JP3273276B2 - Image forming method and image forming developer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a latent image formed after a charging step in which a charging member is brought into contact with an electrophotographic photosensitive member and a voltage is externally applied to perform charging. The present invention relates to an image forming method in which an image is visualized using a developer and transferred and formed on a transfer material.

[0002]

2. Description of the Related Art Electrophotographic photoreceptors have various constitutions in order to obtain required characteristics or according to the type of electrophotographic process to be applied. As a typical example of an electrophotographic photoreceptor, a photoreceptor having a photoconductive layer formed as an image holding layer on a support and a photoreceptor having a laminated photoconductive layer and an insulating layer thereon as the image holding layer 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.

[0003] For 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 (furthermore, for the purpose of eliminating pollution). A representative 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.
No. 0,048, JP-B-41-16429, JP-B-38-15446, JP-B-46-3713, JP-B-42-23910, and JP-B-43-2
No. 4748, JP-B-42-19747, JP-B-36-4121, and the like.

The electrophotographic photoreceptor 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 low resistance, and in particular, the electrostatic charge retention force in high humidity is reduced, and the sharpness of an image is often impaired. Also,
Deposits such as paper dust often lower the charge holding ability of the photoreceptor and cause image deletion.

Further, since the surface of the photoreceptor 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 in which many white dots appear on the entire black image (hereinafter, abbreviated as solid black) easily occurs.

Second, when a photoreceptor is manufactured, 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 manufactured or mounting it on an electrophotographic apparatus, for example, when a human hand touches or comes into contact with various oils used in the apparatus, a crack occurs on the photoreceptor, resulting in a defective image. Appear.

Third, since the surface has a large coefficient of friction, when it is cleaned with urethane rubber or the like, the amount of shaving increases, and it is difficult to increase the number of durable sheets.

On the other hand, as a toner used in electrophotography, generally, a coloring agent composed of a dye or pigment is melt-mixed in a thermoplastic resin and uniformly dispersed, and then a desired particle size is obtained by a pulverizer or a classifier. Toner by pulverization method for producing toner having
No. 0799 and No. 51-14895 have proposed a method for producing a toner by a suspension polymerization method. In the suspension polymerization method, a polymerizable monomer, a colorant, a polymerization initiator and, if necessary, a crosslinking agent, a charge control agent, and other additives are uniformly dissolved or dispersed to form a monomer composition. ,
A method of dispersing this monomer composition in a continuous phase containing a dispersion stabilizer, for example, an aqueous phase using a suitable stirrer and simultaneously performing a polymerization reaction to obtain toner particles having a desired particle size. Are known.

According to this method, since no pulverizing step is included, the toner does not need to be brittle, and a soft material can be used. Further, the colorant is not exposed on the surface of the particles and the like. 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.

A corona discharger has been conventionally known as a charging means in an electrophotographic apparatus or the like. However, corona dischargers have problems such as the need to apply a high voltage and the generation of a large amount of ozone.

Therefore, recently, the use of contact charging means without using a corona discharger has been studied. More specifically, a voltage is applied to a conductive roller serving as a charging member, and the roller is brought into contact with a photosensitive member serving as a charged member to charge the surface of the photosensitive member to a predetermined potential. If such a contact charging means is used, the voltage can be reduced as compared with a corona discharger, and the amount of generated ozone can be reduced.

However, when the above-mentioned contact charging means is used, if it is not possible to maintain sufficient contact with the member to be charged,
There is a problem that charging failure occurs.

In Japanese Patent Application Laid-Open No. 3-59572, in order to solve this problem, the toner used is made spherical, so that the charging member and the surface of the photoreceptor are prevented from being damaged, scraped, and fixed by the developer. As a result, it has been proposed that the contact between the charging member and the photoconductor can be sufficiently maintained.

In recent years, electrophotography has been further improved in image quality,
High durability is desired. In response to this requirement, the shape of the toner has more irregularities on the toner surface than a true spherical shape,
It has been found that those having a flat shape are preferable. That is, when the toner has a true spherical shape, an external additive such as a fluidity imparting agent for the toner is easily buried in the toner surface, and as a result, transferability is deteriorated and image quality is deteriorated.

However, such deformed toner tends to easily cause scratches, abrasion, and sticking to the surface of the photoreceptor, as described above.

[0017]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an image forming method which solves the problems of the prior art as described above.

That is, an object of the present invention is to provide a high-quality image forming process comprising a photosensitive member and a toner, which is excellent in fixability and transferability and which has a high durability and prevents toner sticking, scraping and scratching on the photosensitive member. It is to provide a forming method.

[0019]

The above objects are achieved by the present invention described below.

That is, a charging roller having a surface layer formed of a release coating is applied to an electrophotographic photosensitive member by a contact pressure of 5 to 50.
0 g / cm, and after applying a voltage to the charging roller from the outside to charge the charging roller, a latent image is formed, and the latent image is visualized using a developer to form a latent image on a transfer material. In the image forming method for transfer formation, a) an organic compound and a substance having fluorine and / or silicon atoms are present in a surface layer of the electrophotographic photoreceptor, and a fluorine atom or silicon atom and carbon A) using a photoreceptor whose atomic ratio satisfies the following relationship: F / C = 0.03 to 1.00, Si / C = 0.03 to 1.00, and b) the toner in the developer is a polymerizable monomer. Suspension polymerization of a polymerizable monomer composition containing 100 parts by mass, 10 to 40 parts by mass of a polyalkylene as a release agent, a colorant, and a polar polymer or a polar copolymer in an aqueous medium Particles obtained directly by The polar polymer or the polar copolymer is a polymer of a nitrogen-containing monomer or a styrene and an unsaturated carboxylic acid ester. A nitrile monomer; a halogen-containing monomer;
A polymer of a monomer selected from the group consisting of unsaturated carboxylic acids, unsaturated dibasic acids, unsaturated dibasic anhydrides and nitro monomers, or This is achieved by at least one selected from the group consisting of a copolymer; a polyester; and an epoxy resin.

