotographic photosensitive member used in the present invention will be described.

The photoreceptor used in the present invention has a photosensitive layer having a laminated structure having a charge generation layer and a charge transport layer on a conductive substrate. Further, in the present invention, a configuration in which a protective layer is provided on the charge transport layer may be used.

In the present invention, a fluorine-containing compound and / or
Alternatively, it is characterized by containing a silicon compound.

Further, as a means for more effectively achieving the object of the present invention, it is preferable that the charge transport layer and / or the protective layer contain polycarbonate.

Further, in the present invention, the polycarbonate preferably contains a polycarbonate synthesized using an asymmetric diol.

The materials used for the photoreceptor of the present invention are described below.

As specific examples of the fluorine-based compound, known fluorine-based resins may be mentioned, and ethylene tetrafluoride, ethylene trifluoride chloride, ethylene tetrafluoride hexafluoropropylene,
One or more types are appropriately selected from vinyl fluoride, vinylidene fluoride, ethylene difluoride diethylene chloride, and copolymers thereof.

Further, carbon fluoride or the like can be used.

In the present invention, a block containing a fluorine-containing segment synthesized from polymerization or copolymerization with a fluorine-based polymerizable monomer or a non-fluorine-based polymerizable monomer,
The graft polymer, surfactant, macromonomer and the like can be used alone or in combination with the above-mentioned fluororesin.

In particular, the combined use with a fluorine-based graft polymer having a continuous fluorine-based segment is also preferable from the viewpoint of facilitating the dispersion of the fluorine-based resin and the control of the surface F / C ratio which is a feature of the present invention.

Preferred specific examples of the above-mentioned fluorine-based polymerizable monomer are shown below, but the range of usable compounds is not limited to the above-mentioned range.

[0152]

[Outside 1] (In the above compounds, R ₁ represents a hydrogen atom, a halogen atom or a methyl group, R ₂ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a nitrile group, and may be a combination of several kinds thereof; An integer of 4 and m is 1 to 5
K + m = 5, and Rf is at least 1
It represents an alkyl group substituted with at least two fluorine atoms. )

Examples of the non-fluorinated polymerizable monomers include low-molecular-weight linear unsaturated hydrocarbons, vinyl halides, vinyl esters of organic acids, vinyl aromatic compounds, acrylic and methacrylic esters, N-vinyl One or more compounds such as a compound, a vinylsilicon compound, maleic anhydride, maleic acid and fumaric acid esters can be used, and a charge transport layer to which the formed fluorine-based graft polymer is added; It is preferable to select one that is compatible with the resin layer of the protective layer, or one that has a similar structure, even if not completely compatible, and that has a slight affinity between the two.

Specific examples of the silicon-based compound include three-dimensionally crosslinked monomethylsiloxane, dimethylsiloxane-
Monomethylsiloxane three-dimensional crosslinked products, ultrahigh molecular weight polydimethylsiloxane, block polymers containing polydimethylsiloxane segments, graft polymers, surfactants, macromonomers, terminal-modified polydimethylsiloxane, and the like are used. In the case of a three-dimensional crosslinked product, the particle size used in the form of fine particles or the like can be used in the range of 0.01 to 5 μm. In the case of a polydimethylsiloxane compound, its molecular weight can be used in the range of 3000 to 5,000,000. The fine particles are dispersed as a photosensitive layer composition together with a binder resin. As a dispersion method, a sand mill, a ball mill, a roll mill, a homogenizer, a nanomizer, a paint shaker, an ultrasonic wave, or the like is used. At the time of dispersion, it is preferable to use the above-mentioned graft, block polymer and surfactant as a dispersing aid, and it is also preferable to use them together for controlling the Si / C ratio which is a feature of the present invention.

The polycarbonate soluble in the aromatic hydrocarbon solvent or the halogenated aromatic hydrocarbon solvent used in the charge transport layer and / or the protective layer of the present invention can be obtained by lowering the crystallinity. . Specifically, for example, 1) bisphenol A and one or two or more asymmetric diol compounds 2) a general polycarbonate synthesis method such as a phosgene method using one or two or more asymmetric diol compounds Can be obtained by Further, it can also be obtained by using a diol compound having a substituent having 3 or more carbon atoms in a side chain.

The typical specific examples of the asymmetric diol compound used in the present invention are shown below, but the present invention is not limited thereto.

[0157]

[Outside 2]

[0158]

[Outside 3]

[0159]

[Outside 4]

[0160]

[Outside 5]

[0161]

[Outside 6]

The proportion of the asymmetric diol compound in the above-mentioned polycarbonate copolymer with bisphenol A is preferably at least 20% by weight, more preferably at least 50% by weight in the diol compound. 20% by weight of the asymmetric diol compound
If it is below, the solubility in the aromatic hydrocarbon solvent or the halogenated aromatic hydrocarbon solvent becomes insufficient, and the temporal stability of the coating liquid also deteriorates. The solubility (the number of grams of polycarbonate in 100 g of the solution at a temperature of 25 ° C.) of the polycarbonate soluble in the above-mentioned aromatic hydrocarbon solvent or halogenated aromatic hydrocarbon solvent is 1 g or more,
Particularly, 5 g or more is preferable. When the solubility is 1 g or less,
For example, when a coating solution for a charge transport layer is prepared, the viscosity of the coating solution is so low that an appropriate film thickness required for the charge transport layer cannot be obtained.

The effect of the polycarbonate used in the present invention can be enhanced particularly when used as a binder resin for a charge generation layer or a charge transport layer.

Examples of aromatic hydrocarbon solvents include benzene, toluene and xylene, and examples of halogenated aromatic hydrocarbon solvents include monochlorobenzene and dichlorobenzene.

When the electrophotographic photosensitive member used in the present invention is manufactured, a cylindrical cylinder or a film of metal such as aluminum or stainless steel, paper, plastic or the like is used as the conductive substrate. On these substrates,
An undercoat layer (adhesive layer) having a barrier function and an undercoat function can be provided.

The undercoat layer is used for improving the adhesion of the photosensitive layer, improving the coating property, protecting the substrate, covering defects on the substrate, improving the charge injection property from the substrate, protecting the photosensitive layer against electrical breakdown, and the like. It is formed. Examples of the material of the undercoat layer include polyvinyl alcohol, poly-N-vinyl imidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, ethylene-acrylic acid copolymer, casein, polyamide,
Copolymerized nylon, glue, gelatin and the like are known. These are dissolved in a suitable solvent and applied onto a substrate. Its film thickness is about 0.2 to 2 μm.

