JP2001092167A - Image forming method, image forming device and developer used for the device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method which is the image forming method using a photoreceptor free of the reduction of the film thickness on its surface and is capable of forming images stable for a long period of time without the occurrence of image blur, stripe-like and dotty image defects and without the occurrence of an image fluctuation by an environmental fluctuation, an image forming device and a developer used for this device. SOLUTION: The image forming method for developing the latent image on the electrophotographic photoreceptor by the developer and transferring the developed toner image onto a recording medium material, then cleaning the toners remaining on the photoreceptor is the image forming method characterized in that the electrophotographic photoreceptor is the electrophotographic photoreceptor having a resin layer containing a siloxane resin having a structural unit possessing charge transfer performance on a conductive base and having a crosslinked structure and the toner used for the developer are the toners prepared by adding particulates of at least 201 to 2,000 nm in number average particle size at 0.1 to 3.0 wt.% to coloring particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to an image forming method, an image forming apparatus, and a developer used therein.

[0002]

2. Description of the Related Art In recent years, image forming techniques such as copying machines, printers, and facsimile machines have been remarkably developed, and the most frequently used one belongs to an electrostatic image forming method represented by an electrophotographic system. It is.

[0003] The reason is that an electrostatic image forming method such as an electrophotographic method can obtain a high-quality image at a high speed, can form not only a monochrome image but also a color image, and has a durability that can withstand long-term use. It is considered to have stability.

In the electrophotographic method, after the entire surface of a photosensitive member is charged, an exposure corresponding to an image to be formed is given to form an electrostatic latent image. This method forms an image by visualizing the electrostatic latent image with toner.

In recent years, an organic photoconductor containing an organic photoconductive substance has been most widely used as an electrophotographic photoconductor. Organic photoreceptors are advantageous over other photoreceptors in that materials that can be used for various exposure light sources from visible light to infrared light can be easily developed, materials that do not pollute the environment can be selected, and manufacturing costs are low. However, the only drawback is that the mechanical strength is weak, and the surface of the photoreceptor is deteriorated or scratched when a large number of sheets are copied or printed.

[0006] Such a photoreceptor is generally formed by depositing an organic charge-generating substance on a conductive support made of aluminum or an aluminum alloy, or using an organic charge-generating substance and an organic polymer resin as a binder. To form a charge generation layer by applying a coating liquid in which a solvent is mixed with a solvent, and then apply a coating liquid in which an organic charge transporting substance and an organic polymer resin as a binder are mixed with a solvent. To form a charge transport layer.

In general, in an electrophotographic apparatus of the Carlson method, after a photosensitive member is uniformly charged, an electric charge is erased imagewise by exposure to form an electrostatic latent image, and the electrostatic latent image is formed by toner. The toner is transferred and fixed on paper or the like.

However, not all of the toner on the photoreceptor is transferred, and a part of the toner remains on the photoreceptor. When an image is repeatedly formed in this state, the formation of a latent image is disturbed by the effect of the residual toner. Therefore, it is not possible to obtain a high-quality copy without contamination. Therefore, it is necessary to remove the residual toner. The cleaning means is typically a fur brush, a magnetic brush, a blade, or the like, but a blade is mainly used in terms of performance, configuration, and the like. At this time, a plate-shaped rubber elastic body is generally used as the blade member.

As described above, since the surface of the electrophotographic photosensitive member is directly applied with an electrical or mechanical external force by a charger, a developing device, a transfer means, a cleaning device, etc., the surface thereof is required to have durability. In particular, it is required to have mechanical durability against abrasion and scratches on the surface of the photoreceptor due to rubbing, film intrusion of foreign matter, and film peeling due to impact during paper jam processing. Above all, there is a demand for higher durability against scratches and film peeling due to impact.

In order to satisfy the various characteristics required as described above, various things have been studied so far.

Regarding the mechanical durability, BPZ polycarbonate is coated on the surface of the organic photoreceptor with a binder (binder resin).
It has been reported that the use of the compound improves surface abrasion characteristics and toner filming characteristics. Japanese Patent Application Laid-Open No. Hei 6-118681 reports that a curable silicone resin containing colloidal silica is used as a surface protective layer of a photoreceptor.

However, a photoreceptor using a BPZ polycarbonate binder still lacks abrasion resistance and does not have sufficient durability. On the other hand, in the surface layer of the curable silicone resin containing colloidal silica, the abrasion resistance is improved, but the electrophotographic properties after repeated use are insufficient, and fogging and image blur are liable to occur. Not enough.

As a method for improving such a defect, Japanese Patent Application Laid-Open No. 9-124943 and Japanese Patent Application Laid-Open No. 9-190004
In Japanese Patent Application Laid-Open No. H11-264, a photoreceptor having a resin layer in which an organosilicon-modified hole transporting compound is bound in a curable organosilicon polymer as a surface layer is proposed. However, in this technique, since the surface layer is hardened, the surface of the photoconductor is not polished. As a result, water adsorbed in a high-temperature, high-humidity environment cannot be removed, resulting in image blur,
There is a problem that filming of paper powder or toner is apt to occur, and that streak-like or spot-like image defects are likely to occur.

[0014]

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art as described above.

That is, an object of the present invention is to provide an image forming method using a photoreceptor without depletion of the photoreceptor, without causing image blur, streak-like or spot-like image defects, and reducing image fluctuation due to environmental fluctuation. An object of the present invention is to propose an image forming method capable of forming a stable image over a long period of time.

[0016]

The above object is achieved by the following constitution.

1. An image forming method for developing a latent image on an electrophotographic photoreceptor with a developer, transferring the visualized toner image to a recording material, and cleaning the toner remaining on the photoreceptor, Is an electrophotographic photoreceptor having a resin layer containing a siloxane-based resin having a cross-linked structure having a structural unit having charge transport performance on a conductive support, and the toner used in the developer is colored The particles have a number average primary particle diameter of at least 201 to 200
An image forming method, characterized in that the toner is formed by adding 0.1 to 3.0% by weight of 0 nm fine particles.

2. 2. The image forming method according to item 1, wherein the siloxane-based resin having the structural unit having the charge transporting performance and having the cross-linking structure is a siloxane-based resin having a compound group having the charge transporting performance as a partial structure. .

3. The siloxane-based resin having the structural unit having the charge transporting performance and having a crosslinked structure is obtained by reacting an organic silicon compound having a hydroxyl group or a hydrolyzable group with a charge transporting compound having a hydroxyl group. 3. The image forming method according to the above 1 or 2.

4. An image forming apparatus having a cleaning unit that develops a latent image on an electrophotographic photosensitive member with a developer, transfers a visualized toner image to a recording material, and then removes toner remaining on the photosensitive member. The electrophotographic photoreceptor has a structural unit having charge transport performance on a conductive support,
And an electrophotographic photoreceptor having a resin layer containing a siloxane-based resin having a cross-linked structure, wherein the toner used for the developer contains at least a number average primary particle diameter of fine particles having a number average primary particle diameter of from 201 to 2,000 nm by 0.1 An image forming apparatus characterized in that the toner is a toner to which about 3.0% by weight is added.

5. A latent image on an electrophotographic photoreceptor having a resin layer containing a siloxane-based resin having a crosslinked structure and having a structural unit having a charge transporting property on a conductive support is developed with a developer to visualize the latent image. After the transferred toner image is transferred to the recording material, in a developer used in an image forming method for cleaning the toner remaining on the photoreceptor, the toner used in the developer has at least a number average primary particle diameter of the colored particles. Fine particles of 201-2000 nm
A developer comprising 3.0% by weight of a toner.

6. An image forming method for developing a latent image on an electrophotographic photoreceptor with a developer, transferring the visualized toner image to a recording material, and cleaning the toner remaining on the photoreceptor, Is an electrophotographic photoreceptor having a resin layer containing a siloxane-based resin having a cross-linked structure having a structural unit having charge transport performance on a conductive support, and the toner used in the developer is colored The particles have at least a number average primary particle diameter of 5 to 49 nm and 50 to 200 nm, respectively.
An image forming method, wherein the toner is added by 3.0% by weight.

7. 7. The image forming method according to the item 6, wherein the siloxane-based resin having the structural unit having the charge-transporting performance and having the cross-linking structure is a siloxane-based resin having a compound group having the charge-transporting performance as a partial structure. .

8. The siloxane-based resin having the structural unit having the charge transporting performance and having a crosslinked structure is obtained by reacting an organic silicon compound having a hydroxyl group or a hydrolyzable group with a charge transporting compound having a hydroxyl group. 8. The image forming method according to the above item 6 or 7.

9. An image forming apparatus having a cleaning unit that develops a latent image on an electrophotographic photosensitive member with a developer, transfers a visualized toner image to a recording material, and then removes toner remaining on the photosensitive member. The electrophotographic photoreceptor has a structural unit having charge transport performance on a conductive support,
And an electrophotographic photoreceptor having a resin layer containing a siloxane-based resin having a cross-linking structure, wherein the toner used for the developer is a colored particle in which at least a number average primary particle diameter is at least 5 to 49 nm and 50 to 200 nm. An image forming apparatus, wherein the toner is obtained by adding 0.1 to 3.0% by weight of each of the fine particles.

10. A latent image on an electrophotographic photoreceptor having a resin layer containing a siloxane-based resin having a crosslinked structure and having a structural unit having a charge transporting property on a conductive support is developed with a developer to visualize the latent image. After the transferred toner image is transferred to the recording material, in a developer used in an image forming method for cleaning the toner remaining on the photoreceptor, the toner used in the developer has at least a number average primary particle diameter of the colored particles. 5-49nm fine particles and 50-2000n
m, a toner comprising 0.1 to 3.0% by weight of each of fine particles of m.

Hereinafter, the present invention will be described in detail.

As a result of intensive studies, the present inventors have analyzed the problems in the case of using a photoreceptor with little wear in consideration of the adhesion to the photoreceptor, and have completed the present invention.

According to the present invention, image blurs or streaks in a high-temperature and high-humidity environment, which occur when a photoreceptor with little wear is used,
Alternatively, the solution to the spot-like image defect can be taken as a factor on the toner side and solved.

The present inventors have found that the external additive itself exerts its abrasiveness effectively to remove substances causing image deletion such as moisture adhering to the surface of the photoreceptor. The present inventors have found that the problem can be solved by preventing filming caused by paper dust or toner which causes spot-like image defects, and have completed the present invention.

That is, the present inventors have a method of effectively removing minute deposits formed on a photoreceptor surface by adsorption or the like with a small decrease in film thickness due to abrasion, before filming having a strong adhesive force. It has been found that it is effective to add fine particles having a large particle diameter to the toner and to carry the fine particles on the surface of a cleaning member (such as a cleaning blade) during cleaning. That is, by externally adding fine particles having a large particle diameter to the toner, the adsorbed components on the photoreceptor surface can be effectively removed, and the problem of image deletion, streak-like or spot-like image defects can be solved. And completed the present invention.

Furthermore, it has been found that by effectively controlling the abrasiveness of the external additive, the deposits can be effectively removed without substantially damaging the surface of the photoreceptor.

The inventors have found a means that can effectively exhibit the abrasiveness even if the external additive is not a large particle size.

That is, fine particles having a number average primary particle diameter of 5 to 50 nm and fine particles having a number average
It has been found that the present invention can be achieved by using a toner to which 3.0% by weight is added.