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems of the prior art, and as a result, have found that while using the above-mentioned contact charging means, sufficient charging between the charging member and the photoreceptor, which is required, is maintained. Scratches and scrapes on the member and photoreceptor surface due to developer,
Deterioration of the external additive due to durability, which is a problem of the spherical toner that can prevent sticking, is suppressed by deforming the toner shape, thereby preventing image quality deterioration.

The toner used in the present invention has a shape factor SF
Is preferably from 105 to 120. When the SF is smaller than 105, deterioration of the external additive is liable to occur.
If it is larger than the above, the surface of the photoconductor and the charging member are easily undesirably scratched and scraped.

The amount of the polyalkylene contained is preferably from 10 to 40 parts by mass based on 100 parts by mass of the polymerizable monomer. When the amount is less than 10 parts by mass, sufficient fixability cannot be obtained, and when the amount is more than 40 parts by mass, the toner tends to adhere to the surface of the photoconductor and the charging member.

Further, in the present invention, it is more preferable to add a polymer / copolymer having a polar group as an additive to the monomer system for polymerization. The polar polymer / copolymer is
Since the toner particles gather at the surface layer of the toner, they form a kind of shell, which gives the toner particles excellent properties such as anti-blocking properties, and has a relatively low molecular weight inside the toner and contributes to the improvement of fixing properties. By performing such polymerization, it is possible to obtain a toner that satisfies the conflicting requirements of fixability and blocking resistance, and to obtain an effect of preventing toner from sticking to the surface of the photoconductor and the charging member. 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 acid esters, etc .; nitrile monomers such as acrylonitrile; Halogen-containing monomers, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, and other unsaturated dibasic acids
Unsaturated dibasic acid anhydrides, polymers such as nitro monomers or copolymers with styrene monomers, polyesters,
Epoxy resins and the like can be mentioned.

The amount of the polar polymer / copolymer added is preferably 0.1 to 10% by mass.

Further, the ratio of an organic compound to a fluorine atom or a silicon atom to a carbon atom in the surface layer of the electrophotographic photosensitive member is F / C 0.03 to 1.00, Si / C 0.03 to 1.00. It has been found that the above-mentioned problems can be solved by making the above-mentioned range exist.

Here, the reason for defining F / C and Si / C is that when the surface of the photoreceptor is combined with the above-mentioned present invention, the object of the present invention is more achieved. That is, F and Si lower the photoreceptor surface energy and lower the transferability and adhesion. On the other hand, the presence of carbon atoms increases its surface energy. The present inventors have found that by defining this ratio, a configuration can be obtained in which the transferability is good and the image quality does not deteriorate and the cleaning failure does not occur.

Here, if the F / C and Si / C of the photoconductor surface layer are less than 0.03 for the toner of the present invention, respectively, the photoconductor surface energy is high and the transferability of the toner is deteriorated. On the other hand, F / C and Si / C are each 1.00.
When the value exceeds, the coefficient of friction with the cleaning member decreases, and conversely, the toner slips through, resulting in poor cleaning.

Still more preferably, the surface layer in the electrophotographic photoreceptor of the present invention contains a polycarbonate, and even more preferably, the polycarbonate is synthesized from an asymmetric diol. . This can provide an electrophotographic photoreceptor having excellent durability characteristics and good productivity. More preferably, the electrophotographic photoreceptor has a protective layer on the photosensitive layer, and the protective layer preferably contains polycarbonate. This results in further stability of the durability characteristics.

A more preferable structure for achieving the object of the present invention is that the ratio of fluorine atoms or silicon atoms to oxygen atoms in the surface layer of the electrophotographic photosensitive member of the present invention is F / O 0.03 in XPS measurement. More preferably, it is Si / O 0.03 or more. By defining the amount of oxygen with respect to F and Si as described above, it is possible to more preferably control the adhesion to the toner containing the resin having a polar component of the present invention.

Hereinafter, the contact charging step applicable to the image forming method of the present invention will be specifically described.

FIG. 1 is a contact band showing an embodiment of the present invention.
It is a schematic structure figure of an electric equipment. 1 is a photoreceptor which is a member to be charged
A drum, an outer periphery of an aluminum drum base 1a
Organic photoconductor (OPC) 1b as photoreceptor layer is formed on the surface
It rotates at a predetermined speed in the direction of the arrow. Real truth
In the embodiment, the photosensitive drum 1 has an outer diameter of 30 mmφ.
You. 2 contacts the photosensitive drum 1 with a predetermined pressure.
A charging roller as a charged charging member, and a metal core 2a
Provided with a conductive rubber layer 2b, and a releasable coating on the peripheral surface thereof.
Is provided on the surface layer 2c. The surface layer in the present embodiment is separated.
It is a moldable film, and providing a release film is related to the present invention.
From the viewpoint of matching with the image forming method. However, release
When the resistance is too high, the photosensitive drum 1 is charged.
If the resistance is too small, a large voltage is applied to the photosensitive drum 1.
Overload, drum damage and pinholes
Therefore, a moderate resistance, that is, a volume resistivity of 10⁹-10¹⁴ Ωm
In this case, the thickness of the release coating should be within 3.0 μm.
preferable. In addition, the lower limit of the film thickness is
If it does not exist, it is considered to be about 5 μm.

In this embodiment, the outer diameter of the charging roller 2 is 12
mmφ, the conductive rubber layer 2b is EPDM, the surface layer 2
A nylon resin having a thickness of 10 μm was used for c. The hardness of the charging roller 2 was 54.5 ° (ASKER-C). E denotes a power supply unit that applies a voltage to the charging roller 2, and supplies a predetermined voltage to the metal core 2 a of the charging roller 2. It is preferable that the applied voltage is obtained by superimposing an AC voltage on a DC voltage.

[0035]

[0036]

[0037]

In this embodiment, the charging member is composed of the conductive rubber layer and the release coating, but the invention is not limited to this. For preventing leakage to the photoconductor between the conductive rubber layer and the surface of the release coating. For this purpose, it is preferable to form a high-resistance layer, for example, a hydrin rubber layer with small environmental fluctuation.