In the function-separated type photoreceptor, selenium-tellurium, pyrylium, thiapyrylium dye, phthalocyanine pigment, anthantrone pigment, dibenzpyrenequinone pigment, pyranthrone pigment, trisazo pigment, diazo pigment, azo pigment , Indigo pigment,
Quinacridone pigments, asymmetric quinocyanines, quinocyanines or amorphous silicon described in JP-A No. 54-143645 can be used. Examples of the charge transporting substance include pyrene, N-ethylcarbazole, N-isopropylcarbazole, and N-isopropylcarbazole. Methyl-N-phenylhydrazino-3-methylidene-9-ethylcarbazole, N,
N-diphenylhydrazino-3-methylidene-9-ethylcarbazole, N, N-diphenylhydrazino-3-
Methylidene-10-ethylphenothiazine, N, N-diphenylhydrazino-3-methylidene-10-ethylphenoxazine, P-diethylaminobenzaldehyde-
N, N-diphenylhydrazone, P-diethylaminobenzaldehyde-N-α-naphthyl-N-phenylhydrazone, P-pyrrolidinobenzaldehyde-N, N-diphenylhydrazone, 1,3,3-tramethylindolenine-ω-aldehyde Hydrazones such as -N, N-diphenylhydrazone, P-diethylbenzaldehyde-3-methylbenzthiazolinone-2-hydrazone, 2,
5-bis (P-diethylaminophenyl) -1,3,4
-Oxadiazole, 1-phenyl-3- (P-diethylaminostyryl) -5- (P-diethylaminophenyl) pyrazoline, 1- [quinolyl (2)]-3- (P-
Diethylaminostyryl) -5- (P-diethylaminophenyl) pyrazoline, 1 [pyridyl (2)]-3-
(P-diethylaminostyryl) -5- (P-diethylaminophenyl) pyrazoline, 1- [6-methoxy-pyridyl (2)]-3- (P-diethylaminostyryl)
-5- (P-diethylaminophenyl) pyrazolin, 1
-[Pyridyl (3)]-3- (P-diethylaminostyryl) -5- (P-diethylaminophenyl) pyrazolin, 1- [repidyl (2)]-3- (P-diethylaminostyryl) -5- (P- Diethylaminophenyl) pyrazolin, 1- [pyridyl (2)]-3-3 (P-diethylaminostyryl) -4-methyl-5- (P-diethylaminophenyl) pyrazolin, 1- [pyridyl (2)]-3- ( α-methyl-P-diethylaminostyryl) -5- (P-diethylaminophenyl) pyrazoline, 1-phenyl-3- (P-diethylaminostyryl) -4-methyl-5- (P-diethylaminophenyl) pyrazoline, 1-phenyl -3- (α-benzyl-
Pyrazolines such as P-diethylaminostyryl) -5- (P-diethylaminofail) pyrazoline and spiropyrazoline, 2- (P-diethylaminostyryl) -6-
Oxazole compounds such as diethylaminobenzoxazole, 2- (P-diethylaminophenyl) -4- (P-dimethylaminophenyl) -5- (2-chlorophenyl) oxazole, 2- (P-diethylaminostyryl) -6-diethylaminobenzo A thiazole compound such as thiazole, a triarylmethane compound such as bis (4-diethylamino-2-methylphenyl) -phenylmethane, 1,1-bis (4-N, N-diethylamino-
Polyarylalkanes such as 2-methylphenyl) heptane and 1,1,2,2-tetrakis- (4-N, N-dimethylamino-2-methylphenyl) ethane can be used.

The charge generation layer was prepared by adding the above-mentioned charge generation pigment to 0.1%.
With 3 to 4 times the amount of binder resin and solvent, well dispersed by a method such as homogenizer, ultrasonic wave, ball mill, vibrating ball mill, sand mill, attritor, roll mill, etc.
It is formed by coating and drying. Its thickness is 0.1-1μ
It is about.

When the above-mentioned polycarbonate resin is used for the charge generation layer, the charge generation substance may be dissolved together with the polycarbonate in an aromatic hydrocarbon solvent or a halogenated aromatic hydrocarbon solvent alone or in a mixed solvent thereof. ,
It is formed by applying a coating liquid obtained by dispersing a charge generating substance in a solution in which the above-mentioned polycarbonate resin is dissolved in the above-mentioned solvent. The proportion of the charge generation material in the charge generation layer can be 30% by weight or more, preferably 80% by weight or more. As solvents, toluene, xylene or monochlorobenzene are particularly useful. As a method of applying the coating solution, for example, a dip coating method, a spray coating method, a spinner coating method, a curtain coating method, or the like can be used.

When the above-mentioned polycarbonate resin is used for the charge transport layer, the charge transport material and the above-mentioned polycarbonate are used alone or in a mixture of the above-mentioned aromatic hydrocarbon solvents or halogenated aromatic hydrocarbon solvents. It is obtained by applying a coating solution prepared by dissolution. The mixing ratio of the charge transport material and the above-described polycarbonate resin used as a binder is about 2: 1 to 1: 2 by weight. Particularly useful solvents are toluene, xylene or monochlorobenzene.

As a method of applying this solution, for example, a dip coating method, a spray coating method, a spinner coating method, a curtain coating method and the like are known. The dip coating method is the best for efficient and accurate production of electrophotographic photoreceptors and mass production. Especially, the pot life in the dip coating method can be greatly improved by using the above-mentioned polycarbonate. The productivity of manufacturing using the coating method can be greatly improved. After applying and forming the charge transport layer, air drying or still drying is performed at a temperature of 10 ° C to 200 ° C, preferably 20 ° C to 150 ° C for 5 minutes to 5 hours, preferably 10 minutes to 2 hours. A charge transport layer of 20 μ is obtained.

[0172]

The present invention will be specifically described below with reference to examples. They do not limit the invention in any way.

In the present invention, the particle size distribution was measured by the following method.

As a measuring device, Coulter Counter T
A-II type (manufactured by Coulter), number average distribution,
Interface to output volume average distribution (made by Nikkaki)
And CX-1 personal computer (manufactured by Canon)
And the electrolyte is 1% Na using primary grade sodium chloride.
Prepare a Cl aqueous solution.

The measuring method is as follows.
In 50 ml, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant, and 0.5 to 50 mg of a measurement sample is further added. The electrolytic solution in which the sample was suspended was subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and was subjected to a dispersion treatment using the Coulter Counter TA-II using a 100 μm aperture as an aperture.
The particle size distribution of the μm particles is measured to determine a volume average distribution and a number average distribution.

From the obtained volume average distribution and number average distribution, a weight average particle size D4 is obtained.

In the present invention, the triboelectric charge was measured by the following measuring method.

FIG. 1 is an explanatory view of an apparatus for measuring a triboelectric charge amount of a toner. First, in a metal measuring container 12 having a 500-mesh screen 13 at the bottom, a mixture of a toner and a carrier in a weight ratio of 1:19 to be measured for triboelectric charge is put into a polyethylene bottle having a capacity of 50 to 100 ml, and Shake by hand for about 5 to 10 minutes, and mix (developer)
About 0.5 to 1.5 g is put and a metal lid 14 is formed. At this time, the weight of the entire measurement container 12 is weighed and defined as W ₁ (g). Next, in the suction device 11 (at least the portion in contact with the measurement container 12 is an insulator), the pressure of the vacuum gauge 15 is adjusted to 250 mmA by adjusting the air volume control valve 16 by suctioning from the suction port 17.
q. In this state, suction is sufficiently performed, preferably for 2 minutes, to remove the toner by suction. The potential of the electrometer 19 at this time is set to V (volt). Here, reference numeral 18 denotes a capacitor having a capacity of C (μF). Further, the weight of the whole measurement container after suction is weighed to be W ₂ (g). The triboelectric charge (μc / g) of this toner is calculated as in the following equation.

[0179]

[Outside 7] (However, measurement conditions are 23 ° C. and 60% RH.)