Although the reason is not clear, it can be considered as follows. That is, 50 to 200 nm
Even if the particles are medium-sized particles, the abrasiveness can be expanded by effectively presenting the particles on the toner surface, and a substance that induces image deletion can be removed. By allowing fine particles having a small particle size of 5 to 49 nm to coexist there, particles of a medium size can exhibit abrasiveness effectively. Although the reason for this is not clear, the external additive having a small particle size has a high adhesiveness and selectively adheres to the surface of the toner particles. The external additive having a medium particle diameter selectively adheres to the toner surface to which the external additive having a small particle diameter adheres.As a result, the external additive is present on the toner surface with low adhesiveness, and the toner is developed. Then, at the stage of the transfer, a relatively large amount of a medium external additive remains on the surface of the photoreceptor. It is presumed that the remaining medium additive remaining on the cleaning member adhered to the cleaning member and was able to exert a polishing effect.

As described above, when the external additive having the small particle size and the medium particle size is used, the abrasion of the cleaning member is reduced as compared with the case where the external additive having the large particle size is used. Has the added advantage that it can be used for long periods without replacement.

Next, the materials, requirements, devices and the like used in the present invention will be further described.

The toner used in the present invention may be a pulverized toner or a granulated polymer toner.
The description will be made in the order of the pulverized toner.

The materials of the suspension polymerization toner and the resin particle fused toner used in the present invention and the production method will be described.

<< Materials >> [Monomer] As the polymerizable monomer, a radical polymerizable monomer is used as an essential component, and a crosslinking agent can be used if necessary. Further, at least one of the following radically polymerizable monomers having an acidic group or a radically polymerizable monomer having a basic group may be contained.

(1) Radical polymerizable monomer The radical polymerizable monomer component is not particularly limited, and a conventionally known radical polymerizable monomer can be used. Also, to satisfy the required characteristics,
Species or a combination of two or more can be used.

Specifically, aromatic vinyl monomers, (meth) acrylate monomers, vinyl ester monomers, vinyl ether monomers, monoolefin monomers, diolefin monomers Monomers, halogenated olefin monomers and the like can be used.

Examples of the aromatic vinyl monomer include, for example,
Styrene, o-methylstyrene, m-methylstyrene,
p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, p-ethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n- Styrene-based monomers such as octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, 2,4-dimethylstyrene, and 3,4-dichlorostyrene, and derivatives thereof. .

(Meth) acrylic ester monomers include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate Butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, propyl γ-aminoacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.

Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, vinyl benzoate and the like.

Examples of the vinyl ether monomer include vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl phenyl ether and the like.

Examples of the monoolefin-based monomer include ethylene, propylene, isobutylene, 1-butene, 1-pentene, 4-methyl-1-pentene and the like.

The diolefin-based monomer includes butadiene, isoprene, chloroprene and the like.

Examples of the halogenated olefin monomer include:
Vinyl chloride, vinylidene chloride, vinyl bromide and the like.

(2) Crosslinking Agent As the crosslinking agent, a radical polymerizable crosslinking agent may be added in order to improve the properties of the toner. Examples of the radical polymerizable crosslinking agent include divinylbenzene, divinylnaphthalene,
Examples thereof include those having two or more unsaturated bonds such as divinyl ether, diethylene glycol methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and diallyl phthalate.

(3) Radical polymerizable monomer having acidic group or radical polymerizable monomer having basic group Radical polymerizable monomer having acidic group or radical polymerizable monomer having basic group For example, an amine compound such as a carboxyl group-containing monomer, a sulfonic acid group-containing monomer, a primary amine, a secondary amine, a tertiary amine, and a quaternary ammonium salt may be used. it can.

Examples of the radical polymerizable monomer having an acidic group include carboxylic acid group-containing monomers such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, monobutyl maleate, And monooctyl maleate.

Examples of the sulfonic acid group-containing monomer include styrene sulfonic acid, allyl sulfosuccinic acid, octyl allyl sulfosuccinate and the like.

These may have a structure of an alkali metal salt such as sodium or potassium or an alkaline earth metal salt such as calcium.

Examples of the radical polymerizable monomer having a basic group include amine compounds, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and the quaternary of the above four compounds. Ammonium salt, 3-dimethylaminophenyl acrylate, 2-hydroxy-3-methacryloxypropyltrimethylammonium salt, acrylamide, N-butylacrylamide, N, N-dibutylacrylamide,
Piperidylacrylamide, methacrylamide, N-butylmethacrylamide, N-octadecylacrylamide, vinylpyridine, vinylpyrrolidone, vinyl N-methylpyridinium chloride, vinyl N-ethylpyridinium chloride, N, N-diallylmethylammonium chloride, N, N- Diallylethylammonium chloride and the like can be mentioned.

As the radical polymerizable monomer used in the present invention, a radical polymerizable monomer having an acidic group or a radical polymerizable monomer having a basic group is 0.1 to 15% of the whole monomer. Preferably, the radical polymerizable cross-linking agent is used in the range of 0.1 to 10% by weight, based on the total radical polymerizable monomer, depending on its properties.

[Chain transfer agent] For the purpose of adjusting the molecular weight, a commonly used chain transfer agent can be used.

The chain transfer agent is not particularly restricted but includes, for example, mercaptans such as octyl mercaptan, dodecyl mercaptan and tert-dodecyl mercaptan, and styrene dimers.

[Polymerization Initiator] The radical polymerization initiator used in the present invention is preferably oil-soluble in the case of suspension polymerization.

Specific examples of the oil-soluble polymerization initiator include benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, cumene hydroperoxide, acetyl peroxide, and propionyl peroxide. Peroxides such as 2,2'-azobisisobutyronitrile, 2,2 '
Azobis polymerization initiators such as -azobis (2,4-valeronitrile), 2,2'-azobis-2-methylvaleronitrile, and 2,2'-azobis-2,4-dimethylvaleronitrile. it can.

As the polymerization temperature, any temperature may be selected as long as it is higher than the minimum radical generation temperature of the polymerization initiator. However, the polymerization temperature should be in a temperature range in which the half life of the polymerization initiator is about 2 hours to 10 hours. preferable. Although the temperature range varies depending on the polymerization initiator, for example, a range of 50 to 90 ° C. is preferably used.

The amount of the polymerization initiator to be added is determined by the molecular weight of the required resin as the final toner, and is generally 0.1 to 10% by weight based on the radical polymerizable monomer. Preferably it is 0.2 to 5% by weight.

Further, the dispersion stabilizer is finally filtered,
Those which can be easily removed in the washing stage are preferred, and inorganic hardly water-soluble dispersion stabilizers are particularly preferably used. Specific examples include calcium carbonate, tricalcium phosphate, aluminum oxide, barium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium oxide, silicon oxide, iron hydroxide, and the like. Particularly preferred dispersion stabilizers are Tricalcium phosphate. A small amount of a surfactant may be used as a dispersing aid in addition to the poorly water-soluble inorganic dispersion stabilizer. In this case, any of nonionic, anionic, cationic and amphoteric surfactants can be used, but anionic surfactants are more preferred.

The dispersion stabilizer is used by dispersing it in an aqueous medium. In this case, it is preferable to use about 1 to 10% by weight based on the oil phase component to be dispersed. If the amount is less than this range, the dispersion stability decreases, and coalescence of particles occurs. On the other hand, if the amount is larger than this range, the dispersion is promoted, so that a small particle size component is excessively generated.

Further, the surfactant is preferably added in an amount of about 0.05 to 1% by weight with respect to the inorganic dispersion stabilizer.
If it is less than this range, the effect of improving dispersion stability cannot be exhibited. On the other hand, when used beyond this range, emulsification of the radical polymerizable monomer occurs, so-called latex particles are generated in the system, there is a problem that the particle size distribution is widened, and removal of the surfactant is There is a problem of causing moisture adsorption.

In the case of a production method in which resin particles are prepared by so-called emulsion polymerization, and then the resin particles are formed by salting out and fusing, if a water-soluble polymerization initiator is used, it is appropriately used. Is possible. For example, persulfates (potassium persulfate, ammonium persulfate, etc.), azo compounds (4,4′-azobis-4-cyanovaleric acid and salts thereof,
2,2'-azobis (2-amidinopropane) salt and the like),
Peroxide compounds and the like.

Further, the above radical polymerization initiator can be used as a redox initiator in combination with a reducing agent, if necessary. By using a redox-based initiator, the polymerization activity is increased, the polymerization temperature can be reduced, and a further reduction in the polymerization time can be expected.

As the polymerization temperature, any temperature may be selected as long as it is equal to or higher than the lowest radical generation temperature of the polymerization initiator. For example, a temperature in the range of 50 to 90 ° C. is used. However, by using a polymerization initiator started at room temperature, for example, a combination of hydrogen peroxide and a reducing agent (such as ascorbic acid), polymerization can be performed at room temperature or higher.

[Colorant] Examples of the colorant include inorganic pigments and organic pigments.

Conventionally known inorganic pigments can be used. Specific inorganic pigments are exemplified below.

Examples of black pigments include furnace black, channel black, acetylene black,
Carbon black such as thermal black and lamp black, and magnetic powder such as magnetite and ferrite are also used.

These inorganic pigments can be used alone or in combination of two or more as desired. The amount of the pigment to be added is 2 to 20% by weight, preferably 3 to 15% by weight, based on the polymer.

When used as a magnetic toner, the above-mentioned magnetite can be added. In this case, from the viewpoint of imparting predetermined magnetic characteristics, 20 to 6
It is preferable to add 0% by weight.

Conventionally known organic pigments can also be used. Specific organic pigments are exemplified below.

The pigments for magenta or red include:
C. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 5, C.I. I. Pigment Red 6, C.I. I. Pigment Red 7, C.I. I. Pigment Red 15, C.I. I. Pigment Red 16,
C. I. Pigment Red 48: 1, C.I. I. Pigment Red 53: 1, C.I. I. Pigment Red 57:
1, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 139,
C. I. Pigment red 144, C.I. I. Pigment Red 149, C.I. I. Pigment Red 166, C.I.
I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 222 and the like.

Examples of pigments for orange or yellow include C.I. I. Pigment Orange 31, C.I. I. Pigment Orange 43, C.I. I. Pigment Yellow 12,
C. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I.
I. Pigment Yellow 17, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I.
Pigment Yellow 138 and the like.

The pigments for green or cyan include:
C. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3,
C. I. Pigment Blue 16, C.I. I. Pigment Blue 60, C.I. I. Pigment Green 7 and the like.

These organic pigments can be used alone or in combination of two or more as desired. The amount of the pigment to be added is 2 to 20% by weight, preferably 3 to 15% by weight, based on the polymer.

The colorant can be used after surface modification. As the surface modifier, a conventionally known one can be used, and specifically, a silane coupling agent, a titanium coupling agent, an aluminum coupling agent and the like can be preferably used.

<< Manufacturing Process of Suspension Polymerized Toner >> In the manufacturing process of the polymerized toner of the present invention, a polymerization initiator and components necessary for constituting a toner such as a pigment and a release agent are contained in a radical polymerizable monomer. A step of dispersing and containing, a step of dispersing the dispersion liquid in which pigments and the like are dispersed in water and dispersing them into droplets having a desired particle size of a toner, a polymerization step, removing and washing a dispersion stabilizer,
It comprises a filtration step and a drying step.

The dispersing machine used for dispersing the pigment and the like is not particularly limited, but is preferably an ultrasonic dispersing machine, a mechanical homogenizer, a pressure dispersing machine such as Manton-Gaulin or a pressure homogenizer, a sand grinder, a Getzman mill, or the like. A medium-type disperser such as a diamond fine mill can be used. In addition, since it is necessary to add a polymerization initiator, it is preferable to cool and disperse so as not to be affected by heat at the time of dispersion.

Further, when dispersing the above-mentioned dispersion liquid in an aqueous medium, it is necessary to adjust the formed droplets to have a desired toner particle diameter. Examples of the dispersing device used in this case include a TK homomixer, a TK homojetter, a rotating double cylinder, and an ultrasonic disperser. When dispersing, observe the particle size of the dispersed droplets with a microscope etc.,
By a method of stopping the dispersion at a predetermined time, a droplet having a desired dispersion diameter can be formed.