Further, instead of nylon resin, PVDF (polyvinylidene fluoride), PVDC
(Polyvinylidene chloride) may be used. As the photoconductor, amorphous silicon, selenium, ZnO or the like can be used. In particular, when amorphous silicon is used for the photoconductor, compared to the case where other materials are used, even if the softening agent of the conductive rubber layer adheres to the photoconductor even to a small extent, the image flow becomes severe, so The effect of the insulating coating is great.

The mechanical or electric pressure applied between the charging member and the photosensitive member is an element according to the gist of the present invention, and the contact pressure of the charging member with the photosensitive member is 5 to 500 g.
/ Cm, the DC voltage applied to the charging member has an absolute value of 20
When an AC voltage is applied to 0 to 900 V, the peak-peak voltage is 500 to 5,000 V, and the frequency is 50 to 3,000.
It is desirable that each be adjusted to 0 Hz.

For example, it is preferable that the applied voltage has a peak-to-peak voltage value that is at least twice the charging start voltage value for the photosensitive member.

The present invention is particularly effective for an image forming apparatus in which the surface of a latent image carrier is an organic compound. When the organic compound forms the surface layer, it has good adhesion to the binder resin contained in the toner.Particularly, when using the same material, a chemical bond occurs at the contact point, and the transfer property is low. Is to be reduced.

The surface material of the latent image carrier used in the present invention includes, but is not limited to, silicone resin, vinylidene chloride, ethylene-vinyl chloride, styrene-acrylonitrile, styrene-methyl methacrylate, styrene, polyethylene terephthalate, polycarbonate and the like. However, other monomers or copolymerization or blending between the exemplified resins can be used.

The present invention is particularly effective for an image forming apparatus in which the diameter of the latent image carrier is 50 mm or less. This is because, in the case of a small-diameter drum, even if the line pressure is the same, the curvature is large, so that the pressure tends to concentrate at the contact portion.

It is considered that the same phenomenon occurs in the belt photoreceptor, and the present invention is also effective for an image forming apparatus having a radius of curvature of 25 mm or less at the transfer portion.

Next, the configuration of the electrophotographic photosensitive member used in the present invention will be described.

The photoreceptor of the present invention has 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, the charge transport layer and / or the protective layer serving as the photoreceptor surface layer contain a fluorine compound and / or
Alternatively, it is characterized by containing a silicon compound. Furthermore, 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. Furthermore, 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.

Specific examples of the fluorine compound include known fluorine resins, and include ethylene tetrafluoride, ethylene trifluoride ethylene, tetrafluoroethylene, propylene hexafluoride, and the like.
One or more kinds are appropriately selected from vinyl fluoride, vinylidene fluoride, ethylene difluoride and copolymers thereof. Also, carbon fluoride and the like can be used.

In the present invention, a block or graft polymer containing a fluorine-containing segment synthesized from polymerization and copolymerization with a fluorine-based polymerizable monomer or a non-fluorine-based polymerizable monomer, a surfactant, A monomer or 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 dispersion of the fluorine-based resin and easy control of the surface F / C ratio which is a feature of the present invention.

The preferred specific examples of the above-mentioned fluorine-based polymerizable monomer are shown below, but the range of compounds that can be used is not limited to the above-mentioned ranges.

[0054]

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(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. Is an integer of 1 to 4, m is an integer of 1 to 5, k + m = 5, and Rf
Represents an alkyl group substituted by at least one fluorine atom. Examples of the non-fluorinated polymerizable monomer include low-molecular-weight linear unsaturated hydrocarbons, vinyl halides, vinyl esters of organic acids, vinyl aromatic compounds, acrylic acid and methacrylic acid esters, N-vinyl compounds, One or more kinds of vinylsilicon compounds, maleic anhydride, esters of maleic acid and fumaric acid can be used, and the charge transport layer to which the formed fluorine-based graft polymer is added and / or It is preferable to select a material compatible with the resin layer of the protective layer, or a material having a similar structure even if not completely compatible with each other and having a little affinity between the two.

Specific examples of the silicon compound include a 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 3,000 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 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, it can be obtained by a general polycarbonate synthesis method such as 1) bisphenol A and one or two or more asymmetric diol compounds, 2) a phosgene method using one or two or more asymmetric diol compounds. it can. Further, it can also be obtained by using a diol compound having a substituent having 3 or more carbon atoms in a side chain.

Representative specific examples of the asymmetric diol compound used in the present invention are shown below.

[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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The proportion of the asymmetric diol compound in the above-mentioned copolymerized polycarbonate with bisphenol A is preferably at least 20% by weight, particularly preferably at least 50% by weight in the diol compound. 20% by weight of the asymmetric diol compound
If less than, the solubility in an aromatic hydrocarbon solvent or a halogenated aromatic hydrocarbon solvent becomes insufficient,
The stability over time of the coating liquid also deteriorates. The solubility of the polycarbonate soluble in the above-mentioned aromatic hydrocarbon solvent or halogenated aromatic hydrocarbon solvent (solution 10 at a temperature of 25 ° C.)
(G number of polycarbonate in 0 g) is 1 g or more, especially 5 g.
g or more is preferable. When the solubility is less than 1 g, for example, when a coating solution for a charge transport layer is prepared, the viscosity of the coating solution is too low to obtain an appropriate film thickness required for the charge transport layer.