[Photoreceptor Production Example A] Conductive titanium oxide (tin oxide coating, average primary particle size of 0.1%).
4μ) 10 parts by weight, phenolic resin precursor (resole type) 10 parts by weight, methanol parts by weight, and butanol 1
0 parts by weight are dispersed in a sand mill and then dip-coated on an aluminum cylinder having an outer diameter of 80 mm and a length of 360 mm.
After curing at 140 ° C., a conductive layer having a volume resistance of 5 × 10 ⁹ Ωcm and a thickness of 20 μ was provided.

Next, 10 parts by weight of the following methoxymethylated nylon (methoxymethylation degree: about 30%)

[0182]

[Outside 8] And 150 parts by weight of isopropanol were mixed and dissolved, and then dip-coated on the conductive layer to provide a 1 μm undercoat layer.

Next, 10 parts by weight of the following azo pigment:

[0184]

[Outside 9] The following polycarbonate resin (bisphenol A molecular weight 3
0000) 5 parts by weight,

[0185]

[Outside 10] And 700 parts by weight of cyclohexanone were dispersed in a sand mill, and this dispersion was applied by dip coating on the undercoat layer.
A charge generation layer of 0.05 μ was obtained.

Next, 10 parts by weight of the following triphenylamine:

[0187]

[Outside 11] Polycarbonate resin of the following structure (Bisphenol Z
Mold, molecular weight 20,000) 10 parts by weight

[0188]

[Outside 12] 50 parts by weight of monochlorobenzene and dichloromethane 1
After stirring and mixing 5 parts by weight, dip coating was performed on the charge generation layer. The coated cylinder was dried with hot air to form a 20 μm charge transport layer.

Next, 1 part by weight of carbon fluoride fine powder (average particle size: 0.23 μm, manufactured by Central Glass Co., Ltd.) and the following polycarbonate resin (bisphenol Z, molecular weight 800
00) 6 parts by weight,

[0190]

[Outside 13] The following perfluoroalkyl acrylate-methyl methacrylate block copolymer (molecular weight 30,000) 0.1
Parts by weight

[0191]

[Outside 14] Monochlorobenzene (120 parts by weight) and dichloromethane (80 parts by weight) were dispersed and mixed in a sand mill. 3 parts by weight of the following triphenylamine

[0192]

[Outside 15] Was added and mixed and dissolved, and the mixture was applied in the form of a charge transport layer by spray coating.

[F / C Ratio XPS Measurement] After exfoliating the surface of the photoconductor A, an ESCAL manufactured by VG
Surface elements were quantified using an AB200-X type X-ray photoelectron spectrometer. Using MgCa (300 W) as an X-ray source, the measurement was performed at a depth of several に つ い て over a 2 × 3 mm area.
The surface of the photoconductor A of Production Example A had 5, 2% of F atoms and 81.3% of C atoms, and the F / C ratio was 0.064.

[Photoreceptor Production Example B] Conductive titanium oxide (tin oxide coat, average primary particle size of 0.1%).
4μ) 10 parts by weight of a phenolic resin precursor (resole type), 10 parts by weight of methanol, and 10 parts by weight of butanol were dispersed in a sand mill, and the outer diameter was 80 m.
m, dip-coated on an aluminum cylinder with a length of 360 mm, cured at 140 ° C., and had a volume resistance of 5 × 10 ⁹ cm.
A conductive layer having a thickness of 20 μ was provided.

Next, 10 parts by weight of the following methoxymethylated nylon (degree of methoxymethylation: about 30%)

[0196]

[Outside 16] And 150 parts by weight of isopropanol were mixed and dissolved, and then dip-coated on the conductive layer to provide a 1 μm undercoat layer.

Next, 10 parts by weight of the following azo pigment:

[0198]

[Outside 17] The following polycarbonate resin (bisphenol A molecular weight 3
0000) 5 parts by weight,

[0199]

[Outside 18] And 700 parts by weight of cyclohexanone were dispersed in a sand mill, and this dispersion was applied by dip coating on the undercoat layer.
A charge generation layer of 0.05 μ was obtained.

Next, 10 parts by weight of the following triphenylamine:

[0201]

[Outside 19] Polycarbonate resin of the following structure (Bisphenol Z
Mold, molecular weight 20,000) 10 parts by weight

[0202]

[Outside 20] 50 parts by weight of monochlorobenzene and dichloromethane 1
After stirring and mixing 5 parts by weight, dip coating was performed on the charge generation layer. The coated cylinder was dried with hot air to form a 20 μm charge transport layer.

Next, 1 part by weight of spherical three-dimensionally crosslinked polysiloxane fine particles (average particle size: 0.29 μm, manufactured by Toshiba Silicone Co., Ltd.) and the following polycarbonate resin (bisphenol Z,
(Molecular weight: 80000) 6 parts by weight,

[0204]

[Outside 21] The following polydimethylsiloxane methacrylate-methyl methacrylate block copolymer (molecular weight 50,000, S
i amount 12 wt%) 0.1 part by weight

[0205]

[Outside 22] Monochlorobenzene (120 parts by weight) and dichloromethane (80 parts by weight) were dispersed and mixed in a sand mill. 3 parts by weight of the following triphenylamine

[0206]

[Outside 23] Was added and mixed and dissolved, and the mixture was applied in the form of the charge transport layer by spray coating.

[Si / C Ratio XPS Measurement] After peeling off the surface of the photoconductor B, an ESCAL manufactured by VG
Surface elements were quantified using an AB200-X type X-ray photoelectron spectrometer. Using MgCa (300 W) as an X-ray source, the measurement was performed at a depth of several に つ い て over a 2 × 3 mm area.
The surface of the photoreceptor B of Production Example B has 10.2% of Si atoms and C
The atomic ratio was 69.3%, and the Si / C ratio was 0.147.

[Photoreceptor Production Example C] In the photoreceptor A of photoreceptor production example A, a photoreceptor C was obtained by applying a charge transport layer without a protective layer.

Table 1 shows the F / C ratio and the F / O ratio of the surface layers of the photoconductors A and C.
Table 2 shows the / C ratio and the Si / O ratio.

[0210]

[Table 1]

[0211]

[Table 2]

[Preparation of External Additive (a)] Hydrophilic titanium oxide fine particles (particle size: 0.05 μm) were added to an aqueous system, and mixed and stirred by a mechanical method. A surface treatment was carried out while adding and dispersing vinyltriethoxysilane as a coupling agent in a treatment amount of 30% by weight based on the weight part and hydrolyzing. At this time, the particles were not coalesced. After that, it is dried and crushed to have an average particle size of 0.05 μm and a hydrophobicity of 60%.
Titanium oxide having a light transmittance of 81% at 400 nm was obtained.

[Preparation of External Additives (b) to (e)] The particle size of the titanium oxide used in the preparation of the external additive (a), the treatment amount of the silane coupling agent, and the type of the silane coupling agent External additives (b), (c), (d) and (e) were prepared in the same manner except that the composition was changed to the configuration shown in Table 3.

Table 3 shows the constitution and physical properties of the external additives (a) to (e).

[0215]

[Table 3]

[Particle Size of External Additive] The particle size of the external additive was measured using a transmission electron microscope.

[Degree of Hydrophobization of External Additive] The degree of hydrophobicity of the external additive was measured by a methanol titration test as follows.

