JP2003262968A - Electrophotographic photoreceptor, method for manufacturing the same, process cartridge and electrophotographic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prepare such a coating solvent for a charge transfer layer as a non-halogen solvent, that is capable of preferably dissolving a binder resin having a siloxane framework and/or a CF<SB>3</SB>side chain, of forming a charge transfer layer in a favorable state, and of developing favorable electrophotographic characteristics further as well as printing durability, and as a result, to provide a method for manufacturing an electrophotographic photoreceptor satisfying requirements for the above characteristics, an electrophotographic photoreceptor, a process cartridge and an electrophotographic device. <P>SOLUTION: In the method for manufacturing an electrophotographic photoreceptor having layers of a charge generating layer and a charge transfer layer on a supporting body, the following coating liquid for the charge transfer layer is used. The coating liquid constituting the charge transfer layer comprises as the structural component, a combination of cyclic ether having a ≤90°C boiling point under 1 atom, an aromatic hydrocarbon solvent having a substituent, and a binder resin having either a siloxane framework or a CF<SB>3</SB>side chain or both of them. The photoreceptor is obtained by the above method, and the process cartridge and the electrophotographic device are equipped with the above photoreceptor. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an electrophotographic photoreceptor,
More specifically, it relates to a manufacturing method, a process cartridge, and an electrophotographic apparatus, and more specifically, a manufacturing method of an electrophotographic photoreceptor in which a specific binder resin is dissolved in a specific non-halogen solvent to apply a charge transport layer, and the method is obtained by the manufacturing method. The present invention relates to an electrophotographic photosensitive member, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic photosensitive member, an inorganic electrophotographic photosensitive member having a photosensitive layer mainly containing an inorganic photoconductive compound such as selenium, zinc oxide, cadmium sulfide and silicon has been widely used. It was However, these are not always satisfactory in sensitivity, thermal stability, moisture resistance, durability, etc., and some inorganic electrophotographic photoreceptors contain substances harmful to the human body in the electrophotographic photoreceptor, There is a problem with disposal.

For the purpose of overcoming the drawbacks of these inorganic electrophotographic photoreceptors, research and development of organic electrophotographic photoreceptors having a photosensitive layer containing various organic photoconductive compounds as a main component have been actively conducted in recent years. . In particular, the function-separated electrophotographic photosensitive member in which different substances have the charge generating function and the charge transporting function, respectively, can be selected from a wide range of each material, the electrophotographic photosensitive member having a desired performance. Much research has been done because it can be prepared relatively easily, and many have been put to practical use.

To produce these organic electrophotographic photoreceptors, a compound having a charge generating function and a charge transporting function is laminated and coated on a conductive support. Therefore, it usually has a multi-layered structure, and each layer is solvent-coated with a coating liquid prepared by dissolving a solid compound in a solvent using various coating methods.

However, halogen-based solvents are widely used as organic solvents, especially solvents that are suitable for industrial production at a low cost and have a high dissolving power and an appropriate boiling point, but waste liquid treatment / regeneration and ecological considerations From the point of view, there is a movement to switch to a non-halogen solvent, which has less restrictions on handling after use, and with the progress of electrophotographic technology, the components of the electrophotographic photoreceptor such as the charge generating material, charge transporting material and binder resin. On the other hand, while the development of the above has been focused on, the investigation of the solvent composition for dispersing / dissolving these is also in progress.

As a matter of course, as long as it is a solvent used for producing an electrophotographic photoreceptor, it cannot be used unless it has a dissolving ability and an appropriate boiling point and does not adversely affect the characteristics as an electrophotographic photoreceptor. In recent years, the need for solvents that satisfy all of these requirements has been increasing.

On the other hand, a binder resin having a siloxane skeleton and CF ₃ atomic groups has new functions in addition to the original properties of the binder, such as improvement of water repellency, suppression of solvent crack due to stress relaxation, and increase of intramolecular bonding force. In order to contribute to high printing durability, by including in the surface layer of the electrophotographic photosensitive member, to impart slipperiness and suppress deterioration of the binder chain due to charging of the electrophotographic photosensitive member. The frequency of use as a constituent component of the surface layer of a photographic photoreceptor is increasing.

As an example of the binder resin containing such a siloxane skeleton, Japanese Patent Laid-Open No. 5-72753,
JP-A-5-188629 and JP-A-7-1336
There are polycarbonates containing a siloxane skeleton described in JP-A No. 5 and polyarylate resins containing a siloxane skeleton described in JP-A 2000-75533. As an example of a binder resin containing a CF ₃ chain, there is JP-A-6-295075.