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 manufacturing the electrophotographic photosensitive member of the present invention,
As the conductive substrate, a cylindrical cylinder or a film of metal such as aluminum or stainless steel, paper, plastic, or the like is used. 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 properties, 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. Known materials for the undercoat layer include polyvinyl alcohol, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, ethylene-acrylic acid copolymer, casein, polyamide, copolymerized nylon, glue, gelatin, and the like. 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 are used as charge generating substances. , Indigo pigment,
Quinacridone pigments, asymmetric quinocyanines, quinocyanines or amorphous silicon described in JP-A No. 54-143645 can be used. As the charge transporting substance, pyrene, N-ethylcarbazole, N-
Isopropylcarbazole, N-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-
Hydrazones such as N, N-diphenylhydrazone, 1,3,3-tramethylindolenine-ω-aldehyde-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) pyrazolin, 1 [pyridyl (2)]-3- (P-dieltiaminostyryl) -5-
(P-diethylaminophenyl) pyrazolin, 1- [6
-Methoxy-pyridyl (2)]-3- (P-diethylaminostyryl) -5- (P-diethylaminophenyl)
Pyrazoline, 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) pyrazolin, 1-phenyl-3- (P-diethylaminostyryl) -4-methyl-5- ( Pyrazolines such as P-diethylaminophenyl) pyrazolin, 1-phenyl-3- (α-benzyl-P-diethylaminostyryl) -5- (P-diethylaminophenyl) pyrazolin, and spiropyrazolin; 2- (P-diethylaminostyryl) -6; -Diethylaminobenzoxazole, 2-
Oxazole compounds such as (P-diethylaminophenyl) -4- (P-dimethylaminophenyl) -5- (2-chlorophenyl) oxazole and thiazole compounds such as 2- (P-diethylaminostyryl) -6-diethylaminobenzothiazole , Triarylmethane compounds such as bis (4-diethylamino-2-methylphenyl) -phenylmethane, 1,1-bis (4-N, N-diethylamino-2-methylphenyl) heptane, 1,1,
2,2-tetrakis- (4-N, N-dimethylamino-
Polyarylalkanes such as 2-methylphenyl) ethane and the like can be used.

The charge generation layer contains the above-described charge generation pigment in 0.1%.
It is well dispersed with a binder resin and a solvent in an amount of 3 to 4 times by a method such as a homogenizer, an ultrasonic wave, a ball mill, a vibrating ball mill, a sand mill, an attritor, and a roll mill, and is formed by coating and drying. Its thickness is 0.1 ~
It is about 1 μm.

When the above-described 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 the solvent, toluene,
Xylene or monochlorobenzene is 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-based solvent or halogenated aromatic hydrocarbon-based solvent. It is obtained by applying a coating solution prepared by dissolution. The mixing ratio of the charge transport material and the above-mentioned polycarbonate resin used as a binder was 2: 1 to 1: 2 by weight.
It is about. As the solvent, toluene, xylene or monochlorobenzene is particularly useful.

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 coating and forming the charge transport layer, 10 ° C to 200 ° C (preferably 20 ° C to 150 ° C)
Air drying or still drying for 5 minutes to 5 hours (preferably 10 minutes to 2 hours) at a temperature of 5 to 20 μm
Is obtained.

On the other hand, the polymerizable monomer which can be used in the polymerized toner of the present invention includes styrene / o-methylstyrene / styrene.
Styrene-based monomers such as m-methylstyrene / p-methylstyrene / p-methoxystyrene / p-ethylstyrene; methyl acrylate / ethyl acrylate / n-butyl acrylate / isobutyl acrylate / n-propyl acrylate -N-octyl acrylate-dodecyl acrylate-2-ethylhexyl acrylate-stearyl acrylate-2-chloroethyl acrylate-acrylates such as phenyl acrylate, methyl methacrylate-ethyl methacrylate-n-propyl methacrylate N-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate
Examples include methacrylic acid esters such as diethylaminoethyl methacrylate and other monomers such as acrylonitrile, methacrylonitrile and acrylamide. 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 a mixture with another monomer, from the viewpoint of the developing characteristics and durability of 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, etc., 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 red calcium salt,
Brilliant Carmine 3B, Fast Violet B,
Pigments such as methyl violet lake, navy blue, cobalt blue, alkali blue lake, Victoria blue lake, quinacridone, rhodamine lake, phthalocyanine blue, fast sky blue, pigment green B, malachite green lake, final yellow green G and the like. In the present invention, in order to obtain the 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, aluminum coupling without polymerization inhibition It is better to perform hydrophobic treatment with an agent, a silane coupling agent, a titanium coupling agent, or the like. 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. In addition, the carbon black may be treated with a substance that reacts with the surface functional group of the carbon black, for example, a polyorganosiloxane, in addition to the same treatment as the above 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 properties and aqueous phase migration properties 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 at the time of hot roll fixing, 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, in addition to oxides and grafted products, higher fatty acids, metal salts thereof, amide waxes, and natural or synthetic ester waxes may be mentioned. These waxes have a softening point of 4 according to the ring and ball method (JIS K 2531).
When the softening point is less than 40 ° C, the blocking resistance and the shape retention of the toner are insufficient. Will be insufficient.

These release agents may be used alone or in combination. The addition amount is preferably 0.1 to 50% by mass.

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 mass% is preferable.

As the polymerization initiator, any suitable polymerization initiator, for example, 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,
Peroxide-based polymerization initiators such as diisopropyl peroxycarbonate, 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 mass of the polymerizable monomer, and may be used alone or in combination.

In the present invention, known crosslinking agents and chain transfer agents may be added in order to control the molecular weight. The preferable addition amount is 0.001 to 15% by mass.
It is.

The additive for imparting various toner properties 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 this additive
The average particle diameter obtained by observing the surface of the toner particles with an electron microscope is meant. As additives for imparting these properties, for example, the following are used.

1) Fluidity imparting agents: metal oxides (silicon oxide, aluminum oxide, etc.), carbon black, carbon fluoride, etc. Those subjected to a hydrophobic treatment are more preferable. 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) , Calcium carbonate) and the like.

3) Lubricants: fluorinated resin powder (vinylidene fluoride, polytetrafluoroethylene, etc.), fatty acid metal salts (zinc stearate, calcium stearate, etc.).

4) Charge controllable particles: metal oxides (such as tin oxide, titanium oxide, zinc oxide, silicon oxide, and aluminum oxide) and carbon black.

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.

In the present invention, any suitable stabilizer is used as the dispersion medium used in the polymerization method. 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 And bentonite / silica / alumina. As organic compounds, polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose,
The sodium salt of carboxymethylcellulose, polyacrylic acid and salts thereof, starch and the like can be used by dispersing them in an aqueous phase. It is preferable to use 0.2 to 20 parts by mass of these stabilizers based on 100 parts by mass of the polymerizable monomer.