External additive (titanium oxide) 0.2 g serving as sample
Is added to 50 ml of water in a 250 ml Erlenmeyer flask. Methanol is titrated from the burette until all of the titanium oxide is wetted. At this time, the solution in the flask is constantly stirred with a magnetic stirrer. The end point is observed by the suspension of the entire amount of titanium oxide in the liquid, and the degree of hydrophobicity is expressed as the percentage of methanol in the liquid mixture of methanol and water at the end point.

[Permeability of External Additive] The transmittance of the external additive was measured by the following procedure. 1. Sample 0.10g Alkyd resin 13.20 * 1 Melamine resin 3.30 * 2 Thinner 3.50 * 3 Glass media 50.00 * 1 Bekkosol 323-60-EL manufactured by Dainippon Ink Ink Superbeckamine manufactured by Dainippon Ink J-820-
60 * 3 Amirac thinner manufactured by Kansai Paint The above composition is collected in a 150 cc mayonnaise bottle, and dispersed for 1 hour using a paint conditioner manufactured by Red Devil. 2. After the dispersion, the PET film is applied to the PET film with a doctor blade for 2 minutes. 3.2. Is heated at 120 ° C. for 10 minutes to perform baking. 4.3. The transmittance of the sheet of 320 to 800 nm is measured by U-BEST 50 manufactured by JASCO Corporation and compared.

[Production Example AA of Polymerized Toner] To 710 g of ion-exchanged water, 450 g of a 0.1 M Na ₃ PO ₄ aqueous solution was charged, heated to 60 ° C., and then a TK homomixer (manufactured by Tokushu Kika Kogyo). Using 12000 rp
m. A 1.0 M CaCl ₂ aqueous solution 6
8 g was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .

Styrene
167 g n-butyl acrylate 33 g C.I. I. Pigment Blue 15: 3 10 g Di-tert-butylsalicylate metal compound 2 g Styrene-butadiene block copolymer (copolymerization ratio 8
0:20) 3 g

The above formulation was heated to 60 ° C., and was subjected to 12000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo).
To dissolve and disperse uniformly. In addition, polymerization initiator 2,
2'-azobis (2,4-dimethylvaleronitrile) 1
0 g was dissolved to prepare a polymerizable monomer composition.

The above polymerizable monomer composition was put into the aqueous medium, and the mixture was stirred at 10,000 rpm for 20 minutes with a TK homomixer at 60 ° C. in an N ₂ atmosphere. Was granulated. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 80 ° C., and the reaction was performed for 10 hours.

After the completion of the polymerization reaction, a part of the aqueous medium was distilled off under reduced pressure, the solution was cooled, hydrochloric acid was added to dissolve the calcium phosphate, followed by filtration, washing with water and drying to give a weight average diameter of about 8 μm.
m sharp colored suspension particles (toner particles) were obtained.

To 100 parts by weight of the obtained toner particles, 1.5 parts by weight of an external additive (a) shown in Table 3 was externally added to obtain a suspension polymerization toner AA.

[Production Example BB of Polymerized Toner] To 100 parts by weight of the toner particles used in Production Example AA of the polymerized toner, 1.5 parts by weight of the external additive (b) shown in Table 3 was externally added and suspended. Polymerized toner BB was obtained.

[Production Example CC of Polymerized Toner] 465 g of a 0.1 M Na ₃ PO ₄ aqueous solution was charged into 695 g of ion-exchanged water and heated to 60 ° C., and then a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Using 12000 rp
m. A 1.0 M CaCl ₂ aqueous solution 6
8 g was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .

Styrene
167 g n-butyl acrylate 33 g C.I. I. Pigment Yellow 177 g Di-tert-butylsalicylic acid metal compound 2 g Styrene-butadiene copolymer (copolymerization ratio 80:20)
5g

The above-mentioned formulation was heated to 60 ° C., and was subjected to 12000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo).
To dissolve and disperse uniformly. In addition, polymerization initiator 2,
2'-azobis (2,4-dimethylvaleronitrile) 1
0 g was dissolved to prepare a polymerizable monomer composition.

The polymerizable monomer composition was charged into the aqueous medium, and the mixture was stirred at 60 ° C. under a N ₂ atmosphere with a TK homomixer at 10,000 rpm for 20 minutes. Was granulated. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 80 ° C., and the reaction was performed for 10 hours.

After the completion of the polymerization reaction, a part of the aqueous medium was distilled off under reduced pressure, the mixture was cooled, hydrochloric acid was added to dissolve calcium phosphate, and the mixture was filtered, washed with water and dried to give a weight average diameter of about 8 μm.
m sharp colored suspension particles (toner particles) were obtained.

To 100 parts by weight of the obtained toner particles, 1.5 parts by weight of an external additive (b) shown in Table 3 was externally added to obtain a suspension polymerization toner CC.

[Production Example DD of Polymerized Toner] 450 g of a 0.1 M Na ₃ PO ₄ aqueous solution was charged into 710 g of ion-exchanged water and heated to 60 ° C., and then a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Using 12000 rp
m. A 1.0 M CaCl ₂ aqueous solution 6
8 g was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .

Styrene
167 g n-butyl acrylate 34 g C.I. I. Pigment Blue 15: 3 10 g Di-tert-butylsalicylate metal compound 3 g Styrene-butadiene copolymer (copolymerization ratio 80:20)
40g

The above-mentioned formulation was heated to 60 ° C., and was subjected to 12000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo).
To dissolve and disperse uniformly. In addition, polymerization initiator 2,
2'-azobis (2,4-dimethylvaleronitrile) 1
0 g was dissolved to prepare a polymerizable monomer composition.

The above-mentioned polymerizable monomer composition was put into the aqueous medium, and the mixture was stirred at 10,000 rpm for 20 minutes with a TK homomixer at 60 ° C. in an N ₂ atmosphere. Was granulated. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 80 ° C., and the reaction was performed for 10 hours.

After the completion of the polymerization reaction, a part of the aqueous medium was distilled off under reduced pressure, the mixture was cooled, hydrochloric acid was added to dissolve the calcium phosphate, and the mixture was filtered, washed with water and dried to give a weight average diameter of about 8.
8 μm of colored suspension particles (toner particles) were obtained.

To 100 parts by weight of the obtained toner particles, 1.5 parts by weight of an external additive (d) shown in Table 3 was externally added to obtain a suspension polymerization toner DD.

[Production Example EE of Polymerized Toner] 1.5 parts by weight of the external additive (c) shown in Table 3 was externally added to 100 parts by weight of the toner particles used in Production Example AA of the polymerized toner. Polymerized toner EE was obtained.

[Production Example FF of Polymerized Toner] A BET specific surface area as an external additive (f) was 200 with respect to 100 parts by weight of the toner particles used in Production Example CC of the polymerized toner.
0.8 parts by weight of m ² / g hydrophobic silica was externally added to obtain a suspension polymerization toner FF.