With the speeding up and diversification of electrophotographic apparatuses, electrophotographic photosensitive members are required to have means for high durability. To make full use of such characteristics of the modified binder resin, The need for establishing means to use non-halogen type solvents instead of halogen type is increasing year by year.

In the case of a laminated electrophotographic photoreceptor in which the functions of charge generation and charge transport are separated to form a laminated structure, most of the film thickness of the photosensitive layer is the charge transport layer (about 10 to 40 μm). The solvent used for the coating solution for the layer has high solubility, does not remain in the photosensitive layer due to having an appropriate boiling point, does not drip the coating solution because the boiling point is too high, and remains as an impurity, which adversely affects electrophotographic properties. Such as not exceeding
Various required characteristics are required.

However, at present, it is difficult to find a non-halogen solvent which satisfies all the various requirements required for a coating solvent when containing such a modified binder resin.

Various requirements for the coating solvent for the charge transport layer
Among them, siloxane skeleton and CF ₃Binder
ー Where it becomes sparingly soluble by introducing it into the composition
The first issue is how to overcome.

[0013]

SUMMARY OF THE INVENTION The object of the present invention is to dissolve a binder resin having a siloxane-containing skeleton and / or a CF ₃ side chain well, to form a charge transport layer well, and to further improve electrophotographic properties. Another object of the present invention is to provide a method for producing an electrophotographic photosensitive member using a non-halogen solvent as a coating solvent for a charge transport layer, which can also exhibit good printing durability.

Another object of the present invention is to provide an electrophotographic photosensitive member obtained by the method for producing an electrophotographic photosensitive member, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.

[0015]

According to the present invention, in a method for producing an electrophotographic photosensitive member comprising a conductive support and a charge generation layer and a charge transport layer laminated on the conductive support, a coating solution for the charge transport layer is prepared. As a constituent, the boiling point at 1 atm is 9
It is manufactured using a charge-transporting coating liquid containing a combination of a cyclic ether having a temperature of 0 ° C. or lower, an aromatic hydrocarbon solvent having a substituent and a siloxane skeleton, and a binder resin having one or both of CF ₃ side chains. A method for producing a featured electrophotographic photoreceptor is provided.

According to the present invention, there are also provided an electrophotographic photosensitive member obtained by the above-described method for producing an electrophotographic photosensitive member, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below.

In the case of an electrophotographic photosensitive member, particularly an organic electrophotographic photosensitive member, when a photosensitive layer is formed by a step of drying after applying a solution, each solid material constituting them is dissolved in a solvent. Applying is a general manufacturing method.

Recently, polycarbonate and polyarylate binder resins, which are widely used as the binder resin for the charge transport layer, are used as the binder having excellent printing durability in the surface layer of the electrophotographic photoreceptor.

Further, there are reports of polycarbonate and polyarylate which are provided with advantages such as lubricity, improvement of mechanical strength, and resistance to solvent cracks by introducing a siloxane skeleton and / or a CF ₃ side chain by utilizing these characteristics. .

However, these siloxane skeletons and CF ₃
As the solvent showing good solubility in the binder resin having a side chain, methylene chloride, ethylene chloride,
A combination of halogen-containing organic solvents such as chloroform, monochlorobenzene and dichlorobenzene, or
It is a simple substance.

However, due to the situation that the load required for the treatment / regeneration of the halogen-containing organic solvent waste liquid increases, and the facilities for using / reproducing these are limited, such restrictions are relatively small. Studies are in progress to switch to less halogen-free solvents.

Examples of the halogen-free organic solvent include hydrocarbons such as pentane and hexane, alcohols such as methanol and ethanol, esters such as methyl acetate and acetic acid, aliphatic such as ketones such as acetone and methyl ethyl ketone, and cyclohexane. Various cyclic compounds such as dioxane and cyclohexanone, aromatics such as benzene, and the like, which are many in number, but have excellent strength and lubricity, are soluble in these siloxane skeletons and binder resins having CF ₃ side chains, and have a coating film. It has been difficult to find a non-halogen-based solvent that satisfies all necessary properties in a well-balanced manner, such as no sagging during formation (having an appropriate boiling point) and excellent sensitivity when it becomes an electrophotographic photoreceptor.