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

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

The polymerized toner used in the present invention is obtained by the following method. That is, the release agent in the polymerizable monomer
Add a colorant, charge control agent, polymerization initiator, and other additives, and uniformly dissolve or disperse the monomer system using a homogenizer, ultrasonic disperser, etc., in a water phase containing a dispersion stabilizer by ordinary stirring. Disperse using a homogenizer or 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. Thereafter, by the action of the dispersion stabilizer, the particles may be stirred to such an extent that the particle state is maintained and the particles are prevented from settling. The polymerization is performed at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. Further, the temperature may be raised in the latter half of the polymerization reaction, and further, in order to remove unreacted polymerizable monomers and by-products which cause odor at the time of fixing the toner, the second half of the reaction, or the end of the 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 usually preferable to use 300 to 3000 parts by mass of water as a dispersion medium with respect to 100 parts by mass of the monomer system.

Further, it is necessary that the toner of the present invention has been subjected to a deforming treatment, and any method may be used as a treatment method as long as it is generally known. Some processing examples are given below. Mechanochemical method: After mixing the toner particles and the resin fine particles, the resin fine particles are fused to the surface of the toner particles by the mechanochemical method. Dry heat treatment method: After mixing toner particles and resin fine particles,
Mixing and heating are performed in the fluidized heating layer to fuse the resin fine particles to the surface of the toner particles. Wet heat treatment method: After mixing toner particles and resin fine particles in a liquid or gas, heat treatment is performed in the liquid to fuse the resin fine particles to the surface of the toner particles. Method of adding resin fine particles during polymerization: When toner particles are obtained by a polymerization method, the resin fine particles are added to a monomer in advance, or the resin fine particles are added during the polymerization to control the physical properties of the resin fine particles and the dispersion medium. By doing so, the resin fine particles are transferred to the surface of the toner particles, and the polymerization is completed. Drying method after swelling: After the toner particles are immersed in a solvent to swell, they are dried in a heated air flow or under reduced pressure. There is also a method of disturbing the stability of suspended particles during suspension polymerization to obtain irregularly shaped particles such as potato-shaped and daruma-shaped. As a method of disturbing the stability of the suspended particles, there are a method of changing the rotation speed of the disperser in the middle and a method of changing the pH value in the polymerization system. A method in which toner particles are deformed by applying mechanical force after the completion of the suspension polymerization reaction.

XP on electrophotographic photosensitive member surface in the present invention
The S 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.

Further, in the present invention, the shape factor S of the toner
F was determined as follows.

The toner was randomly added to the toner by a field emission scanning electron microscope S-800 manufactured by Hitachi, Ltd.
More than one, and an image processing and analysis device Luze manufactured by Nireco
It was determined by the following equation using x3.

[0098]

(Equation 1)

[0099]

The present invention will be described below with reference to examples.
They do not limit the invention in any way. Production examples of the toner and the drum used in the examples and the comparative examples of the present invention are described below.

[Production Example 1 of Polymerized Toner] Ion-exchanged water 7
To 10 g, was charged 0.1M-Na ₃ PO ₄ aqueous solution 450 g, followed by heating to 60 ° C., using a TK-type homomixer (manufactured by Tokushu Kika Kogyo), and stirred at 12000 rpm. 68 g of a 1.0 M CaCl ₂ aqueous solution was gradually added thereto to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .

On the other hand, styrene 165 g n-butyl acrylate 35 g hydrophobized magnetic material 140 g metal di-t-butylsalicylate 1 g styrene-methacrylic acid copolymer 10 g paraffin wax (mp 60 ° C.) 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
0 g was dissolved to prepare a polymerizable monomer composition. The above-mentioned polymerizable monomer composition is charged into the aqueous medium,
Under N ₂ atmosphere, use a TK homomixer for 100
The mixture was stirred at 00 rpm for 20 minutes to granulate the polymerizable monomer composition. Thereafter, the temperature was raised to 80 ° C. while stirring with a paddle stirring blade, and the reaction was performed for 10 hours.

After the completion of the polymerization reaction, the mixture was cooled, hydrochloric acid was added to dissolve calcium phosphate, and then filtered, washed with water and dried to obtain colored suspended particles having a weight average diameter of about 8 μm. The SF of the particles was 102.

With respect to 100 parts by mass of the obtained particles, BE
0.8 parts by mass of hydrophobic silica having a specific surface area of 200 m ² / g by the T method was externally added to obtain a suspension-polymerized toner a.

[0105]

[Production Example 2 of Polymerized Toner] After mixing the colored suspension particles obtained in Production Example 1 with resin fine particles, the resin fine particles are fused to the surface of the colored particles by a mechanochemical technique, and irregularities are formed on the surface. To obtain colored particles. The SF of the particles was 115.

In the same manner as in Production Example 1, the suspension polymerization toner b
I got

[Production Example 3 of Polymerized Toner] The colored suspension particles obtained in Production Example 1 were immersed in a solvent to swell, and then dried under reduced pressure to obtain colored particles having irregularities on the surface. The SF of the particles was 150.

In the same manner as in Production Example 1, the suspension polymerization toner c
I got

[Production Example 4 of Polymerized Toner] Ion-exchanged water 7
450 g of a 0.1 M Na ₃ PO ₄ aqueous solution was added to 10 g, heated to 60 ° C., and then stirred at 12000 rpm using a TK homomixer. 1.0M-
68 g of CaCl ₂ aqueous solution is gradually added, and Ca ₃ (PO
₄ ) An aqueous medium containing ₂ was obtained.

On the other hand, styrene 165 g n-butyl acrylate 35 g phthalocyanine blue 10 g metal di-t-butylsalicylate 2 g styrene-methacrylic acid copolymer 8 g paraffin wax (mp 70 ° C.) 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
0 g was dissolved to prepare a polymerizable monomer composition. Said,
The above polymerizable monomer composition was charged into an aqueous medium,
Under a N ₂ atmosphere at ℃ 1 with a TK homomixer
The mixture was stirred at 0000 rpm for 20 minutes to granulate the polymerizable monomer composition. Then, while stirring with a paddle stirring blade, 80
C., and reacted for 10 hours.