Here, the toner of the present invention preferably has a volume average particle diameter of 3 to 9 μm. The volume average particle diameter of these toners can be measured using a Coulter Counter TA-II, Coulter Multisizer, SLAD1100 (Shimadzu Corporation laser diffraction particle size analyzer), or the like. In the Coulter Counter TA-II and the Coulter Multisizer, those measured using an aperture having an aperture diameter of 100 μm and a particle size distribution in the range of 2.0 to 40 μm are shown.

In the polymerization step, the polymerization is carried out at a temperature not lower than the decomposition temperature of the polymerization initiator. Generally, it is preferable to polymerize at about 50 to 90 ° C.

After completion of the polymerization, it is preferable to add an acid in order to cool and remove the dispersion stabilizer. Hydrochloric acid, sulfuric acid and the like can be used as the acid. Then, filter,
The toner can be obtained by washing with water and drying.

<< Step of Manufacturing Salting-Out and Fusing Toner >> The step of manufacturing the salting-out and fusing-type toner of the present invention includes a polymerization step of preparing resin particles or resin particles containing a colorant by emulsion polymerization. A step of fusing resin particles and colorant particles or resin particles containing a colorant in an aqueous medium using the resin particle dispersion, removing the resulting particles from the aqueous medium to remove a surfactant, etc. A washing step, a step of drying the obtained particles, and a step of adding an external additive to the particles obtained by drying. Here, the resin particles may be colored particles.
Further, non-colored particles can be used as the resin particles.In this case, the colorant can be further colored by adding a colorant particle dispersion to the dispersion of the resin particles and then fusing the dispersion in an aqueous medium. it can.

In particular, as a fusion method, a method of performing salting out using resin particles produced in the polymerization step and performing fusion is preferable. When non-colored resin particles are used, the resin particles and the colorant particles can be salted out and fused in an aqueous medium.

Further, in addition to the colorant and the release agent, a charge control agent or the like, which is a component of the toner, can be added as particles in this step.

Here, the aqueous medium is composed of water as a main component, and indicates that the total amount of water is 50% by weight or more. Examples of the solvent other than water include an organic solvent soluble in water, such as methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran. Methanol, an organic solvent that does not dissolve the resin,
Alcohol organic solvents such as ethanol, isopropanol and butanol are particularly preferred.

The disperser for dispersing the magnetic material is not particularly limited, but is preferably an ultrasonic disperser, a mechanical homogenizer,
Examples thereof include a pressure disperser such as Menton Gorin and a pressure homogenizer, and a medium disperser such as a sand grinder, a Getzman mill and a diamond fine mill.

As the surfactant used here, the above-mentioned surfactants can be used. In the step of performing salting out / fusion, a salting out agent composed of an alkali metal salt, an alkaline earth metal salt, or the like is added as a coagulant having a critical coagulation concentration or more in water in which resin particles and magnetic particles are present, Then, heating is performed at a temperature higher than the glass transition point of the resin particles to promote salting out and simultaneously perform fusion. In this step, a method may be used in which an organic solvent that is infinitely soluble in water is added, and the glass transition temperature of the resin particles is substantially lowered to effectively perform fusion.

Here, the alkali metal salt and alkaline earth metal salt as salting-out agents include lithium, potassium, sodium and the like as alkali metals, and magnesium, calcium, strontium, barium and the like as alkaline earth metals. And preferably potassium, sodium, magnesium, calcium and barium. Examples of the constituents of the salt include chloride, bromide, carbonate, sulfate and the like.

When the fusion of the present invention is carried out by salting out / fusing, it is preferable to minimize the time of standing after adding the salting out agent. Although the reason for this is not clear, the aggregation state of the particles fluctuates depending on the standing time after salting out,
There are problems that the particle size distribution becomes unstable and the surface properties of the fused toner fluctuate. The temperature at which the salting-out agent is added must be at least equal to or lower than the glass transition temperature of the resin particles. The reason for this is that if the temperature at which the salting-out agent is added is higher than the glass transition temperature of the resin particles, the salting-out / fusion of the resin particles proceeds rapidly, but the particle size cannot be controlled, and There is a problem that particles having a particle size are generated. The range of the addition temperature may be lower than the glass transition temperature of the resin, but is generally 5 to 55 ° C, preferably 10 to 45 ° C.

In the present invention, it is preferable to use a method in which a salting-out agent is added at a temperature lower than the glass transition temperature of the resin particles, and thereafter, the temperature is raised as quickly as possible, and the temperature is raised to a temperature higher than the glass transition temperature of the resin particles. The time until the temperature rise is preferably less than 1 hour. Further, it is necessary to raise the temperature promptly, but the rate of temperature increase is preferably 0.25 ° C./min or more. The upper limit is not particularly clear, but if the temperature is raised instantaneously, salting out proceeds rapidly, and there is a problem that particle size control is difficult to perform.

Here, the particle diameter of the toner obtained by fusing according to the present invention is preferably 3 to 9 μm in terms of volume average particle diameter. These toners have a volume average particle diameter of Coulter Counter TA-II, Coulter Multisizer, SLAD110
0 (Shimadzu Corporation laser diffraction particle size analyzer) or the like. Coulter counter T
For A-II and Coulter Multisizer, 2.0 to 40 μm using an aperture with an aperture diameter of 100 μm
Is measured using the particle size distribution in the range of.

Next, the pulverized toner used in the present invention will be described.

In the case of the pulverization method, a resin, a colorant and other necessary components are added and preliminarily mixed, and then kneaded and dispersed using a kneading apparatus such as a twin screw extruder, and coarse and fine pulverization is performed. It is prepared by classification.

The toner of the present invention contains fine particles having at least a number average primary particle diameter of from 201 to 2,000 nm in an amount of from 0.1 to 3.
0% by weight, a toner obtained by externally mixing the colored particles,
Alternatively, at least fine particles having a number average primary particle diameter of 5 to 49 nm and fine particles of 50 to 200 nm are each contained in 0.1 to 3.
0% by weight of the toner externally added to the colored particles, and is characterized by having a remarkable effect in achieving the object of the present invention.

Hereinafter, the above-mentioned external additives will be described.

As the external additive fine particles, the following various inorganic fine particles and organic fine particles can be used.

As a material constituting the inorganic fine particles, various inorganic oxides, nitrides, borides and the like are preferably used.
For example, silica, alumina, titania, zirconia, barium titanate, aluminum titanate, strontium titanate, magnesium titanate, zinc oxide, chromium oxide, cerium oxide, antimony oxide, tungsten oxide, tin oxide, tellurium oxide, manganese oxide, Examples include boron oxide, silicon carbide, boron carbide, titanium carbide, silicon nitride, titanium nitride, boron nitride, and the like. further,
The above-mentioned inorganic fine particles may be subjected to a hydrophobic treatment. When performing the hydrophobizing treatment, it is preferable to perform hydrophobizing treatment with a so-called coupling agent such as various titanium coupling agents and silane coupling agents, and silicone oil, and further, aluminum stearate, zinc stearate, and calcium stearate. Hydrophobization treatment with a higher fatty acid metal salt such as described above is also preferably used.

Examples of the treating agent for performing the hydrophobizing treatment include titanium coupling agents such as tetrabutyl titanate, tetraoctyl titanate, isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, and bis (dioctyl pyrophosphate). ) Oxyacetate titanate. Further, as the silane coupling agent, γ-
(2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) γ-amino Propyltrimethoxysilane hydrochloride, hexamethyldisilazane, methyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, phenyltrimethoxy Examples include silane, o-methylphenyltrimethoxysilane, p-methylphenyltrimethoxysilane and the like. Examples of fatty acids and metal salts thereof include undecylic acid, lauric acid, tridecylic acid, dodecylic acid, Long-chain fatty acids such as stinic acid, palmitic acid, pentadecylic acid, stearic acid, heptadecylic acid, arachinic acid, montanic acid, oleic acid, linoleic acid, and arachidonic acid are listed. And salts with metals such as calcium, sodium and lithium. Further, as the silicone oil, dimethyl silicone oil, methylphenyl silicone oil, amino-modified silicone oil and the like can also be mentioned as surface treatment agents.

These compounds are preferably coated by adding 1 to 10% by weight to the inorganic fine particles.
3-7% by weight. Further, these materials can be used in combination.

As organic fine particles, styrene resin particles,
Styrene acrylic resin particles, polyester resin particles, urethane resin particles, and the like can be given.

The composition of the resin fine particles is not particularly limited. Generally, vinyl-based organic fine particles are preferable. The reason for this is that it can be easily produced by a production method such as an emulsion polymerization method or a suspension polymerization method. Specifically, styrene, α-methylstyrene, p-chlorostyrene, 3,4-dichlorostyrene,
p-phenylstyrene, p-ethylstyrene, 2,4-
Styrene or styrene derivatives such as dimethylstyrene, pt-butylstyrene, etc., methyl methacrylate,
Ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, methacrylate derivatives such as 2-ethylhexyl methacrylate, methyl acrylate,
Ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-octyl acrylate, acrylate derivatives such as 2-ethylhexyl acrylate, ethylene,
Olefins such as propylene and isobutylene, vinyl chlorides such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, and vinylidene fluoride; vinyl esters such as vinyl propionate and vinyl acetate; vinyl methyl ether and vinyl ethyl Vinyl ethers such as ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl hexyl ketone; N-vinyl compounds such as N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalene, vinyl pyridine and the like. Vinyl compounds, acrylonitrile, methacrylonitrile, acrylamide, N-butylacrylamide, N, N-dibutylacrylamide, methacrylamide, N-butylmethacrylamide, N-octadecylacrylamide, etc. Is acrylic acid or methacrylic acid derivatives. These vinyl monomers can be used alone or in combination.

The fine resin particles can be produced by an emulsion polymerization method or a suspension polymerization method. The emulsion polymerization method is a method in which the above-mentioned monomer is added to water containing a surfactant and emulsified, followed by polymerization. As the surfactant, sodium dodecylbenzenesulfonate, polyvinyl alcohol, an ethylene oxide adduct, Any substance that is used as a surfactant such as alcohol sodium sulfate can be used and is not particularly limited. Further, the use of a reactive emulsifier, a hydrophilic monomer, for example, polymerization with a persulfate initiator such as vinyl acetate or methyl acrylate, a method of copolymerizing a water-soluble monomer, a water-soluble resin, So-called non-emulsion polymerization methods such as a method using an oligomer, a method using a decomposable emulsifier, and a method using a cross-linkable emulsifier are also suitable. Examples of the reactive emulsifier include sulfonic acid salts of acrylic acid amide and salts of maleic acid derivatives. The non-emulsion polymerization method is not affected by the residual emulsifier, and is suitable when organic fine particles are used alone.

Polymerization initiators necessary for synthesizing resin fine particles include peroxides such as benzoyl peroxide and lauryl peroxide, and azo-based polymerization initiators such as azobisisobutyronitrile and azobisisovaleronitrile. Agents. The addition amount of these is preferably 0.1 to 2% by weight based on the monomer. If the amount is less than this, the polymerization reaction becomes insufficient, and the problem of residual monomer itself occurs. Further, when the amount is too large, a decomposition product of the polymerization initiator remains and affects the chargeability, and furthermore, the polymerization reaction is too early to cause a problem that the molecular weight becomes small. Further, in an emulsion polymerization method or the like, potassium persulfate, sodium thiosulfate, or the like can be used as a polymerization initiator.