Particularly in the case of the charge transport layer, the film thickness is usually 15 μm.
Since more than m is required, these siloxane skeletons and C
It is necessary that the solubility of the binder resin having the F ₃ side chain is sufficient.

When a solvent which does not contain halogen and dissolves a polycarbonate or polyarylate having a siloxane skeleton and / or a CF ₃ side chain is examined, those showing good solubility are very limited, and a non-halogen type solvent is used. , There is no suitable solvent for the aliphatic hydrocarbon solvent having a suitable boiling point, and there is almost no solvent that can completely dissolve the aromatics, and the cyclic ethers are barely a halogen-free siloxane skeleton and / or CF. _It has been found that a binder resin having ₃ side chains can be dissolved.

However, when only cyclic ether is used as a solvent for the charge transport layer in dip coating, a low boiling point substance such as tetrahydrofuran or dioxolane has a uniform film thickness (film sagging) when the boiling point is 90 ° C. or lower. However, whitening (brushing) due to heat absorption of the support is a harmful effect in a normal coating environment due to rapid evaporation (this is very small when the surface of the charge transport layer is magnified and observed). You can see it with bubbles). In order to avoid this, it is necessary to control the temperature and humidity within a narrow range and / or heat the object to be coated.

Although the reason is not clear, it was also found that the electrophotographic characteristics were slightly deteriorated as compared with the conventional halogen-containing organic solvent such as chlorobenzene.

Therefore, when a combination of an aromatic hydrocarbon solvent having a substituent with a cyclic ether (suppressing rapid evaporation by a high boiling point solvent) is used, not only whitening can be suppressed but also electrophotographic characteristics (sensitivity and residual It was found that the potential) did not deteriorate, and such characteristics were not observed in a solvent other than aromatic (for example, a solvent other than aromatic such as cyclohexanone or acetylacetone).

The possible reason for this is that the aromatic solvent, which evaporates slower than the cyclic ether, can swell the resin (various acetal resins, etc.) used in the charge generation layer, so that the charge generation layer and the charge transport layer can be formed. Since the coating solution for the charge transport layer can sufficiently wet the charge generation layer while leaving the interface, as a result, it is possible to form the charge generation layer / charge transport layer interface having a very large area. This is considered to be a factor in sensitivity.

As a further effect, compared with the case where the coating solution for the charge transport layer is composed of a cyclic ether or an aromatic solvent alone,
By using the combination solvent of the present invention as the coating liquid for the charge transport layer, the printing durability of the electrophotographic photoreceptor is improved, and the solid components of the binder resin and the charge transport material are not changed, The result was that the amount of scraping was reduced.

Although the reason for these is not clear, an appropriate amount of aromatic solvent (slow evaporation is slow) is added to the cyclic ether solvent of the coating solution of the charge transport layer of the electrophotographic photosensitive member in which the charge transport layer is laminated on the charge generation layer. The low boiling cyclic ether solvent has good solubility in both the charge transport material and the binder resin. The high-boiling point aromatic solvent dissolves the charge transport material sufficiently, but does not completely dissolve the binder resin.

Due to the subtle difference in solubility as described above, when the low boiling point solvent at the beginning of drying is preferentially dried, a binder component containing a siloxane skeleton and / or a CF ₃ side chain is formed near the surface layer. On the other hand, when the high-boiling-point solvent, which has a slow evaporation rate, evaporates preferentially, the charge-transporting material dissolved in the high-boiling-point solvent preferentially precipitates from near the surface. as a result,
The binder is rich near the surface layer and inside (charge generation layer /
The vicinity of the interface of the charge transport layer) can be rich in the charge transport material. As a result, since the binder ratio is high until the surface layer is scraped to some extent, it is considered that the scraped amount will be small.

The rich presence of the charge transport material at the interface of the charge generation layer / charge transport layer helps to improve the electrophotographic characteristics. In addition, if it is an aromatic organic compound, even if it remains in a small amount in the photosensitive layer, it will hinder the electric conductivity and mobility of electric charge compared with other aliphatic saturated hydrocarbons and organic compounds with strong polarity. Can be expected to be somewhat smaller.

As described above, the siloxane skeleton and / or C
When a polycarbonate having an F ₃ side chain or a polyarylate binder resin is used as a binder resin for the charge transport layer, a cyclic ether having a boiling point of 90 ° C. or less under 1 atmosphere as a low boiling point solvent and a substituent group as a high boiling point solvent are used. By using a combination of aromatic hydrocarbon solvents, the solid components (charge transport material and binder resin)
Is sufficiently dissolved to prevent whitening over a wide temperature / humidity range in the coating-drying process, to prevent film thickness sagging, and to be equivalent to a solvent that is a preferred combination of halogenated hydrocarbons and halogenated aromatic hydrocarbons. It has been found that a non-halogen solvent can further improve electrophotographic characteristics and printing durability.