[Developer and Evaluation Method 1] A developer was obtained by mixing 95 parts by weight of an acrylic-coated ferrite carrier (particle size: 50 μm) with 5 parts by weight of the toner. This is Canon full color laser copier C
The LC-500 was modified and images were obtained using the photoconductors A to C. The development conditions were: Vcont = 360 V,
Vback = −140 V, and the sleeve peripheral speed was 170 rpm. The image appearance evaluation was performed by using the developer under low temperature and low humidity (150
10% RH: L / L) under normal temperature and normal humidity (23 ° C., 60
% RH: N / N) and under high temperature and high humidity (30 ° C., 80% R)
(H: H / H) for 1 day, 10,000 images were taken out in each environment, and the printing test image after 10,000 sheets was compared with the original chart. Evaluation was made by focusing on image density, highlight reproducibility, fog, and carrier adhesion.

Further, the developing device was idly rotated at a speed of 200 rpm for 30 minutes to evaluate image formation.

Further, the granulation property during the production of the toner was evaluated.

[Examples 1 to 4 and Comparative Examples 1 to 3] The above toners AA to FF and photoconductors A to C were used in combination shown in Table 4, and the above [Developer Preparation and Evaluation Method 4] was used. , A developer was prepared, and the image output was evaluated.

The evaluation results are shown in Table 4.

In Example 1, excellent results were obtained in both durability and environmental characteristics. Further, the granulation property during the production of the toner was remarkably good.

In Example 2, excellent results in both durability and environmental characteristics were obtained. Further, the granulation property during the production of the toner was good.

In Example 3, the durability and L / L
The image quality under the environment was good, but the scattering under the H / H environment was at a practically feasible level.
The granulation property during the production of the toner was good.

In Example 4, excellent results were obtained in both durability and environmental characteristics. Further, the granulation property during the production of the toner was remarkably good.

In Comparative Example 1, the results that both the durability and the environmental characteristics were significantly deteriorated were obtained. Further, the granulation property during the production of the toner was extremely poor.

In Comparative Example 2, although the image quality under the L / L environment was slightly good, poor results were obtained with respect to durability and scattering under the H / H environment.

In Comparative Example 3, a result was obtained in which both the durability and the environmental characteristics were significantly deteriorated.

[0253]

[Table 4]

[Production Example GG of Polymerized Toner] 440 g of a 0.1 M Na ₃ PO ₄ aqueous solution was charged into 700 g of ion-exchanged water, heated to 60 ° C., and then a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Using 12000 rp
m. A 1.0 M CaCl ₂ aqueous solution 6
8 g was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .

Styrene
170 g n-butyl acrylate 30 g C.I. I. Pigment Blue 15:38 g Di-tert-butylsalicylate metal compound 4 g Styrene-butadiene copolymer 3 g Styrene 1.0% by weight modified polyester resin (acid value: 2
0mgKOH / g) 5g

The above-mentioned formulation was heated to 60 ° C., and was subjected to 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo).
To dissolve and disperse uniformly. In addition, polymerization initiator 2,
2'-azobis (2,4-dimethylvaleronitrile) 1
5 g was dissolved to prepare a polymerizable monomer composition.

The polymerizable monomer composition was charged into the aqueous medium, and the mixture was stirred at 10,000 rpm for 20 minutes with a TK homomixer at 60 ° C. in an N ₂ atmosphere. Was granulated. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 80 ° C., and the reaction was performed for 10 hours.

After the completion of the polymerization reaction, a part of the aqueous medium was distilled off under reduced pressure, the mixture was cooled, hydrochloric acid was added to dissolve calcium phosphate, and the mixture was filtered, washed with water and dried to give a weight average diameter of about 8 μm.
m sharp colored suspension particles (toner particles) were obtained.

To 100 parts by weight of the obtained toner particles, 1.5 parts by weight of the external additive (a) shown in Table 3 was externally added to obtain a suspension polymerization toner GG.

[Production Example HH of Polymerized Toner] 1.5 parts by weight of an external additive (b) shown in Table 3 was externally added to 100 parts by weight of the toner particles used in Production Example GG of the polymerized toner. Polymerized toner HH was obtained.

[Production Example II of Polymerized Toner] 440 g of a 0.1 M Na ₃ PO ₄ aqueous solution was charged into 700 g of ion-exchanged water, heated to 60 ° C., and then a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Using 12000 rp
m. A 1.0 M CaCl ₂ aqueous solution 6
8 g was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .

Styrene
170 g n-butyl acrylate 30 g C.I. I. Pigment Yellow 17 10 g Metal compound di-tert-butylsalicylate 5 g Styrene-butadiene copolymer 5 g 0.5% by weight of styrene modified polyester resin (acid value: 4
5mgKOH / g) 5g

The above-mentioned formulation was heated to 60 ° C., and was subjected to 12000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo).
To dissolve and disperse uniformly. In addition, polymerization initiator 2,
2'-azobis (2,4-dimethylvaleronitrile) 1
5 g was dissolved to prepare a polymerizable monomer composition.

The polymerizable monomer composition was charged into the aqueous medium, and the mixture was stirred at 10,000 rpm for 20 minutes at 60 ° C. in a N ₂ atmosphere using a TK homomixer to obtain a polymerizable monomer composition. Was granulated. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 80 ° C., and the reaction was performed for 10 hours.

After the completion of the polymerization reaction, a part of the aqueous medium was distilled off under reduced pressure, the mixture was cooled, hydrochloric acid was added to dissolve the calcium phosphate, followed by filtration, washing with water and drying to give a weight average diameter of about 8 μm.
m sharp colored suspension particles (toner particles) were obtained.

To 100 parts by weight of the obtained toner particles, 1.5 parts by weight of an external additive (b) shown in Table 3 was externally added to obtain a suspension polymerization toner II.

[Production Example JJ of Polymerized Toner] 440 g of a 0.1 M Na ₃ PO ₄ aqueous solution was put into 700 g of ion-exchanged water, heated to 60 ° C., and then a TK homomixer (manufactured by Tokushu Kika Kogyo). Using 12000 rp
m. A 1.0 M CaCl ₂ aqueous solution 6
8 g was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .

Styrene
170 g n-butyl acrylate 30 g C.I. I. Pigment Blue 15: 3 10 g Di-tert-butylsalicylate metal compound 5 g Styrene-butadiene copolymer 30 g Styrene 0.8% by weight modified polyester resin (acid value: 1
5 mg KOH / g) 20 g

The above-mentioned formulation was heated to 60 ° C., and was subjected to 12000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo).
To dissolve and disperse uniformly. In addition, polymerization initiator 2,
2'-azobis (2,4-dimethylvaleronitrile) 1
5 g was dissolved to prepare a polymerizable monomer composition.

The polymerizable monomer composition was charged into the aqueous medium, and the mixture was stirred at 10,000 rpm for 20 minutes with a TK homomixer at 60 ° C. in an N ₂ atmosphere. Was granulated. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 80 ° C., and the reaction was performed for 10 hours.

After the completion of the polymerization reaction, a part of the aqueous medium was distilled off under reduced pressure, the mixture was cooled, hydrochloric acid was added to dissolve the calcium phosphate, and the mixture was filtered, washed with water and dried to give a weight average diameter of about 8 μm.
m sharp colored suspension particles (toner particles) were obtained.

To 100 parts by weight of the obtained toner particles, 1.5 parts by weight of an external additive (d) shown in Table 3 was externally added to obtain a suspension polymerization toner JJ.