After completion of the polymerization reaction, the mixture was cooled, hydrochloric acid was added to dissolve calcium phosphate, followed by filtration, washing with water and drying to obtain colored suspension particles having a weight average diameter of about 8 μm. Then, colored particles having irregularities on the surface were obtained in the same manner as in Production Example 2. The SF of the particles was 110.

With respect to 100 parts by mass of the obtained particles, BE
0.8 parts by mass of hydrophobic silica having a specific surface area of 200 m ² / g by T method was externally added to obtain a suspension polymerization toner d.

For 5 parts by mass of this toner, 95 parts by mass of an acrylic-coated ferrite carrier were used as a mixed fat and a developer.

[Production Example A of Photoconductor] 10 parts by mass of conductive titanium oxide (tin oxide coating, average primary particle size 0.4 μm), 10 parts by mass of phenol resin precursor (resole type),
After 10 parts by mass of methanol and 10 parts by mass of butanol are dispersed in a sand mill, the outer diameter is 80 mm, and the length is 360 mm.
And then cured at 140 ° C. to provide a conductive layer having a volume resistance of 5 × 10 ⁹ Ωcm and a thickness of 20 μm.

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

[0118]

Embedded image

After mixing and dissolving 150 parts by mass of isopropanol, dip coating was performed on the conductive layer to provide a subbing layer of 1 μm.

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

[0121]

Embedded image

5 parts by mass of the following polycarbonate resin (bisphenol A molecular weight: 30,000)

[0123]

Embedded image

Then, 700 parts by mass of cyclohexanone was dispersed in a sand mill, and this dispersion was applied by dip coating on the undercoat layer to obtain a 0.05 μm charge generation layer.

Next, 10 parts by mass of the following triphenylamine:

[0126]

Embedded image

10 parts by mass of a polycarbonate resin having the following structure (bisphenol Z type, molecular weight 20,000)

[0128]

Embedded image

After stirring and mixing 50 parts by mass of monochlorobenzene and 15 parts by mass of dichloromethane, 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 mass 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: 80
000) 6 parts by mass,

[0131]

Embedded image

The following perfluoroalkyl acrylate:
Methyl methacrylate block copolymer (molecular weight 300
00) 0.1 part by mass

[0133]

Embedded image

120 parts by mass of monochlorobenzene and 80 parts by mass of dichloromethane were dispersed and mixed in a sand mill. 3 parts by mass of the following triphenylamine

[0135]

Embedded image Was added and mixed and dissolved, and the mixture was applied on the charge transport layer by spray coating to form a photoreceptor drum provided with a protective layer of 5 μm.

<F / C Ratio XPS Measurement> After peeling the surface of the photoreceptor, an ESCALAB200-X model manufactured by VG was used.
The surface elements were fixed with an 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 of Production Example A had 5.2% of F atoms and 81.3% of C atoms.
The C ratio was 0.064.

[Production Example B of Photoreceptor] Aluminum cylinder,
The same layers as in Production Example A were prepared up to the conductive layer, the undercoat layer, and the charge generation layer.

Next, 10 parts by mass of the following triphenylamine:

[0139]

Embedded image Polycarbonate resin of the following structure (Bisphenol Z
(Type, molecular weight 20,000) 10 parts by mass

[0140]

Embedded image 50 parts by mass of monochlorobenzene and 15 parts of dichloromethane
After stirring and mixing the mass parts, 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, 3 parts by mass 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: 80
000) 5 parts by mass,

[0142]

Embedded image 0.3 parts by mass of the following perfluoroalkyl acrylate-methyl methacrylate block copolymer (AB type copolymer, molecular weight 30,000)

[0143]

Embedded image Monochlorobenzene 110 parts by mass and dichloromethane 8
0 parts by mass was dispersed and mixed by a sand mill. 2.5 parts by mass of the following triphenylamine

[0144]

Embedded image Was added and mixed and dissolved, and the mixture was applied on the charge transporting layer by spray coating to provide a 6 μm protective layer to obtain a photosensitive drum.

This photoreceptor has 10.2% F atoms and 7 C atoms.
At 6.7%, the F / C was 0.133.

[Production Example C of Photoconductor] Aluminum cylinder,
The same layers as in Production Example A were prepared up to the conductive layer, the undercoat layer, and the charge generation layer.

Next, 3 parts by mass of the following triphenylamine:

[0148]

Embedded image 7 parts by mass of the following triphenylamine,

[0149]

Embedded image Polycarbonate resin of the following structure (Bisphenol Z
(Type, molecular weight 20,000) 10 parts by mass

[0150]

Embedded image 50 parts by mass of monochlorobenzene and 15 parts of dichloromethane
After stirring and mixing the mass parts, 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, 3 parts by mass of carbon fluoride fine powder (average particle size 0.27 μm, manufactured by Central Glass Co., Ltd.) and the following polycarbonate resin (bisphenol Z molecular weight 80
000) 5.5 parts by mass,

[0152]

Embedded image 0.3 parts by mass of the following fluorine-substituted graft polymer (F content: 27% by mass, molecular weight: 25,000)

[0153]

Embedded image 120 parts by mass of monochlorobenzene and dichloromethane 8
0 parts by mass was dispersed and mixed by a sand mill. 2.5 parts by mass of the following triphenylamine

[0154]

Embedded image Was mixed and dissolved, and 120 parts by mass of the charged monochlorobenzene and 80 parts by mass of dichloromethane were dispersed and mixed in a sand mill by spray coating. 2 parts by mass of the following triphenylamine

[0155]

Embedded image Was added and mixed and dissolved, and the mixture was applied on the charge transport layer by spray coating, and a 4 μm protective layer was provided to form a photosensitive drum.

This photosensitive member has 11.3% of F atoms and 7 atoms of C atoms.
At 5.5%, the F / C was 0.150.

[Production Example D of Photoreceptor] The photoreceptor of Production Example D was prepared by applying the photoreceptor of Production Example A up to the charge transport layer without the protective layer.

[Production Example E of Photoconductor] Aluminum cylinder,
The same layers as in Production Example A were prepared up to the conductive layer, the undercoat layer, and the charge generation layer.