Of these, those which are preferably used as the material of the fine particles having a size of from 201 to 2,000 nm are preferably various organic fine particles, particularly styrene-based or acrylic-based or styrene-acrylic-based ones from the viewpoint of hardness. Further, as inorganic fine particles, titanium oxide, silica,
Strontium titanate, barium titanate, calcium titanate, cerium oxide and the like can also be preferably used. Among them, those having a small specific surface area are more effective in preventing filming as the inorganic fine particles, and those having a BET value of 20 m ² / g or less are preferable. Furthermore, it is more preferred that the surface is hydrophobicized.

[0109] The amount of addition is 0.1 to 0.1% in the toner.
It is 3.0% by weight, preferably 0.5 to 2.0% by weight. Beyond this range, the effect on cleaning increases, but there is a problem that large-diameter fine particles themselves are released, and the scattered particles cause contamination of the band electrode and transfer electrode, resulting in an image such as a white stripe. This can cause defects. On the other hand, if it is too small, the cleaning effect cannot be exhibited.

Materials preferably used as the material of the fine particles of 50 to 200 nm include, for example, silica, alumina,
Examples include titania, zirconia, barium titanate, strontium titanate, magnesium titanate, zinc oxide, chromium oxide, and cerium oxide.

Materials preferably used as the material of the fine particles of 5 to 49 nm include silica, alumina, titania, zirconia and the like.

Each of the fine particles is contained in the toner in an amount of 0.1.
It is 1 to 3.0% by weight, preferably 0.3 to 2.5% by weight. If added beyond this range, the cleaning performance itself is improved, but there is a problem that the fine particles themselves are separated, and the scattered particles cause contamination of the band electrode and the transfer electrode, resulting in image defects such as white stripes. Cause Further, since the fine particles are present in the toner in a free state, they cause damage to the photoconductor, cause damage to the photoconductor, and cause so-called black spots and white spots. On the other hand, if it is too small, the cleaning effect cannot be exhibited.

The above particle diameter is a number average primary particle diameter, which is magnified 2000 times by observation with a transmission electron microscope.
0 particles are observed and are shown by image analysis.

In addition to the fine particle external additive, a lubricant may be added to the toner of the present invention. For example, salts of zinc, aluminum, copper, magnesium, calcium, etc. of stearic acid, zinc, manganese, iron, copper, salts of magnesium, etc. of oleic acid, zinc, copper, magnesium of palmitic acid,
Metal salts of higher fatty acids such as salts of calcium and the like, salts of zinc and linoleic acid such as calcium, salts of ricinoleic acid such as zinc and calcium and the like. The amount of these lubricants added
It is preferably about 0.1 to 5% by weight based on the toner.

[Tonerization Step] As a method for adding the external additive, various known mixing apparatuses such as a turbulent mixer, a Hensiel mixer, a Nauter mixer, and a V-type mixer can be used.

The toner may contain a material capable of imparting various functions as a toner material in addition to the colorant and the release agent. Specific examples include a charge control agent. These components are added at the stage of emulsion polymerization of the resin particles, the dispersion is added, the resin particles and the colorant particles are added at the same time in the salting-out / fusion step, and the toner particles are included in the toner. It can be added by various methods such as a method of adding it to an aqueous solution. As a preferable method, a method in which the charge control agent particles and / or the fixability improving agent particles are added in a dispersion state at the stage of the emulsion polymerization of the resin particles, and the above-described salting out /
In the fusing step, a method in which the charge control agent particles and / or the fixability improving agent particles are added together with the resin particles and the colorant particles in the form of a dispersion and then salted out / fused is used.

It is preferable to use various known release agents which can be dispersed in water. Specifically, olefinic waxes such as polypropylene and polyethylene, modified products thereof, natural waxes such as carnauba wax and rice wax,
An amide wax such as a fatty acid bisamide can be used. It has already been mentioned that these are preferably added as release agent particles and are preferably salted out / fused together with the resin or colorant.

The charge control agents are also various known ones.
What can be dispersed in water can also be used. Specifically, nigrosine dyes, metal salts of naphthenic acid or higher fatty acids, alkoxylated amines,
Quaternary ammonium salt compounds, azo-based metal complexes, salicylic acid metal salts or metal complexes thereof.

The particles of the release agent and the charge control agent preferably have a number average primary particle diameter of about 10 to 500 nm in a dispersed state.

<< Developer >> The toner used in the present invention is:
Although a one-component developer or a two-component developer may be used, a two-component developer is preferable.

When the toner is used as a one-component developer, there is a method of using the toner as it is as a non-magnetic one-component developer. However, usually, magnetic particles of about 0.1 to 5 μm are contained in toner particles so that the magnetic one-component developer is used. Used as a developer. As a method of containing the same, it is common to make the non-spherical particles contain the same as the coloring agent.

Further, it can be used as a two-component developer by mixing with a carrier. In this case, as the magnetic particles of the carrier, conventionally known materials such as metals such as iron, ferrite and magnetite, and alloys of these metals with metals such as aluminum and lead are used. Particularly, ferrite particles are preferable. The magnetic particles have a volume average particle size of 15
-100 μm, more preferably 25-60 μm.

The volume average particle size of the carrier is typically measured by a laser diffraction type particle size distribution analyzer “HELOS” equipped with a wet disperser (SYMPATIC (SYMPIC)
(ATEC)).

The carrier is preferably a carrier in which magnetic particles are further coated with a resin, or a so-called resin-dispersed carrier in which magnetic particles are dispersed in a resin. Although there is no particular limitation on the resin composition for coating, for example, an olefin resin, a styrene resin, a styrene / acrylic resin, a silicone resin, an ester resin, a fluorine-containing polymer resin, or the like is used. The resin for forming the resin dispersion type carrier is not particularly limited, and known resins can be used.For example, styrene acrylic resin, polyester resin, fluorine resin, phenol resin, and the like can be used. it can.

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

In the present invention, the siloxane-based resin is produced by a known method using an organosilicon compound having a hydroxyl group or a hydrolyzable group. The organosilicon compound is represented by the following general formulas (A) to (D).

[0127]

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(In the formula, R _{1 to} R ₆ represent an organic group in which carbon is directly bonded to silicon in the formula, and Z _{1 to} Z ₄ represent a hydroxyl group or a hydrolyzable group.) When Z _{1 to} Z ₄ are a hydrolyzable group, the hydrolyzable group includes a methoxy group, an ethoxy group, a methylethylketoxime group, a diethylamino group, an acetoxy group, a propenoxy group, a propoxy group, a butoxy group, a methoxyethoxy group and the like. No. Examples of the organic group in which carbon is directly bonded to silicon represented by R _{1 to} R ₆ include alkyl groups such as methyl, ethyl, propyl and butyl, aryl groups such as phenyl, tolyl, naphthyl and biphenyl, and γ-glycidyl. Epoxy-containing groups such as xypropyl and β- (3,4-epoxycyclohexyl) ethyl, (meth) acryloyl-containing γ-acryloxypropyl and γ-methacryloxypropyl, γ-hydroxypropyl, 2,3-dihydroxy A hydroxyl group such as propyloxypropyl, a vinyl group such as vinyl and propenyl, a mercapto group such as γ-mercaptopropyl, an amino group such as γ-aminopropyl and N-β (aminoethyl) -γ-aminopropyl; γ-chloropropyl, 1,1,1-trifluoropropyl, nonafluorohexyl, perfluorooctylethyl And nitro and cyano-substituted alkyl groups. Further, R _{1 to} R ₆ may have the same or different organic groups.

In the present invention, the organosilicon compound used as a raw material of the siloxane-based resin having a structural unit having a charge transporting property and having a cross-linked structure generally has a hydrolyzable group bonded to a silicon atom. When the number n is 1, the polymerization reaction of the organosilicon compound is suppressed.
When n is 2, 3 or 4, a polymerization reaction is likely to occur, and especially when 3 or 4, the crosslinking reaction can be advanced to a high degree. Therefore, by controlling these, it is possible to control the preservability of the obtained coating layer liquid, the hardness of the coating layer, and the like.

Further, as a raw material of the polysiloxane curable resin, a hydrolyzed condensate obtained by hydrolyzing the organosilicon compound under acidic or basic conditions to oligomerize or polymerize can be used.

As described above, the siloxane-based resin of the present invention is obtained by reacting a monomer, oligomer, or polymer having a siloxane bond in a chemical structural unit in advance (hydrolysis reaction, reaction in which a catalyst or a crosslinking agent is added, etc.). (Included) means a resin that has formed and cured a three-dimensional network structure. That is, it means a polysiloxane resin formed by promoting a siloxane bond by a hydrolysis reaction and subsequent dehydration condensation of an organosilicon compound having a siloxane bond to form a three-dimensional network structure.

The siloxane-based resin may be a resin in which colloidal silica having a hydroxyl group or a hydrolyzable group is contained in the resin, and silica particles are incorporated in a part of the crosslinked structure.

In the present invention, the charge transport ability is defined by a known method capable of detecting the charge transport ability of the ordinary Time-Of-Flight method, in which a detection current caused by charge transport can be obtained. I can do it.

In the present invention, the siloxane-based resin having a structural unit having charge-transporting ability and having a crosslinked structure is a siloxane-based resin having a partial structure having charge-transporting ability. In other words, it is a resin in which a chemical structure having electron or hole drift transfer characteristics (= compound group having charge transport performance) is incorporated as a chemical structure in a siloxane-based resin. Specifically, the siloxane-based resin having a structural unit having charge transport performance and having a crosslinked structure according to the present invention refers to a compound generally used as a charge transport material (hereinafter, also referred to as a charge transport compound or CTM). It has a chemical structure in the siloxane-based resin.

A charge transporting compound capable of forming a compound group having a charge transporting performance as a partial structure in a siloxane-based resin by reaction with an organosilicon compound will be described below.

For example, hole transport type CTM: xazole, oxadiazole, thiazole, triazole, imidazole, imidazolone, imidazoline, bisimidazolidin, styryl, hydrazone, benzidine, pyrazoline,
Stilbene compound, amine, oxazolone, benzothiazole, benzimidazole, quinazoline, benzofuran, acridine, phenazine, aminostilbene, poly-N-vinylcarbazole, poly-1-vinylpyrene,
A chemical structure such as poly-9-vinylanthracene is contained as a partial structure of the siloxane-based resin.

On the other hand, electron transport type CTMs include succinic anhydride, maleic anhydride, phthalic anhydride, pyromellitic anhydride, melitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, nitrobenzene, dinitrobenzene, trinitrobenzene, Tetranitrobenzene, nitrobenzonitrile, picryl chloride, quinone chlorimide, chloranil, bromanyl, benzoquinone, naphthoquinone, diphenoquinone, tropoquinone, anthraquinone, 1-chloroanthraquinone, dinitroanthraquinone, 4-nitrobenzophenone, 4,4'-dinitrobenzophenone, 4-nitrobenzalmalonedinitrile, α-cyano-β- (p-cyanophenyl) -2-
(P-chlorophenyl) ethylene, 2,7-dinitrofluorene, 2,4,7-trinitrofluorenone, 2,
4,5,7-tetranitrofluorenone, 9-fluorenylidenedicyanomethylenemalononitrile, polynitro-9-fluoronylidenedicyanomethylenemalonodinitrile, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, 3, Chemical structures such as 5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, phthalic acid and melitic acid are contained as partial structures of the siloxane-based resin.

In the present invention, the compound group having a preferable charge transporting property includes a charge transporting compound which is usually used as described above, and via the carbon atom or silicon atom constituting the charge transporting compound or the charge transporting compound. It is present in the siloxane-based resin via a linking atom or a linking group of Y in the following formula via a carbon atom or a silicon atom of the compound having an acidic compound as a partial structure.