[Production Example of Polymerized Toner KK] 440 g of a 0.1 M Na ₃ PO ₄ aqueous solution was charged into 700 g of ion-exchanged water and heated to 60 ° C., and then a TK homomixer (manufactured by Tokushu Kika Kogyo) Using 12000 rp
m. A 1.0 M CaCl ₂ aqueous solution 6
8 g was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .

Styrene
160 g n-butyl acrylate 40 g carbon black 10 g metal compound di-tert-butylsalicylate 5 g styrene-butadiene copolymer 10 g

The above-mentioned formulation was heated to 60 ° C., and was subjected to 12000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo).
To dissolve and disperse uniformly. In addition, polymerization initiator 2,
2'-azobis (2,4-dimethylvaleronitrile) 2
0 g was dissolved to prepare a polymerizable monomer composition.

The polymerizable monomer composition was charged into the aqueous medium, and the mixture was stirred at 60 ° C. under a N ₂ atmosphere with a TK homomixer at 10,000 rpm for 20 minutes to obtain a polymerizable monomer composition. Was granulated. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 80 ° C., and the reaction was performed for 10 hours.

After the completion of the polymerization reaction, a part of the aqueous medium was distilled off under reduced pressure, the mixture was cooled, hydrochloric acid was added to dissolve the calcium phosphate, followed by filtration, washing with water and drying to give a weight average diameter of about 8 μm.
m sharp colored suspension particles (toner particles) were obtained.

To 100 parts by weight of the obtained toner particles, 1.5 parts by weight of an external additive (c) shown in Table 3 was externally added to obtain a suspension polymerization toner KK.

[Production Example LL of Polymerized Toner] A BET specific surface area of 200 parts by weight as an external additive (f) was used for 100 parts by weight of the toner particles used in Production Example II of the polymerized toner.
0.8 parts by weight of m ² / g hydrophobic silica was externally added to obtain a suspension polymerization toner LL.

[Developer and Evaluation Method 2] A developer was obtained by mixing 95 parts by weight of an acrylic-coated ferrite carrier (particle size: 50 μm) with 5 parts by weight of the toner. This is Canon full color laser copier C
The LC-500 was modified and images were obtained using the photoconductors A to C. The development conditions were: Vcont = 360 V,
Vback = −140 V, and the sleeve peripheral speed was 180 rpm. The evaluation of image output was carried out using a developer under low temperature and low humidity (10
10% RH: L / L) under normal temperature and normal humidity (23 ° C., 60
% RH: N / N) and under high temperature and high humidity (30 ° C., 85% R)
(H: H / H) for one day, 10,000 images were taken out in each environment, and the image of the printing test after 15,000 sheets was compared with the original chart. The evaluation was made by focusing on the image density, highlight reproducibility, fog, and carrier adhesion.

Further, the developing device was idly rotated at a speed of 200 rpm for 30 minutes to evaluate image formation.

Further, the chargeability of the toner and the granulation during the production of the toner were evaluated.

[Examples 5 to 8 and Comparative Examples 4 and 6] The toners GG to LL and the photoconductors A to C were used in combination shown in Table 5, and according to the above [Development of developer and evaluation method 2]. , A developer was prepared, and the image output was evaluated.

The evaluation results are shown in Table 5.

In Example 5, excellent results were obtained in both durability and environmental characteristics. Further, the chargeability of the toner and the granulation property during the production of the toner were remarkably good.

In Example 6, excellent results in both durability and environmental characteristics were obtained. Further, the chargeability of the toner and the granulation property during the production of the toner were remarkably good.

In Example 7, the durability was H / H
Although the scattering under the environment was good, the image quality under the L / L environment was at a slightly better level. The chargeability of the toner and the granulation during toner production were good.

In Example 8, excellent results were obtained in both durability and environmental characteristics. Further, the chargeability of the toner and the granulation during the production of the toner were remarkably good.

In Comparative Example 4, a result was obtained in which both the durability and the environmental characteristics were significantly deteriorated. Further, the chargeability of the toner was at a practically feasible level, but the granulation property during the production of the toner was extremely poor.

In Comparative Example 5, good results were obtained in both the durability and the environmental characteristics, but the charge amount of the toner was slightly reduced after being left under high humidity for a long time.

In Comparative Example 6, a result was obtained in which both the durability and the environmental characteristics were significantly deteriorated.

[0292]

[Table 5]

[Production Example of Polymerized Toner MM] 450 g of 0.1 M Na ₃ PO ₄ aqueous solution was charged into 710 g of ion-exchanged water, heated to 60 ° C., and then subjected to TK homomixer (manufactured by Tokushu Kika Kogyo). Using 12000 rp
m. A 1.0 M CaCl ₂ aqueous solution 6
8 g was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .

Styrene
165 g n-butyl acrylate 35 g C.I. I. Pig. Blue 15: 3 10 g Di-tert-butylsalicylic acid metal compound 2 g Styrene 0.5% by weight modified polyester resin (oxidation: 1
0 mg KOH / g) 5 g Styrene-methacrylic acid copolymer (acid value: 20 mg KO)
H / g) 5 g Polyethylene wax 4 g

The above-mentioned formulation was heated to 60 ° C., and was subjected to 12000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo).
To dissolve and disperse uniformly. In addition, polymerization initiator 2,
2'-azobis (2,4-dimethylvaleronitrile) 1
0 g was dissolved to prepare a polymerizable monomer composition.

The above-mentioned polymerizable monomer composition was put into the aqueous medium, and the mixture was stirred at 60 ° C. under a N ₂ atmosphere with a TK homomixer at 10,000 rpm for 20 minutes to obtain a polymerizable monomer composition. Was granulated. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 80 ° C., and the reaction was performed for 10 hours.

After the completion of the polymerization reaction, a part of the aqueous medium was distilled off under reduced pressure, the mixture was cooled, hydrochloric acid was added to dissolve the calcium phosphate, and the mixture was filtered, washed with water and dried to give a weight average diameter of about 8 μm.
m sharp colored suspension particles (toner particles) were obtained.

To 100 parts by weight of the obtained toner particles, 0.12 parts by weight of an external additive (a) shown in Table 3 was externally added.
A suspension polymerization toner MM was obtained.

[Production Example of Polymerized Toner NN] Production Example of Polymerized Toner 0.5% by weight of styrene used in MM
6mgKOH / g oxidation instead of modified polyester resin
Using a polyester resin of 20 mg KO
The same procedure was followed except that a 15 mg KOH / g styrene-methacrylic acid copolymer was used in place of the H / g styrene-methacrylic acid copolymer.
3 μm toner particles were obtained. Obtained toner particles 100
0.12 parts by weight of the external additive (a) shown in Table 3 was externally added to the parts by weight to obtain a suspension polymerization toner NN.

The toner particles obtained in Production Example NN of the polymerized toner are slightly inferior in the granulation property at the time of toner production as compared with the toner particles obtained in Production Example MM of the polymerized toner.
The particle size distribution with a weight average diameter of 5.02 μm or less was slightly increased.

[Production Example of Polymerized Toner OO] 0.12 parts by weight of an external additive (d) shown in Table 3 was externally added to 100 parts by weight of the toner particles used in Polymerization Toner Production Example MM. Polymerized toner OO was obtained.