Next, 10 parts by mass of the following triphenylamine:

[0160]

Embedded image Polycarbonate resin of the following structure (Bisphenol Z
Type, molecular weight 25000) 10 parts by mass

[0161]

Embedded image 50 parts by mass of monochlorobenzene and 15 parts of dichloromethane
After stirring and mixing the mass parts, 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, 0.3 parts by mass of carbon fluoride fine powder (average particle size 0.27 μm, manufactured by Central Glass Co., Ltd.)
6.4 parts by mass of the following polycarbonate resin (bisphenol Z, molecular weight: 80000)

[0163]

Embedded image The following perfluoroalkyl acrylate-methyl methacrylate block copolymer (molecular weight 30,000) 0.0
3 parts by mass

[0164]

Embedded image 120 parts by mass of monochlorobenzene and dichloromethane 8
0 parts by mass was dispersed and mixed by a sand mill. 3.2 parts by mass of the following triphenylamine

[0165]

Embedded image Was added and mixed and dissolved, and the mixture was applied on the charge transport layer by spray coating, and a 4 μm protective layer was provided to form a photosensitive drum.

This photosensitive member has 0.83% of F atoms and 8 C atoms.
At 5.5%, the F / C was 0.0097.

[Preparation Example F of Photoconductor] A photoconductor drum was prepared by changing the protective layer of the photoconductor of Preparation Example A to the following formulation.

That is, true spherical three-dimensional crosslinked polysiloxane fine particles (average particle size 0.29 μm, manufactured by Toshiba Silicone Co., Ltd.) 1
Parts by mass, the following polycarbonate resin (bisphenol Z
(Molecular weight: 80000) 6 parts by mass,

[0169]

Embedded image

The following polydimethylsiloxane methacrylate-methyl methacrylate block copolymer (molecular weight: 5
0000, Si content 12% by mass) 0.1 part by mass

[0171]

Embedded image

120 parts by mass of monochlorobenzene and 80 parts by mass of dichloromethane were dispersed and mixed in a sand mill. 3 parts by mass of the following triphenylamine

[0173]

Embedded image Was added and mixed and dissolved, and the mixture was applied on the charge transport layer by spray coating to provide a protective layer having a thickness of 3 μm, thereby forming a photosensitive drum.

<Si / C Ratio XPS Measurement> After the photoreceptor surface was peeled off, the surface elements were fixed using an ESCALAB200-X type X-ray photoelectron spectrometer manufactured by VG. X
Using MgCa (300 W) as a radiation source, the measurement was performed at a depth of several Å over a 2 × 3 mm area. The photosensitive member surface of Production Example F had 10.2% of Si atoms and 69.3% of C atoms, and the Si / C ratio was 0.147.

[Production Example G of Photoreceptor] Aluminum cylinder,
The same layers as in Production Example F were prepared up to the conductive layer, the undercoat layer, and the charge generation layer.

Next, 10 parts by mass of the following triphenylamine:

[0177]

Embedded image Polycarbonate resin of the following structure (Bisphenol Z
(Type, molecular weight 20,000) 10 parts by mass

[0178]

Embedded image 50 parts by mass of monochlorobenzene and dichloromethane 1
After stirring and mixing 5 parts by mass, dip coating was performed on the charge generation layer. After drying the coated cylinder with hot air,
Of the charge transport layer.

Next, true spherical three-dimensionally crosslinked polysiloxane fine particles (average particle size 0.29 μm, manufactured by Toshiba Silicone Co., Ltd.) 3
Parts by mass, the following polycarbonate resin (bisphenol Z
Molecular weight of 80000) 4 parts by mass,

[0180]

Embedded image 0.3 parts by mass of the following polydimethylsiloxane methacrylate-styrene block copolymer (molecular weight: 60000, Si content: 14% by mass)

[0181]

Embedded image 2.5 parts by mass of the following triphenylamine

[0182]

Embedded image Was added and mixed and dissolved, and the mixture was applied on the charge transport layer by spray coating to provide a protective layer having a thickness of 3 μm, thereby forming a photosensitive drum.

This photosensitive member had 15.1% of Si atoms and 70.3% of C atoms, and had a Si / C of 0.215.

[Production Example H of Photoconductor] Aluminum cylinder,
The same layers as in Production Example F were prepared up to the conductive layer, the undercoat layer, and the charge generation layer.

Next, 10 parts by mass of the following triphenylamine:

[0186]

Embedded image Polycarbonate resin of the following structure (Bisphenol Z
Type, molecular weight 25000) 10 parts by mass

[0187]

Embedded image 50 parts by mass of monochlorobenzene and dichloromethane 1
After stirring and mixing 5 parts by mass, dip coating was performed on the charge generation layer. After drying the coated cylinder with hot air,
Of the charge transport layer.

Next, true spherical three-dimensionally crosslinked polysiloxane fine particles (average particle size 0.29 μm, manufactured by Toshiba Silicone Co., Ltd.)
0.5 parts by mass, 4 parts by mass of the following polycarbonate resin (bisphenol Z molecular weight 80000),

[0189]

Embedded image 2.5 parts by mass of the following triphenylamine

[0190]

Embedded image Was added and dispersed and mixed, and the mixture was applied on the charge transport layer by spray coating to form a photoreceptor drum provided with a protective layer having a thickness of 3 μm.

This photoreceptor contained 0.53% of Si atoms and 83.3% of C atoms, and had a Si / C of 0.0064.

Tables 1 and 2 summarize the XPS measurement results of the photoconductors A to H obtained above.

[0193]

[Table 1]

[0194]

[Table 2]

Example 1 The contact pressure of the polymerized toner b on the photosensitive member C was 50 g / c in the contact charging device shown in FIG.
m, an image forming apparatus having a DC voltage of −600 V applied to the charging member, an AC voltage of 2,000 Vpp, and a frequency of 150 Hz (a laser beam printer LBP-S manufactured by Canon Inc.).
X remodeling machine) to form a continuous 3000
A live-action test of the sheets was performed.

Table 3 shows the results.

[Examples 2 to 4 and Comparative Examples 1 to 4] Evaluations were performed using the toner and drum shown in Table 3 and the same image forming apparatus as in Example 1. The results are shown in Table 3.