[0139]

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(In the formula, X is a compound group having charge transporting ability, a group bonding to Y in the formula via a carbon atom or a silicon atom constituting the compound group, and Y is an adjacent bonding atom ( It is a divalent or higher atom or group excluding Si and C). However, when Y is a trivalent or higher atom, the bond of Y other than Si and C in the above formula is capable of bonding. It has a structure (group) bonded to any constituent atom in the conductive resin or connected to another atom or molecular group.

In the above formula, an oxygen atom (O), a sulfur atom (S), and a nitrogen atom (N) are particularly preferable as the Y atom.

Here, when Y is a nitrogen atom (N), the linking group is represented by -NR- (R is a hydrogen atom or a monovalent organic group).

Although the charge transport-imparting group X is shown as a monovalent group in the above formula, two or more charge-transporting compounds (hereinafter also referred to as reactive charge-transporting compounds) to be reacted with the siloxane-based resin are used. When it has a reactive functional group, it may be bonded as a divalent or higher crosslink group in the curable resin, or may be bonded simply as a pendant group.

The above-mentioned atoms, ie, the atoms of O, S, and N, are formed by the reaction of a hydroxyl group, a mercapto group, or an amine group introduced into the charge transporting compound with an organic silicon compound having a hydroxyl group or a hydrolyzable group. And a linking group for incorporating a charge transport compound as a partial structure into a siloxane-based resin.

Next, the charge transporting compound having a hydroxyl group, a mercapto group, an amine group, and an organic silicon-containing group in the present invention will be described.

The charge transporting compound having a hydroxyl group is
It is a charge transport substance having a commonly used structure and a compound having a hydroxyl group. That is, typically, a charge transporting compound represented by the following general formula that can form a resin layer by bonding to a curable organosilicon compound can be exemplified, but is not limited to the following structure. Any compound having a charge transporting ability and a hydroxyl group may be used.

X- (R ₇ -OH) _m wherein X: a compound group having charge transporting ability, R ₇ : a single bond, a substituted or unsubstituted alkylene group, an arylene group, m: an integer of 1 to 5 is there.

Among them, the following are typical ones. For example, a triarylamine-based compound has a triarylamine structure such as triphenylamine as a compound group having charge transporting ability = X, and
A compound having a hydroxyl group via a carbon atom constituting or via an alkylene or arylene group extended from X is preferably used.

[0149] 1. Triarylamine compounds

[0150]

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2. Hydrazine compounds

[0152]

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3. Stilbene compounds

[0154]

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4. Benzidine compound

[0156]

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[0157] 5. Butadiene compound

[0158]

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6. Other compounds

[0160]

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Next, a synthesis example of a charge transporting compound having a hydroxyl group will be described.

Synthesis of Exemplified Compound T-1

[0163]

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Step A In a four-headed kolben equipped with a thermometer, a condenser, a stirrer, and a dropping funnel, 49 g of the compound (1) and phosphorus 184 chloride were added.
g was added and dissolved by heating. 117 g of dimethylformamide was gradually added dropwise from the dropping funnel.
The mixture was kept at ９５95 ° C. and stirred for about 15 hours. Next, the reaction solution was gradually poured into a large excess of warm water, and then slowly cooled with stirring.

After the precipitated crystals were filtered and dried, they were purified by adsorption of impurities with silica gel or the like and recrystallization with acetonitrile to obtain Compound (2). Yield 30
g.

Step B 30 g of compound (2) and 100 ml of ethanol were charged into a kolben and stirred. After gradually adding 1.9 g of sodium borohydride, the solution was kept at 40 to 60 ° C. and stirred for about 2 hours. Next, the reaction solution was gradually poured into about 300 ml of water and stirred to precipitate crystals. After filtration, the resultant was sufficiently washed with water and dried to obtain a compound (3). The yield was 30 g.

Synthesis of Exemplified Compound S-1

[0168]

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Step A: C was added to a 300 ml kolben equipped with a thermometer and a stirrer.
Then, 30 g of u, 60 g of K ₂ CO ₃ , 8 g of compound (1) and 100 g of compound (2) were added, and the mixture was heated to about 180 ° C. and stirred for 20 hours. After cooling, the mixture was filtered and purified by column to obtain 7 g of compound (3).

Step B A 100 ml kolben equipped with a thermometer, a dropping funnel, an argon gas introducing device and a stirrer was set to an argon gas atmosphere, and 7 g of the compound (3), 50 ml of toluene, and 3 g of phosphoryl chloride were added thereto. While stirring at room temperature, D
2 g of MF was slowly added dropwise, and then the temperature was raised to about 80 ° C. and the mixture was stirred for 16 hours. The mixture was poured into warm water of about 70 ° C. and cooled. This was extracted with toluene, and the extract was washed with water until the pH of the water reached 7. After drying over sodium sulfate, the mixture was concentrated and purified by column to obtain 5 g of compound (4).

Step C: 100 ml with an argon gas introducing device and a stirring device
1.0 g of t-BuOK and 60 ml of DMF were charged into the Kolben, and the atmosphere was changed to an argon gas atmosphere. Compound (4)
2.0 g and 2.2 g of the compound (5) were added, and the mixture was stirred at room temperature for 1 hour. This was poured into a large excess of water, extracted with toluene, the extract was washed with water, dried over sodium sulfate,
After concentration, column purification was performed, and 2.44 g of compound (6) was obtained.
I got

Step D Toluene was charged into a 100 ml kolben equipped with a thermometer, a dropping funnel, an argon gas introducing device and a stirring device, and an argon gas atmosphere was established. 15 ml of a hexane solution of n-BuLi (1.72 M) was added thereto, and the mixture was heated to 50 ° C. To this, 2.44 g of compound (6) was added in 30 ml of toluene.
The dissolved liquid was added dropwise, and the mixture was stirred at 50 ° C. for 3 hours. After cooling to −40 ° C., 8 ml of ethylene oxide was added, the temperature was raised to −15 ° C., and the mixture was stirred for 1 hour.
Thereafter, the temperature was raised to room temperature, 5 ml of water was added, and ether 2 was added.
After extraction with 00 ml, the extract was washed with saturated saline.
After washing the washing solution to pH, it was dried over sodium sulfate, concentrated and purified by column to obtain 1.0 g of compound (7).

Next, specific examples of the charge transporting compound having a mercapto group are shown below.

The charge transporting compound having a mercapto group is a charge transporting substance having a commonly used structure and a compound having a mercapto group. That is, typically, a charge transporting compound represented by the following general formula that can form a resin layer by bonding to a curable organosilicon compound can be exemplified, but is not limited to the following structure. Any compound may be used as long as it has a charge transporting ability and a mercapto group.

X- (R ₈ -SH) _m wherein X: a compound group having charge transporting ability, R ₈ : single bond, substituted or unsubstituted alkylene, arylene group, m: an integer of 1 to 5 .

Among them, the following are typical ones.

[0177]

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Further, the charge transporting compound having an amino group will be described.

The charge transporting compound having an amino group is a charge transporting substance having a commonly used structure and a compound having an amino group. That is, typically, a charge transporting compound represented by the following general formula that can form a resin layer by bonding to a curable organosilicon compound can be exemplified, but is not limited to the following structure. Any compound having a charge transporting ability and having an amino group may be used.

X- (R ₉ -NR ₁₀ H) _m wherein X: a compound group having charge transport performance R ₉ : a single bond, a substituted or unsubstituted alkylene, a substituted or unsubstituted arylene group, R ₁₀ : A hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, m: an integer of 1 to 5;

[0181] Among them, the following are typical ones.

[0182]

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Among the charge transporting compounds having an amino group, in the case of a primary amine compound (—NH ₂ ), two hydrogen atoms may react with an organosilicon compound and be linked to a siloxane structure. In the case of a secondary amine compound (—NHR ₁₀ ), one hydrogen atom reacts with the organosilicon compound, and R ₁₀ may be a group that remains as a branch or a group that causes a cross-linking reaction, and includes a charge transport material. It may be a compound residue.

Further, the charge transporting compound having a silicon atom-containing group will be described.

The charge transporting compound having a silicon atom-containing group is a charge transporting substance having the following structure. This compound is contained as a partial structure in the siloxane-based resin via a silicon atom in the compound.

X-(-Y-Si (R ₁₁ ) _{3 -a} (R ₁₂ ) _a ) _n (wherein X is a group containing a structural unit having charge transport performance, R ₁₁ is a hydrogen atom, R ₁₂ represents a hydrolyzable group or a hydroxyl group, Y represents a substituted or unsubstituted alkylene group or an arylene group, a represents an integer of 1 to 3, and n represents Represents an integer.) Among them, there are the following as typical examples.

[0187]

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The raw material of the siloxane-based resin, that is, the organosilicon compound of the general formulas (A) to (D) (hereinafter referred to as (A) to (D)) has the following composition ratio:
It is preferable to use 0.05 to 1 mol of the (C) + (D) component per 1 mol of the (A) + (B) component.

When colloidal silica (E) is added, 1 to 30 parts by weight of (E) is used based on 100 parts by weight of the total of components (A) + (B) + (C) + (D). Is preferred.

When the reactive charge transporting compound (F) capable of forming a resin layer by reacting with the organosilicon compound or colloidal silica is added, the above (A) +
It is preferable to use 1 to 500 parts by weight of (F) based on 100 parts by total weight of the components (B) + (C) + (D). When the amount of the components (A) and (B) is small, the siloxane-based resin layer has too low a crosslinking density and insufficient hardness. Also, (A) +
If the component (B) is too large, the crosslink density is too high and the hardness is sufficient, but a brittle resin layer is formed. Excess or deficiency of the colloidal silica component of the component (E) has the same tendency as that of the component (A) + (B). On the other hand, when the amount of the component (F) is small, the charge transporting ability of the siloxane-based resin layer is small, causing a decrease in sensitivity and an increase in residual charge. When the amount of the component (F) is large, the film strength of the siloxane-based resin layer is weakened. There is a tendency.

The siloxane-based resin of the present invention may form a three-dimensional network structure by forming a new chemical bond by adding a catalyst or a crosslinking agent to a monomer, oligomer or polymer having a siloxane bond in the structural unit in advance. A siloxane bond can be promoted by a hydrolysis reaction and a subsequent dehydration condensation to form a three-dimensional network structure from monomers, oligomers and polymers.

In general, a three-dimensional network structure can be formed by a condensation reaction of a composition containing an alkoxysilane or a composition containing an alkoxysilane and colloidal silica.

Examples of the catalyst for forming the three-dimensional network structure include alkali metal salts of organic carboxylic acids, nitrous acid, sulfurous acid, aluminate, carbonic acid and thiocyanic acid, and organic amine salts (tetramethylammonium hydroxide, tetramethylammonium). Ammonium acetate), tin organic acid salts (stannas octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin malate), aluminum, zinc octenoic acid, naphthenate, An acetylacetone complex compound is exemplified.

Further, an antioxidant having a hindered phenol, hindered amine, thioether or phosphite partial structure can be added to the resin layer in the present invention.
This is effective in improving the potential stability and image quality when the environment changes.

Here, hindered phenol refers to compounds having a branched alkyl group at the ortho position to the hydroxyl group of the phenol compound and derivatives thereof (however, the hydroxyl group may be modified to alkoxy).

Examples of the hindered amine include compounds having an organic group represented by the following structural formula.

[0197]

Embedded image

(In the formula, R ₁₃ represents a hydrogen atom or a monovalent organic group, R ₁₄ , R ₁₅ , R ₁₆ , and R ₁₇ represent an alkyl group, and R ₁₈ represents a hydrogen atom, a hydroxyl group, or a monovalent organic group. Examples of the antioxidant having a hindered phenol partial structure include, for example, JP-A-1-118137 (P7 to P14).
The compounds described above are included, but the present invention is not limited thereto.