[Production Example of Polymerized Toner PP] Production Example of Polymerized Toner 0.5% by weight of styrene used in MM
The same operation was performed except that the modified polyester resin and the styrene-methacrylic acid copolymer were not used, to obtain toner particles having a weight average particle diameter of 11.0 μm. To 100 parts by weight of the obtained toner particles, 0.12 parts by weight of the external additive (a) shown in Table 3 was externally added to obtain a suspension polymerization toner PP.

The toner particles obtained in Production Example PP of the polymerized toner have a poor particle-forming property during the production of the toner as compared with the toner particles obtained in Production Example MM of the polymerized toner. A large amount of fine powder was generated.

[Production Example of Polymerized Toner QQ] 0.12 parts by weight of an external additive (e) shown in Table 3 was externally added to 100 parts by weight of the toner particles used in Polymerization Toner Production Example MM and suspended. Polymerized toner QQ was obtained.

[Developer and Evaluation Method 3] A developer was obtained by mixing 95 parts by weight of an acrylic-coated ferrite carrier (particle size: 50 μm) with 5 parts by weight of the toner. This is Canon full color laser copier C
The LC-500 was modified and images were obtained using the photoconductors A to C. The development conditions were: V _cont = 360 V, V
_back = -140V, and the sleeve peripheral speed was 170 rpm. Evaluation of image output was performed by using a developer under low temperature and low humidity (15 ° C., 1
0% RH: L / L) under normal temperature and normal humidity (23 ° C., 60% R)
H: N / N) and under high temperature and high humidity (30 ° C., 80% RH: H)
/ H) in one environment for one day, 10,000 images were taken out in each environment, 10,000 images of the printing test were compared with the original chart, and the image density, Evaluation was made by focusing on highlight reproducibility and fog.

Further, the developing unit was idled at a speed of 200 rpm for 30 minutes to evaluate image formation.

The image density was measured using a Macbeth reflection densitometer (RD).
-918).

[Examples 9 to 12 and Comparative Examples 7 and 8] The toners MM to QQ and the photoconductors A to C were used in combinations shown in Table 6, and according to the above [Development and Evaluation Method 3 of Developer]. , A developer was prepared, and the image output was evaluated.

The results of the evaluation are shown in Table 6.

[0310]

[Table 6]

[0311]

According to the present invention, there is provided a developer for developing an electrostatic image containing a toner and titanium oxide, wherein the titanium oxide comprises
Average particle size of 0.01 to 0.2 μm and 20 to 98%
Has a degree of hydrophobicity of less, it is hardly affected by environmental fluctuations such as temperature and humidity, and a developer having stable triboelectricity under each environment can be obtained. An initial good image is obtained even afterward, and further, a toner used in combination with the titanium oxide includes: (i) at least a polymerizable monomer, a colorant, and styrene-
A toner directly obtained by a suspension-in-solution method using a polymerizable monomer composition containing a butadiene resin, wherein the copolymerization ratio of the styrene-butadiene resin (styrene: butadiene) is from 95: 5 to Since the ratio is 65:35, the coloring power and the granulating property during the production of the toner are improved; A styrene-butadiene resin having a copolymerization ratio (styrene: butadiene) of from 95: 5 to 65: 3.
5, it is excellent in fluidity, chargeability, coloring power, and granulation during toner production; or (iii) a vinyl resin containing at least a polymerizable monomer, a colorant, and an acid component; Since the toner is directly obtained by a suspension polymerization method using a polymerizable monomer composition containing a polyester resin, it has good fixability, fluidity, granulation properties, and chargeability.

Furthermore, the present invention provides a method for forming a latent image using an electrophotographic photosensitive member having at least a conductive support and a photosensitive layer having a laminated structure of a charge generation layer and a charge transport layer. In an image forming method for developing a latent image by using a developer and transferring and forming the latent image on a transfer material, the developer for electrostatic image development is used as the developer, and the surface layer of the electrophotographic photoreceptor further includes: A substance having a fluorine atom and / or a silicon atom is present, and the ratio between the fluorine atom and the carbon atom by XPS measurement is as follows: fluorine atom / carbon atom (F / C) = 0.01 to 1 By using an electrophotographic photoreceptor satisfying 0.000 silicon atom / carbon atom (Si / C) = 0.03 to 1.00 in combination with the developer, excellent transferability and cleaning property can be obtained.
An excellent image can be obtained satisfactorily without the occurrence of cleaning failure even after running many sheets.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of an apparatus for measuring a triboelectric charge amount of a toner.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 11 Suction machine 12 Measurement container 13 Screen 14 Lid 15 Vacuum gauge 16 Air volume control valve 17 Suction port 18 Condenser 19 Electrometer

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI G03G 9/08 325 384 13/08 (72) Inventor Kasugani Rare 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) References JP-A-2-91661 (JP, A) JP-A-2-139575 (JP, A) JP-A-3-80260 (JP, A) JP-A-5-303236 (JP, A) JP-A-5-107811 (JP, A) JP-A-7-77824 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 9/087

Claims (46)