Example 5 and Comparative Example 5 Using an image forming apparatus (a modified NP-8500 made by Canon) having a contact charging device as shown in FIG. 1 using a polymerized toner d and a photoreceptor D or F, A continuous shooting test of 3,000 sheets was continuously performed. The results are shown in Table 3.

[0199]

[Table 3]

[0200]

As described above, according to the present invention, there can be obtained an image forming method comprising a photosensitive member and a toner, which is excellent in transferability, has high image quality, and has a high durability and prevents toner sticking to the photosensitive member. Can be

[Brief description of the drawings]

FIG. 1 is an explanatory view schematically showing a charging roller of the present invention.

[Explanation of symbols]

 Reference Signs List 1 photoconductor drum 2 charging member E power supply

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kasugani Rare 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (56) References JP-A-5-88409 (JP, A) JP-A-3 JP-A-59563 (JP, A) JP-A-64-44964 (JP, A) JP-A-3-196067 (JP, A) JP-A-5-88502 (JP, A) JP-A-1-204081 (JP, A) JP-A-64-66673 (JP, A) JP-A-4-368954 (JP, A) JP-A-5-66599 (JP, A) JP-A-5-61229 (JP, A) JP-A-5-66529 119524 (JP, A) JP-A-61-279864 (JP, A) JP-A-63-65451 (JP, A) JP-A-64-23259 (JP, A) JP-A-2-141761 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03G 5/147 503 G03G 9/087 G03G 5/05 103

Claims (10)

(57) [Claims] 1. A charging roller having a surface layer formed of a releasable coating is brought into contact with an electrophotographic photosensitive member at a pressure of 5 to 500 g.
/ Cm, and after a charging step of applying a voltage to the charging roller from the outside to perform charging, a latent image is formed, and the latent image is visualized using a developer and transferred to a transfer material. In the method of forming an image, a) the electrophotographic photoreceptor contains an organic compound and a substance having fluorine and / or silicon atoms in its surface layer, and a fluorine atom or a silicon atom and a carbon atom determined by XPS measurement. B) using a photoreceptor satisfying the following relationship: F / C = 0.03 to 1.00 Si / C = 0.03 to 1.00 Parts by mass, 10 to 40 parts by mass of a polyalkylene as a release agent, a colorant, and a polymerizable monomer composition containing a polar polymer or a polar copolymer is subjected to suspension polymerization in an aqueous medium. Yes directly Tokura toner particles by The shape factor of the toner is 110-115, and the polar polymer or polar copolymer, the polymer or nitrogen Mototan dimeric styrene and unsaturated carboxylic acid esters of nitrogen-containing monomer Copolymer; nitrile monomer; halogen-containing monomer;
A polymer of a monomer selected from the group consisting of unsaturated carboxylic acids, unsaturated dibasic acids, unsaturated dibasic anhydrides and nitro monomers, or An image forming method, which is at least one selected from the group consisting of a copolymer; a polyester; and an epoxy resin. 2. The electrophotographic photosensitive member according to claim 1, wherein the surface layer comprises:
2. The composition according to claim 1, further comprising polycarbonate.
2. The image forming method according to 1., 3. The surface layer of the electrophotographic photoreceptor,
The image forming method according to claim 1, further comprising a polycarbonate synthesized using an asymmetric diol selected from the following compounds (1) to (29) . Embedded image Embedded image Embedded image Embedded image Embedded image 4. The image forming method according to claim 1, wherein a protective layer is provided on the charge transport layer in the electrophotographic photoreceptor, and the protective layer contains polycarbonate. 5. The image forming apparatus according to claim 1, wherein the charging member has a region where the distance from the surface of the photoconductor increases, and forms an oscillating electric field between the surface of the photoconductor and the region of the charging member. The image forming method according to claim 1. 6. A charging roller having a surface layer formed of a releasable film is brought into contact with an electrophotographic photosensitive member at a pressure of 5 to 500 g.
/ Cm, and after a charging step of applying a voltage to the charging roller from the outside to perform charging, a latent image is formed, and the latent image is visualized using a developer and transferred to a transfer material. An image forming method for forming an electrophotographic photoreceptor, wherein an organic compound is provided on a surface layer of the electrophotographic photoreceptor,
A substance containing fluorine and / or silicon atoms is present, and the ratio of fluorine atoms or silicon atoms to carbon atoms determined by XPS has the following relationship: F / C = 0.03 to 1.00 Si / C = 0.03 In the image forming developer used in the image forming method using a photoreceptor satisfying the following conditions, the toner in the developer contains 100 parts by mass of a polymerizable monomer and polyalkylene 10 to 40 as a release agent. It has a mass portion, a colorant, a polar polymer or a polymerizable monomer composition containing a polar copolymer directly Tokura toner particles by suspension polymerization in an aqueous medium The shape factor of the toner is 110 to 115 , and the polar polymer or the polar copolymer is a polymer of a nitrogen-containing monomer or a mixture of a nitrogen-containing monomer, styrene and an unsaturated carboxylic acid ester. Copolymer; nitrile Monomer;
A halogen-containing monomer; a polymer of a monomer selected from the group consisting of unsaturated carboxylic acids, unsaturated dibasic acids, unsaturated dibasic acid anhydrides and nitro monomers, or copolymer of styrene-based monomers, polyesters, and epoxy resins; image type forming developer which is characterized in that at least one selected from the group consisting of. 7. The electrophotographic photosensitive member according to claim 1, wherein the surface layer comprises:
7. The composition according to claim 6, further comprising polycarbonate.
3. The image forming developer according to item 1. 8. The surface layer of the electrophotographic photoreceptor,
An asymmetric di selected from the following compounds (1) to (29)
Contains polycarbonate synthesized using oars
The image forming developer according to claim 6, wherein: Embedded image Embedded image Embedded image Embedded image Embedded image 9. A charge transport layer in the electrophotographic photoreceptor
Having a protective layer thereon, and the protective layer comprising polycarbonate
The image forming method according to claim 6, further comprising:
Developer. 10. The distance between the charging member and the surface of the photoreceptor.
Is provided with an area where
Forming an oscillating electric field between the charging member and the region.
The image forming developer according to claim 6.