As the antioxidant having a hindered amine partial structure, for example, JP-A-1-118138 (P7-
The compounds described in P9) may also be mentioned, but the present invention is not limited thereto.

The following compounds are commercially available antioxidants, for example, “Irganox 107”.
6, Irganox 1010, Irganox 1098, Irganox 245, Irganox 1330, Irganox 3114, Irganox 1076, 3,5-di-t-butyl-4 −
Hydroxybiphenyl or higher hindered phenol type,
"Sanol LS2626", "Sanol LS765"
"Sanol LS2626", "Sanol LS770",
“Sanol LS744”, “Tinuvin 144”, “Tinuvin 622LD”, “Mark LA57”, “Mark LA”
67 "," Mark LA62 "," Mark LA68 ",
"Mark LA63" or higher, hindered amine type, "Sumilyzer-TPS", "Sumilyzer TP-D" or higher, thioether type, "Mark 2112", "Mark PEP-"
8 "," Mark PEP-24G "," Mark PEP-3 "
6 "," Mark 329K "," Mark HP-10 "or higher phosphites. Among these, hindered phenol and hindered amine antioxidants are particularly preferred. It is preferable to use 0.1 to 10 parts by weight of the antioxidant based on 100 parts by weight of the total resin layer composition.

The layer constitution of the electrophotographic photoreceptor of the present invention is not particularly limited, but may be a charge generation layer, a charge transport layer, or a charge generation / charge transport layer (a single layer having both functions of charge generation and charge transport). It is preferable to adopt a structure in which a photosensitive layer such as a photosensitive layer) and a resin layer of the present invention are provided thereon. Further, each of the charge generation layer, the charge transport layer, or the charge generation / charge transport layer may be composed of a plurality of layers.

Examples of the charge generating substance (CGM) contained in the photosensitive layer according to the present invention include phthalocyanine pigments, polycyclic quinone pigments, azo pigments, perylene pigments, indigo pigments, quinacridone pigments, azurenium pigments, squalilium dyes, cyanine dyes And a pyrylium dye, a thiopyrylium dye, a xanthene dye, a triphenylmethane dye, a styryl dye, and the like. These charge generating substances (CGM) are used alone or in combination with a suitable binder resin to form a layer.

The charge transport material (C) contained in the photosensitive layer
TM) include, for example, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidazolone derivatives, imidazoline derivatives, bisimidazolidine derivatives, styryl compounds, hydrazone compounds, benzidine compounds, pyrazoline derivatives, stilbenes Compound,
Amine derivatives, oxazolone derivatives, benzothiazole derivatives, benzimidazole derivatives, quinazoline derivatives, benzofuran derivatives, acridine derivatives, phenazine derivatives, aminostilbene derivatives, poly-N-vinylcarbazole, poly-1-vinylpyrene, poly-9-vinylanthracene, etc. These charge transport materials (CTM) are usually used to form a layer together with a binder.

As the binder resin contained in the charge generating layer (CGL) and the charge transport layer (CTL) in the case of the single-layered photosensitive layer and the laminated structure, polycarbonate resin, polyester resin, polystyrene resin, methacrylic resin,
Acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl butyral resin, polyvinyl acetate resin, styrene-butadiene resin, vinylidene chloride-acrylonitrile copolymer resin, vinyl chloride-maleic anhydride copolymer resin, urethane resin, silicone Resins, epoxy resins, silicone-alkyd resins, phenol resins, polysilane resins, polyvinyl carbazole, and the like.

In the present invention, the ratio between the charge generating substance and the binder resin in the charge generating layer is from 1:10 to 1 by weight.
0: 1 is preferred. The thickness of the charge generation layer is preferably 5 μm or less, and particularly preferably 0.05 to 2 μm.

The charge transport layer is formed by dissolving the charge transport material and the binder resin in a suitable solvent, and applying and drying the solution. The mixing ratio of the charge transport material and the binder resin is preferably from 10: 1 to 1:10 by weight.

The thickness of the charge transport layer is usually from 5 to 50 μm, particularly preferably from 10 to 40 μm. When a plurality of charge transport layers are provided, the thickness of the upper layer of the charge transport layer is 10
μm or less, and preferably smaller than the total thickness of the charge transport layer provided below the charge transport layer.

When the surface layer is a charge transport layer, the siloxane-based resin layer of the present invention may double as the charge transport layer.
Preferably, it is preferably provided on a photosensitive layer such as a charge transporting layer, a charge generating layer, or a single layer type charge generating / transporting layer as a surface layer separate from these layers. In this case, an adhesive layer may be provided between the photosensitive layer and the resin layer of the present invention.

Next, the electroconductive support of the electrophotographic photoreceptor of the present invention includes: 1) a metal plate such as an aluminum plate or a stainless steel plate; 2) a support such as paper or a plastic film;
A thin metal layer such as aluminum, palladium, or gold provided by lamination or vapor deposition. 3) On a support such as paper or plastic film,
Examples thereof include those in which a layer of a conductive compound such as a conductive polymer, indium oxide, or tin oxide is provided by coating or vapor deposition.

The material of the conductive support used in the present invention is mainly aluminum, copper, brass, steel,
A belt-shaped or drum-shaped metal material such as stainless steel or another plastic material is used. Among them, aluminum excellent in cost, workability and the like is preferably used, and a thin-walled cylindrical aluminum tube usually formed by extrusion or drawing is often used.

The solvent or dispersion medium used in the production of the photoreceptor of the present invention includes n-butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N, N-dimethylformamide, acetone, methylethylketone,
Methyl isopropyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, dichloromethane, 1,2-dichloroethane, 1,2-dichloropropane, 1,1,2-trichloroethane, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethane, Tetrahydrofuran, dioxolan, dioxane,
Methanol, ethanol, butanol, isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide,
Methyl cellosolve and the like. Although the present invention is not limited to these, dichloromethane, 1,2-dichloroethane, methyl ethyl ketone and the like are preferably used. In addition, these solvents can be used alone or as a mixed solvent of two or more kinds.

The coating method for producing the electrophotographic photosensitive member of the present invention includes dip coating, spray coating,
Coating methods such as circular amount control type coating are used, but the coating process on the surface layer side of the photosensitive layer is spray coating or circular amount control type in order to minimize dissolution of the lower layer film and to achieve uniform coating processing. (A typical example is the circular slide hopper type.)
It is preferable to use a coating method such as coating. The spray coating is described in detail in, for example, JP-A-3-90250 and JP-A-3-269238,
The circular amount control type coating is described in, for example, JP-A-58-1.
It is described in detail in JP-A-89061.

After the resin layer is coated and formed, the photoreceptor of the present invention is preferably dried by heating at a temperature of 50 ° C. or higher, preferably 60 to 200 ° C. By this heating and drying, the residual coating solvent can be reduced and the resin layer can be sufficiently cured.

In the present invention, it is preferable to provide an intermediate layer having a barrier function between the conductive support and the photosensitive layer.

Examples of the material for the intermediate layer include casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyvinyl butyral, and phenol resin polyamides (nylon 6, nylon 66, nylon 610, copolymer nylon, alkoxymethyl And an intermediate layer using polyurethane, gelatin, and aluminum oxide, or a hardening intermediate layer using a metal alkoxide, an organic metal chelate, or a silane coupling agent as described in JP-A-9-68870. The thickness of the intermediate layer is preferably from 0.1 to 10 μm, particularly preferably from 0.1 to 10 μm.
5 μm is preferred.

In the present invention, a coating for compensating for surface defects of the support is provided between the support and the intermediate layer. A conductive layer for the purpose of preventing generation and the like can be provided. This conductive layer is made of carbon black,
It can be formed by applying and drying a solution in which conductive powder such as metal particles or metal oxide particles is dispersed in a suitable binder resin. The thickness of the conductive layer is preferably 5 to 40 μm, particularly preferably 10 to 30 μm.

The electrophotographic photoreceptor of the present invention can be applied to general electrophotographic devices such as copiers, laser printers, LED printers, and liquid crystal shutter printers. It can be widely applied to devices such as light printing, plate making, and facsimile.

Next, the cleaning mechanism used in the present invention will be described.

FIG. 1 is a sectional view showing an example of the cleaning mechanism used in the present invention.

In the present invention, preferable values of the contact load P and the contact angle θ of the cleaning blade to the photoreceptor are P = 5 to 40 g / cm and θ = 5 to 35 °.

The free length L of the cleaning blade represents the length from the end of the support member 3 to the tip of the blade before deformation, as shown in FIG. A preferred value of the free length is L = 3 to 15 mm. The thickness of the cleaning blade is preferably 0.5 to 10 mm.

The contact load P is a normal direction vector value of the pressing force P 'when the cleaning blade 2 is brought into contact with the photosensitive drum 1.

The contact angle θ is the angle between the tangent X at the contact point A of the photosensitive member and the blade before deformation (indicated by a dotted line in the drawing).

As the material of the elastic rubber blade used in the blade cleaning method, urethane rubber, silicone rubber, fluorine rubber, chloropyrene rubber, butadiene rubber and the like are known. Of these, urethane rubber is other rubber. It is particularly preferred in that it has excellent wear characteristics as compared with For example, urethane rubber obtained by reacting and curing a polycaprolactone ester and a polyisocyanate described in JP-A-59-30574 is preferable.

By simultaneously controlling the hardness and the rebound resilience among the physical properties of the elastic rubber blade, the reversal of the blade can be more effectively suppressed. When the JISA hardness of the blade at 25 ± 5 ° C. is smaller than 65, the blade is easily inverted, and when it is larger than 80, the cleaning performance is reduced. If the rebound resilience exceeds 75%, reversal of the blade tends to occur. If the rebound resilience is less than 20%, the cleaning performance deteriorates (both JISA hardness and rebound resilience are measured based on the vulcanized rubber physical test method of JIS K6301).

FIG. 2 is a sectional view showing an example of an image forming apparatus having the electrophotographic photosensitive member of the present invention.

In FIG. 2, reference numeral 10 denotes a photosensitive drum (photoreceptor) serving as an image carrier, and an organic photosensitive layer is applied on the drum.
A photoreceptor coated with the resin layer of the present invention thereon is grounded and driven to rotate clockwise. Reference numeral 12 denotes a scorotron charger, which applies uniform charging to the peripheral surface of the photosensitive drum 10 by corona discharge. Prior to the charging by the charger 12, in order to eliminate the history of the photoconductor in the previous image formation, exposure by the exposure unit 11 using a light emitting diode or the like may be performed to remove electricity from the peripheral surface of the photoconductor.

After the photosensitive member is uniformly charged, the image exposing unit 13 performs image exposure based on the image signal. The image exposure device 13 in this figure uses a laser diode (not shown) as an exposure light source. The light on the photosensitive drum is scanned by the light whose optical path is bent by the reflection mirror 132 through the rotating polygon mirror 131, the fθ lens, and the like, and an electrostatic latent image is formed.

Next, the electrostatic latent image is developed by the developing device 14. At the periphery of the photoconductor drum 10, developing devices 14 each containing a developer having a toner and a carrier such as yellow (Y), magenta (M), cyan (C), and black (K) are provided. The color development is performed by a developing sleeve 141 which rotates with a built-in magnet and holding a developer. The developer comprises, for example, a carrier in which an insulating resin is coated around a ferrite core, and a toner in which a pigment corresponding to a color and a charge control agent, silica, titanium oxide, etc. are added using polyester as a main material. The developer is regulated to a layer thickness of 100 to 600 μm on the developing sleeve 141 by a layer forming means (not shown), and is conveyed to a developing area to be developed. At this time, normally, a DC and / or AC bias voltage is applied between the photosensitive drum 10 and the developing sleeve 141 to perform the development.