(57) [Claims] 1. A toner directly obtained by a suspension polymerization method using a polymerizable monomer composition containing at least a polymerizable monomer, a colorant and a styrene-butadiene resin. A developer for electrostatic image development containing a toner having a butadiene resin copolymerization ratio (styrene-butadiene) of 95: 5 to 65:35, wherein the developer has an average of 0.01 to 0.2 μm; Particle size and 20-9
A developer for developing an electrostatic charge image, comprising titanium oxide having a hydrophobicity of 8%. 2. The developer according to claim 1, wherein the content of said styrene-butadiene resin is 0.1 to 10 parts by weight based on 100 parts by weight of the toner. . 3. The developer according to claim 1, wherein the styrene-butadiene resin is a block copolymer. 4. The developer according to claim 1, wherein said titanium oxide is surface-treated by hydrolysis of a coupling agent. 5. The developer according to claim 1, wherein the titanium oxide has a light transmittance at 400 nm of 40% or more. 6. A toner directly obtained by a suspension polymerization method using a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, a polyester resin and a styrene-butadiene resin. The copolymerization ratio of the styrene-butadiene resin (styrene: butadiene) is 95: 5 to 6
A developer for developing an electrostatic image containing a toner of 5:35, comprising titanium oxide having an average particle size of 0.01 to 0.2 μm and a hydrophobicity of 20 to 98%. A developer for developing an electrostatic image. 7. The electrostatic charge according to claim 6, wherein the sum of the contents of the styrene-butadiene resin and the polyester resin is 0.1 to 10 parts by weight based on 100 parts by weight of the toner. Developer for image development. 8. The polyester resin has a content of 30 mg KOH.
An acid value of not more than / g.
The developer for developing an electrostatic image according to the above. 9. The developer for developing an electrostatic image according to claim 6, wherein the polyester resin is modified with a vinyl monomer. 10. The developer for developing an electrostatic charge image according to claim 6, wherein the styrene-butadiene resin is a block copolymer. 11. The developer for developing an electrostatic charge image according to claim 6, wherein said titanium oxide is surface-treated by hydrolysis of a coupling agent. 12. The developer according to claim 6, wherein the titanium oxide has a light transmittance at 400 nm of 40% or more. 13. A polymer obtained directly by a suspension polymerization method using a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, a vinyl resin having an acid component and a polyester resin. A developer for developing an electrostatic image containing toner, characterized in that the developer contains titanium oxide having an average particle size of 0.01 to 0.2 μm and a hydrophobicity of 20 to 98%. Developer for developing electrostatic images. 14. The vinyl resin containing the acid component and the polyester resin satisfy the following conditions: 0.1 ≦ a + b ≦ 10 900 ≧ A × a> B × b (where a is the amount of the vinyl resin to be added) , B indicates the amount of polyester resin added, A indicates the acid value of the vinyl resin (mg KOH / g), and B indicates the acid value of the polyester resin (mg KOH / g). 14. The developer for developing an electrostatic image according to claim 13, wherein 15. The developer for developing an electrostatic image according to claim 13, wherein the polyester resin has an acid value of 30 or less. 16. The developer according to claim 13, wherein the vinyl resin has an acid value of 5 to 100. 17. The developer according to claim 13, wherein the polyester resin is modified with a vinyl monomer. 18. The developer according to claim 13, wherein the titanium oxide is surface-treated by hydrolysis of a coupling agent. 19. The developer according to claim 13, wherein the titanium oxide has a light transmittance at 400 nm of 40% or more. 20. A latent image is formed by using an electrophotographic photosensitive member having at least a conductive support, and a photosensitive layer having a laminated structure of a charge generation layer and a charge transport layer, wherein the latent image is formed. Image forming method using a developer to transfer and form a transfer material on a transfer material, wherein the surface layer of the electrophotographic photoreceptor contains a substance having a fluorine atom and / or a silicon atom, and is measured by XPS. The ratio of the fluorine atom and the silicon atom to the carbon atom is as follows: fluorine atom / carbon atom (F / C) = 0.01 to 1.00 silicon atom / carbon atom (Si / C) = 0.03 to 1 .00, and the developer was directly obtained by a suspension polymerization method using a polymerizable monomer composition containing at least a polymerizable monomer, a colorant and a styrene-butadiene resin. A styrene-butadiene resin; It contains a toner having a copolymerization ratio (styrene: butadiene) of 95: 5 to 65:35 and titanium oxide having an average particle size of 0.01 to 0.2 μm and a hydrophobicity of 20 to 98%. Image forming method. 21. The image forming method according to claim 20, wherein the content of the styrene-butadiene resin is 0.1 to 10 parts by weight based on 100 parts by weight of the toner. 22. The image forming method according to claim 20, wherein said styrene-butadiene resin is a block copolymer. 23. The image forming method according to claim 20, wherein said titanium oxide is surface-treated by hydrolysis of a coupling agent. 24. The image forming method according to claim 20, wherein the titanium oxide has a light transmittance at 400 nm of 40% or more. 25. The image forming method according to claim 20, wherein the surface layer of the electrophotographic photosensitive member contains polycarbonate. 26. The image forming method according to claim 20, wherein the surface layer of the electrophotographic photosensitive member contains a polycarbonate synthesized using an asymmetric diol. 27. The image forming method according to claim 20, wherein the electrophotographic photoreceptor has a protective layer on the photosensitive layer, and the protective layer contains polycarbonate. 28. A latent image is formed by using an electrophotographic photosensitive member having at least a conductive support and a photosensitive layer having a laminated structure of a charge generation layer and a charge transport layer. Image forming method using a developer to transfer and form a transfer material on a transfer material, wherein the surface layer of the electrophotographic photoreceptor contains a substance having a fluorine atom and / or a silicon atom, and is measured by XPS. The ratio of the fluorine atom and the silicon atom to the carbon atom is as follows: fluorine atom / carbon atom (F / C) = 0.01 to 1.00 silicon atom / carbon atom (Si / C) = 0.03 to 1 Is satisfied by a suspension polymerization method using a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, a polyester resin and a styrene-butadiene resin. The resulting toner, - copolymerization ratio of butadiene resins (styrene: butadiene) is 95: 5 to 6
An image forming method comprising: a toner having a ratio of 5:35 and a titanium oxide having an average particle diameter of 0.01 to 0.2 μm and a hydrophobicity of 20 to 98%. 29. The polyester resin comprises 30 mg KO
29. The image forming method according to claim 28, having an acid value of H / g or less. 30. The image forming method according to claim 28, wherein the polyester resin in the toner is modified with a vinyl monomer. 31. The image forming method according to claim 28, wherein the styrene-butadiene resin is a block copolymer. 32. The image forming method according to claim 28, wherein said titanium oxide is surface-treated by hydrolysis of a coupling agent. 33. The image forming method according to claim 28, wherein said titanium oxide has a light transmittance of 40% or more at 400 nm. 34. The image forming method according to claim 28, wherein the surface layer of the electrophotographic photosensitive member contains polycarbonate. 35. The image forming method according to claim 28, wherein the surface layer of the electrophotographic photosensitive member contains a polycarbonate synthesized using an asymmetric diol. 36. The image forming method according to claim 28, wherein the electrophotographic photoreceptor has a protective layer on the photosensitive layer, and the protective layer contains polycarbonate. 37. A latent image is formed by using an electrophotographic photosensitive member having at least a conductive support and a photosensitive layer having a laminated structure of a charge generation layer and a charge transport layer, and the latent image is formed. Image forming method using a developer to transfer and form a transfer material on a transfer material, wherein the surface layer of the electrophotographic photoreceptor contains a substance having a fluorine atom and / or a silicon atom, and is measured by XPS. The ratio of the fluorine atom and the silicon atom to the carbon atom is as follows: fluorine atom / carbon atom (F / C) = 0.01 to 1.00 silicon atom / carbon atom (Si / C) = 0.03 to 1 The developer is obtained by a suspension polymerization method using a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, a vinyl resin having an acid component, and a polyester resin. Toner obtained directly and 0.01 ton Image forming method characterized by containing titanium oxide having an average particle diameter and 20 to 98% of the hydrophobicity of the 0.2 [mu] m. 38. The vinyl resin containing the acid component and the polyester resin satisfy the following conditions: 0.1 ≦ a + b ≦ 10 900 ≧ A × a> B × b (where a represents the amount of the vinyl resin to be added) , B indicates the amount of polyester resin added, A indicates the acid value of the vinyl resin (mg KOH / g), and B indicates the acid value of the polyester resin (mg KOH / g). The image forming method according to claim 37, wherein 39. The image forming method according to claim 37, wherein the polyester resin has an acid value of 30 or less. 40. The image forming method according to claim 37, wherein the vinyl resin has an acid value of 5 to 100. 41. The image forming method according to claim 37, wherein said polyester resin is modified with a vinyl monomer. 42. The image forming method according to claim 37, wherein said titanium oxide has been surface-treated by hydrolysis of a coupling agent. 43. The image forming method according to claim 37, wherein said titanium oxide has a light transmittance of 40% or more at 400 nm. 44. The image forming method according to claim 37, wherein the surface layer of the electrophotographic photosensitive member contains polycarbonate. 45. The image forming method according to claim 37, wherein the surface layer of the electrophotographic photosensitive member contains a polycarbonate synthesized using an asymmetric diol. 46. The image forming method according to claim 37, wherein the electrophotographic photoreceptor has a protective layer on the photosensitive layer, and the protective layer contains polycarbonate.