In the color image formation, after the visualization of the first color is completed, the image forming process for the second color is started, the uniform charging is again performed by the scorotron charger 12, and the latent image of the second color is transferred to the image exposing device. 13. An image forming process similar to that for the second color is performed for the third color and the fourth color, and a visible image of four colors is formed on the peripheral surface of the photosensitive drum 10.

On the other hand, in a monochrome electrophotographic apparatus, the developing device 1
Reference numeral 4 is composed of one kind of black toner and can form an image by one development.

After the image is formed, the recording paper p is fed to the transfer area by the rotation of the paper feed roller 17 at the time when the transfer timing is adjusted.

In the transfer area, a transfer roller (transfer device) 1 is mounted on the peripheral surface of the photosensitive drum 10 in synchronization with the transfer timing.
8, the multicolor image is transferred collectively by sandwiching the fed recording paper p.

Next, the recording paper p is neutralized by a separation brush (separator) 19 which is brought into pressure contact with the transfer roller almost at the same time, separated by the peripheral surface of the photosensitive drum 10, conveyed to a fixing device 20, and heated by a heat roller. 201 and pressure roller 2
After the toner is welded by heating and pressurizing 02, the toner is discharged to the outside of the apparatus via the discharge roller 21. The transfer roller 18 and the separation brush 19 are retracted and separated from the peripheral surface of the photosensitive drum 10 after passing the recording paper p to prepare for the formation of the next toner image.

On the other hand, the photosensitive drum 10 from which the recording paper p has been separated is
The residual toner is removed and cleaned by the pressure contact of the cleaning roller 222 and the cleaning roller 222, and the next image forming process is started upon receiving the charge removal by the exposure unit 11 and the charge by the charger 12 again. When a color image is formed on the photoconductor by superimposition, the blade 221 moves immediately after the cleaning of the photoconductor surface and retreats from the peripheral surface of the photoconductor drum 10.

Reference numeral 30 denotes a detachable process cartridge in which a photosensitive member, a charger, a transfer device / separator and a cleaning device are integrated.

An electrophotographic image forming apparatus is configured by integrally combining the above-described photosensitive member, a developing unit, a cleaning unit, and other components as a process cartridge, and this unit is configured to be detachable from the apparatus main body. You may.
Also, a process cartridge is formed by integrally supporting at least one of a charger, an image exposing unit, a developing unit, a transfer or separating unit, and a cleaning unit together with a photoreceptor. It may be configured to be detachable using a guide means such as a rail of the apparatus body.

When the image forming apparatus is used as a copying machine or a printer, the image exposure is performed by irradiating the photosensitive member with reflected light or transmitted light from the original, or by reading the original with a sensor and converting it into a signal. Scanning of a laser beam, driving of an LED array, or driving of a liquid crystal shutter array is performed by irradiating the photosensitive member with light.

When used as a facsimile printer, the image exposure unit 13 performs exposure for printing received data.

The electrophotographic photoreceptor of the present invention can be applied to general electrophotographic devices such as copiers, laser printers, LED printers, and liquid crystal shutter printers. It can be widely applied to devices such as light printing, plate making, and facsimile.

[0241]

Next, embodiments of the present invention will be specifically described, but the present invention is not limited to these embodiments. In the description, “parts” means “parts by weight”.

Preparation of Colored Particle 1 Styrene = 165 g, n-butyl acrylate = 35
g, carbon black = 20 g, methacrylic acid = 8 g,
20 g of low molecular weight polypropylene was dispersed by a sand grinder while heating to 30 ° C. Next, 2.5 g of 2,2'-azobis (2,4-valeronitrile) was added and dissolved as a polymerization initiator to prepare a polymerizable monomer composition. Then, 0.1 M was added to 710 g of ion-exchanged water.
450 g of an aqueous solution of sodium phosphate was added, and 68 g of 1.0 M calcium chloride was gradually added while stirring at 12,000 rpm with a TK homomixer to prepare a suspension in which tricalcium phosphate was dispersed. The polymerizable monomer composition was added to the suspension, and the mixture was subjected to 10,000 r with a TK homomixer.
After stirring at pm for 20 minutes, the polymerizable monomer composition was dispersed in an aqueous medium, and dispersed in droplets having an average particle size of about 8 μm. Thereafter, the reaction was carried out at 75 ° C. for 10 hours. After cooling, hydrochloric acid was added to dissolve and remove the tricalcium phosphate, followed by filtration, washing and drying to obtain colored particles having a volume average particle size of 7.9 μm. This is referred to as “colored particle 1”.

Preparation of Colored Particles 2 0.90 kg of sodium n-dodecyl sulfate and pure water 1
Add 0.0L and dissolve with stirring. To this solution, with stirring, Regal 330R (carbon black manufactured by Cabot Corporation)
Add 20 kg slowly and stir well for 1 hour after addition. Then, using a sand grinder (medium type disperser),
The dispersion was continued for 20 hours.

After the dispersion, the particle diameter of the dispersion was measured using an electrophoretic light scattering photometer ELS-800 manufactured by Otsuka Electronics Co., Ltd., and as a result, the weight average diameter was 122 nm. The solid content of the dispersion was 16.6 wt% as measured by a static drying method. This dispersion is referred to as “colorant dispersion 1”.

0.055 kg of sodium dodecylbenzenesulfonate was added, and 4.0 L of ion-exchanged water was added.
Stir and dissolve at room temperature. This is designated as an anionic surfactant solution A.

Polyoxyethylene phenyl ether
Add 014 kg, add 4.0 L of ion-exchanged water and stir and dissolve at room temperature. This is designated as nonionic surfactant solution A.

223.8 g of potassium persulfate was added, 12.0 L of ion-exchanged water was added, and the mixture was stirred and dissolved at room temperature. This is designated as initiator solution A.

A reaction vessel equipped with a thermometer, a cooling pipe and a nitrogen introducing device was charged with a wax emulsion (polypropylene emulsion having a number average molecular weight of 3000: number average primary particle diameter = 12).
(0 nm / solid concentration = 29.9%), 3.41 kg, anionic surfactant solution A, nonionic surfactant solution A, and 44.0 L of ion-exchanged water are added and stirred.

The heating is started, and when the liquid temperature reaches 75 ° C., the initiator solution A is added. Thereafter, the liquid temperature is reduced to 7
While controlling the temperature at 5 ° C. ± 1 ° C., 12.1 kg of styrene, 2.88 kg of n-butyl acrylate and 1.0 methacrylic acid were added.
A solution in which 4 kg and 548 g of t-dodecyl mercaptan are uniformly dissolved is charged.

Further, the liquid temperature was raised to 80 ° C. ± 1 ° C.
Heating and stirring were performed for 6 hours.

The temperature of the solution is cooled to 40 ° C. or less, and the stirring is stopped. The mixture was filtered through a pole filter, and this was mixed with latex A1
And

The glass transition temperature of the resin particles in the latex A1 was 57 ° C., the softening point was 121 ° C., and the molecular weight distribution was weight average molecular weight = 1270,000 and weight average particle size was 12
It was 0 nm.

200.7 g of potassium persulfate was added, and 12.0 liters of ion-exchanged water was added. This is designated as initiator solution B.

A WAX emulsion (polypropylene emulsion having a number average molecular weight of 3000: number average primary particle diameter = 12) was placed in a reaction vessel equipped with a thermometer, a cooling pipe, and a nitrogen introducing device.
(0 nm / solids concentration 29.9%) 3.41 kg, anionic surfactant solution A and nonionic surfactant solution A are added, and stirring is started. Then, ion-exchanged water 44.0
1 is input.

The heating is started, and when the liquid temperature reaches 70 ° C., the initiator solution B is added. At this time, styrene 1
1.0 kg, 4.00 kg of n-butyl acrylate, 1.04 kg of methacrylic acid, and t-dodecyl mercaptan 9.
And a solution obtained by previously mixing 02 g with the mixture.

Thereafter, the liquid temperature was controlled at 72 ° C. ± 2 ° C., and the mixture was heated and stirred for 6 hours. Further, the liquid temperature is set to 80 ° C.
The temperature was raised to ± 2 ° C., and the mixture was heated and stirred for 12 hours.

The liquid temperature is cooled to 40 ° C. or less, and the stirring is stopped. The solution was filtered through a pole filter, and the filtrate was used as latex B1.

The glass transition temperature of the resin particles in the latex B1 was 58 ° C., the softening point was 132 ° C., and the molecular weight distribution was weight average molecular weight = 245,000 and weight average particle diameter was 11
It was 0 nm.

Sodium chloride as salting-out agent 5.36k
The aqueous solution consisting of g and ion-exchanged water 20.0 L is referred to as a sodium chloride solution A.

In a reaction vessel equipped with a thermometer, a cooling pipe and a nitrogen introducing device, the latex A1 prepared above was 20.0 kg.
And latex B1 = 5.2 kg and colorant dispersion 1 = 0.
4 kg and 20.0 kg of ion-exchanged water are added and stirred.
Then, the mixture was heated to 40 ° C., and sodium chloride solution G, 6.00 kg of isopropanol, nonionic surfactant solution A
Are added in this order. Then, after leaving for 10 minutes,
The temperature is raised and the temperature is raised to 85 ° C. in 60 minutes. The mixture is heated and stirred at a liquid temperature of 85 ° C. ± 2 ° C. for 6 hours to cause salting out / fusion. Thereafter, the mixture is cooled to 40 ° C. or lower and the stirring is stopped.
The solution is filtered through a sieve having an opening of 45 μm, and this filtrate is used as an association liquid.

Next, the wet cake-like colored particles were collected by filtration from the associated liquid using a Nutsche. Thereafter, the substrate was washed with ion-exchanged water.

The wet cake-like colored particles, which had been washed as described above, were taken out of the nutsche and dried on a shelf at 40 ° C. for 100 hours using a blow dryer.

The dried colored particles in the form of a block are
Crushed with a Henschel mill.

The colored particles obtained as described above are referred to as “colored particles 2”. In addition, the molecular weight of the resin particles which are the components of the “colored particles 2” was such that the weight average molecular weight was 55,000, the softening point was 125 ° C., the glass transition temperature was 57 ° C., and the volume average particle size was 5.8 μm. .

Preparation of Colored Particle 3 Styrene acrylic resin = 100 parts, carbon black 1
0 parts, low molecular weight polypropylene (number average molecular weight = 300
0) = 4 parts were melted, kneaded and pulverized to obtain colored particles having a volume average particle size of 6.9 μm. These particles are referred to as “colored particles 3”.

With respect to the above colored particles 1 to 3, the following Table 1
Add the external additives shown in Table 2 and add 3 with a Henschel mixer.
The toner was mixed under a rotation condition of 0 m / sec.

[0267]

[Table 1]

[0268]

[Table 2]

Preparation of Developer A developer comprising the following toner and carrier was prepared.

Further, a developer having a toner concentration of 6% was prepared by mixing each of the above “Toner 1” to “Toner 16” with a ferrite carrier coated with a styrene acrylic resin and having a volume average particle diameter of 45 μm. Used for evaluation. This developer is referred to as “developer 1” to “developer 16” corresponding to the toner.

Preparation of Photoreceptor Preparation of Photoreceptor 1 As a conductive support, surface roughness Rz (ten-point average roughness) =
An aluminum support having a size of 1.5 μm, a diameter of 80 mm and a height of 355 mm was used.

<Intermediate Layer> Titanium chelate compound (TC-750: manufactured by Matsumoto Pharmaceutical Co., Ltd.) 30 g Silane coupling agent 17 g 2-propanol 150 ml was mixed and dissolved to prepare an intermediate layer coating solution. This coating solution is applied on a cylindrical aluminum substrate by a dip coating method,
After drying at 120 ° C. for 1 hour, an intermediate layer having a thickness of 1.0 μm was formed.

<Charge Generating Layer> Titanyl phthalocyanine (60 g) Silicone resin solution (KR5240, 15% xylene-butanol solution: manufactured by Shin-Etsu Chemical Co., Ltd.) 700 g 2-butanone (2,000 ml) were mixed and dispersed using a sand mill for 10 hours. A coating solution was prepared. This coating solution was applied on the intermediate layer by a dip coating method to form a 0.2 μm-thick charge generation layer.

<Charge Transport Layer> Charge transport substance (4-methoxy-4 '-(4-methyl-α-phenylstyryl) triphenylamine) 200 g Bisphenol Z-type polycarbonate (Iupilon Z300: manufactured by Mitsubishi Gas Chemical Company) 300 g 1 , 2-Dichloroethane (2,000 ml) was mixed and dissolved to prepare a charge transport layer coating solution. This coating solution was applied on the charge generation layer by a dip coating method to form a charge transport layer having a dry film thickness of 25 μm.

<Resin Layer> Trimethoxymethylsilane 180 g 1-butanol 280 ml 1% acetic acid aqueous solution 106 ml was mixed and stirred at 60 ° C. for 2 hours, and then 370 m
1-butanol was added and stirring was continued for 48 hours.

To this were added 67.5 g of dihydroxymethyltriphenylamine (Exemplified Compound T-1), 1.7 g of an antioxidant (Sanol LS2626: manufactured by Sankyo) and 4.5 g of dibutyltin acetate, and mixed. Was applied as a resin layer having a dry film thickness of 1 μm, and was heated and cured at 120 ° C. for 1 hour to produce a photoreceptor 1.

Preparation of Photoreceptor 2 Next, the photoreceptor 1 was replaced with 4- [2- (triethoxysilyl) ethyl] triphenylamine in place of dihydroxytriphenylamine (T-1) in the resin layer. Photoconductor 2 was prepared in the same manner as for photoconductor 1.

Preparation of Photoreceptor 3 Next, Photoreceptor 3 was prepared in the same manner as for Photoreceptor 1, except that dihydroxytriphenylamine (T-1) in the resin layer was removed.

Evaluation The photoreceptors and toners produced as described above were combined as shown in Tables 3 and 4 and evaluated using a digital copying machine “Konica 7050”.

Digital copying machine "Konica 7050"
Adopts a semiconductor laser exposure and reversal development process, and has respective steps of charging, exposure, development, transfer, cleaning, and erasure exposure around the photosensitive member as shown in FIG. The cleaning conditions were as follows. That is, a polyurethane elastic rubber blade having a rubber hardness of JISA 70 °, a rebound resilience of 25, a thickness of 2 mm, and a free length of 9 mm is used with a contact angle of 2 mm.
At 0 °, the photosensitive member was brought into contact with the rotation of the photosensitive member in a counter direction at a pressing force of 20 g / cm by a weight load method.

Incidentally, the developing conditions for the above image evaluation were set under the following conditions.

DC bias; -500 V Dsd (distance between photoconductor and developing sleeve); 600 μm Developer layer regulation; Magnetic H-Cut method Developer layer thickness: 700 μm Developing sleeve diameter: 40 mm Pixel rate under the above evaluation conditions Is 7% character image (A4)
Using the original image of No. 1, a copy image was prepared on a print of 50,000 sheets in a single-sheet intermittent mode under a high temperature and high humidity condition of 35 ° C./80% RH. However, every 10,000 sheets were left for 12 hours.

As an image quality evaluation, a halftone, a solid white image, and a solid black image were printed at the end of 10,000 sheets and after standing for 12 hours, and the maximum image density, fog, and presence or absence of image deletion were evaluated. Further, as an evaluation of cleaning performance, the presence or absence of image defects such as streaks, white or black spots (having a diameter of 0.3 mmφ or more), the presence or absence of deposits on the photoconductor surface, and the amount of cleaning blade edge abrasion were evaluated.

The image density was determined by measuring the absolute reflection density of five solid black images using RD-918 manufactured by Macbeth, and the average value was obtained. For the fog density, a solid white image was measured using a reflection density meter RD-918 manufactured by Macbeth Co., Ltd., and the reflection density of the paper was set to "0".

FIG. 3 is a schematic diagram for explaining a method of measuring the cleaning blade edge wear amount. As shown in FIG. 3, the cleaning blade edge abrasion amount 44 is measured from an image obtained by enlarging the edge portion using an optical or laser microscope. That is, the amount of wear at the blade edge tip after printing 50,000 sheets from the initial edge tip is measured. Regarding the abrasion of the edge, the abrasion amount in terms of 10,000 sheets was shown.

In FIG. 3, reference numeral 41 denotes a photosensitive drum, reference numeral 42 denotes a cleaning blade, reference numeral 43 denotes a blade supporting plate, and reference numeral 44 denotes an edge wear amount.

The evaluation results are shown in Table 5, Table 6, Table 7, and Table 8.

[0288]

[Table 3]

[0289]

[Table 4]

[0290]

[Table 5]

[0291]

[Table 6]

[0292]

[Table 7]

[0293]

[Table 8]

From Table 5, Table 6, Table 7, and Table 8, it can be seen that in the embodiment satisfying the requirements of the present invention, in the actual photographing test of 50,000 sheets,
Even in a copying test under high temperature and high humidity conditions, the image quality such as density and fog is good, and image defects due to poor cleaning such as image deletion, streaks and spots are remarkably improved, and a clearly excellent image is obtained. ing.

[0295]

According to the present invention, an organic electrophotographic photoreceptor having a small amount of wear is combined with a developer having a toner to which a specific external additive is added, so that image blur and streaks can be obtained even in a high temperature and high humidity environment. It is possible to provide an image forming method, an image forming apparatus, and a developer used for the image forming apparatus, which can prevent the occurrence of image defects in a shape of a spot or a spot and obtain a copy image of high durability and high quality.

[Brief description of the drawings]

FIG. 1 is a sectional view of an example of a cleaning mechanism used in the present invention.

FIG. 2 is a cross-sectional view illustrating an example of an image forming apparatus having the electrophotographic photosensitive member of the present invention.

FIG. 3 is a schematic diagram illustrating a method for measuring a cleaning blade edge wear amount.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 photosensitive drum 2 cleaning blade 3 support member 4 pressing spring 5 fulcrum θ contact angle L free length P contact load 10 photosensitive drum (or photosensitive member) 11 exposure unit using light emitting diode 12 charging unit 13 image exposure Device 14 Developing device 17 Paper feed roller 18 Transfer roller (transfer device) 19 Separation brush (separator) 20 Fixing device 21 Paper discharge roller 22 Cleaning device 30 Process cartridge 41 Photoconductor drum 42 Cleaning blade 43 Blade supporting plate 44 Edge wear amount

Continuing from the front page (72) Inventor Hiroyuki Kozuru 2970, Ishikawacho, Hachioji-shi, Tokyo Konica Corporation (72) Inventor Sayuri Kushika 2970, Ishikawacho, Hachioji-shi, Tokyo Konica Corporation (72) Inventor Akihiko Itami Tokyo 2970 Ishikawacho, Hachioji-shi, Tokyo Konica Corporation F term (reference) 2H005 AA08 CB07 CB13 EA05 EA07 2H068 AA02 AA04 AA05 AA20 AA21 BA58 BB32 BB33 BB49 BB57 EA12 FC08 2H077 AD36 EA03 EA13 FA14 EA14

Claims (10)

[Claims] An image forming method for developing a latent image on an electrophotographic photosensitive member with a developer, transferring a visualized toner image to a recording material, and cleaning the toner remaining on the photosensitive member, The electrophotographic photoreceptor is an electrophotographic photoreceptor having a resin layer containing a siloxane-based resin having a cross-linked structure, having a structural unit having charge transport performance on a conductive support, and When the toner used is colored particles having a number average primary particle diameter of at least 201 to 2000
An image forming method, characterized in that the toner is formed by adding 0.1 to 3.0% by weight of fine particles of nm. 2. The siloxane-based resin having a structural unit having a charge-transporting performance and having a cross-linking structure is a siloxane-based resin having a compound group having a charge-transporting performance as a partial structure. 2. The image forming method according to 1. 3. The method according to claim 1, wherein the siloxane-based resin having the structural unit having charge transporting performance and having a cross-linking structure reacts an organosilicon compound having a hydroxyl group or a hydrolyzable group with a charge transporting compound having a hydroxyl group. The image forming method according to claim 1, wherein the image forming method is obtained. 4. An image having a cleaning means for developing a latent image on an electrophotographic photoreceptor with a developer, transferring a visualized toner image to a recording material, and removing toner remaining on the photoreceptor. A forming apparatus, wherein the electrophotographic photosensitive member has a structural unit having a charge transporting property on a conductive support, and has a resin layer containing a siloxane-based resin having a crosslinked structure; and The toner used in the developer contains 0.1 to 3.0% by weight of colored particles of fine particles having at least a number average primary particle diameter of 201 to 2000 nm.
An image forming apparatus, wherein the toner is an added toner. 5. A latent image on an electrophotographic photoreceptor having a resin layer containing a siloxane-based resin having a cross-linked structure and having a structural unit having charge transport performance on a conductive support is developed with a developer. After transferring the visualized toner image to the recording material, the developer used in the image forming method for cleaning the toner remaining on the photoreceptor includes at least some toner used in the developer as colored particles. Fine particles having an average primary particle diameter of 201 to 2000 nm are 0.1 to 3.
A developer comprising 0% by weight of a toner. 6. An image forming method for developing a latent image on an electrophotographic photoreceptor with a developer, transferring a visualized toner image to a recording material, and cleaning the toner remaining on the photoreceptor, The electrophotographic photoreceptor is an electrophotographic photoreceptor having a resin layer containing a siloxane-based resin having a cross-linked structure, having a structural unit having charge transport performance on a conductive support, and When the toner used is colored particles, at least a number average primary particle diameter of fine particles of 5 to 49 nm and a fine particle of 50 to 200 nm are each 0.1 to 0.1 nm.
An image forming method, wherein the toner is added by 3.0% by weight. 7. The siloxane-based resin having a structural unit having a charge-transporting performance and having a cross-linking structure is a siloxane-based resin having a compound group having a charge-transporting performance as a partial structure. 6. The image forming method according to 6. 8. The siloxane-based resin having a structural unit having charge transport performance and having a crosslinked structure is obtained by reacting an organosilicon compound having a hydroxyl group or a hydrolyzable group with a charge transport compound having a hydroxyl group. The image forming method according to claim 6, wherein the image forming method is obtained. 9. An image having a cleaning means for developing a latent image on an electrophotographic photoreceptor with a developer, transferring a visualized toner image to a recording material, and removing toner remaining on the photoreceptor. A forming apparatus, wherein the electrophotographic photosensitive member has a structural unit having a charge transporting property on a conductive support, and has a resin layer containing a siloxane-based resin having a crosslinked structure; and The toner used in the developer is a toner obtained by adding at least 0.1 to 3.0% by weight of fine particles having a number average primary particle diameter of 5 to 49 nm and 50 to 200 nm to colored particles, respectively. Image forming apparatus. 10. A latent image on an electrophotographic photoreceptor having a resin layer containing a siloxane-based resin having a crosslinked structure and having a structural unit having a charge transporting property on a conductive support is developed with a developer. After transferring the visualized toner image to the recording material, the developer used in the image forming method for cleaning the toner remaining on the photoreceptor includes at least some toner used in the developer as colored particles. Fine particles having an average primary particle diameter of 5-49 nm and 50-2000 nm
Wherein the fine particles are added in an amount of 0.1 to 3.0% by weight.