At this time, the mixing ratio of the cyclic ether having a boiling point of 90 ° C. or less and the aromatic hydrocarbon solvent having a substituent is a desired mixing ratio in view of the ease of whitening and the film thickness sag after drying. The cyclic ether / aromatic hydrocarbon = 5/95 to 95/5 (mass ratio), and more preferably 10/90 to 50/50, and the mixed solvent can be constituted in a wide mixing ratio.

Examples of the cyclic ether having a boiling point of 90 ° C. or less at 1 atm of the present invention include tetrahydrofuran (boiling point: 66 ° C.), dioxolane (72 ° C.), oxane (88 ° C.), and these. Having a substituent and a boiling point of 9
Examples thereof include those having a temperature of 0 ° C. or lower, preferably tetrahydrofuran, dioxolane and oxane.

Further, examples of the aromatic hydrocarbon having a substituent in the present invention include toluene, xylene (including structural isomers), ethylbenzene, anisole and the like,
Preferred are xylene and ethylbenzene.

Cyclic ethers such as tetrahydrofuran, dioxolane and oxane are binders such as polycarbonate and polyarylate which are not found in other halogen-free aliphatic solvents such as other aliphatic hydrocarbons, alcohols, ketones, esters, carboxylic acids and ethers. Not only resin,
A good coating liquid for an electrophotographic photoreceptor that can dissolve well a siloxane skeleton and a binder resin having a CF ₃ side chain, and can also sufficiently dissolve a low molecular weight functional material such as a charge transport material. It is a solvent.

The higher the boiling point of the cyclic ether which is a low boiling point solvent, the slower the evaporation rate of the coating liquid of the charge transport layer, and the larger the film sagging. Further, as the difference from the boiling point of the high-boiling point solvent becomes smaller, the printing durability (the amount of scraping of the charge-transporting layer) becomes superior to the case where the charge-transporting layer is formed with a single low-boiling point or high-boiling point solvent. Since it does not appear, the boiling point of the cyclic ether is empirically required to be 90 ° C. or lower in order to obtain superiority in printing durability. Within this range, evaporation characteristics suitable for the coating solvent of the electrophotographic photosensitive member can be provided.

Aromatic solvents having a substituent also show good solubility in binder resins such as polycarbonate and polyarylate, and low molecular weight functional materials such as charge transport materials, because other aliphatic hydrocarbons and alcohols It is a characteristic not found in non-halogen aliphatic solvents such as ketones, esters, carboxylic acids and ethers. On the other hand, when a siloxane skeleton or CF ₃ side chain is partially introduced into a binder resin such as polycarbonate or polyarylate, the binder resin is dissolved, but the transparency of the solution is lowered, and the poorly soluble site is partially present. Suggest to do.

Further, by containing a substituent in the aromatic hydrocarbon, the liquidity at the time of dissolving the charge transport material and the binder resin can be improved. Moreover, none of the unsubstituted ones has a suitable boiling point in practice. By including a substituent, the boiling point rises as compared with the unsubstituted one,
The boiling point is preferably less than 200 ° C. The reason is that if the temperature exceeds 200 ° C., the solvent may continue to exist as a residual solvent inside the charge transport layer after coating / drying, which may adversely affect printing durability and electrophotographic properties. Empirically, the boiling point range of 130 to 150 ° C., which is the boiling point of xylene (and structural isomers) or ethylbenzene, is a component that does not evaporate rapidly as a high boiling point solvent of the coating liquid for the charge transport layer ( It is considered to be an appropriate range that has the contradictory characteristics of (from the viewpoint of wettability with the charge generation layer) / not being a component that easily remains.

Thus, by dissolving a binder resin having a siloxane skeleton and / or a CF ₃ side chain in a solvent composition in which a cyclic ether having a boiling point of 90 ° C. or lower and an aromatic hydrocarbon having a substituent are combined. It is possible to achieve whitening and electrophotographic properties, which are the drawbacks of cyclic ethers, and on the other hand, insoluble matter residue of binder components and film thickness sagging during coating film formation, which is a drawback of aromatic solvents, and further suppression of residual components. It has become possible to form a charge transport layer having not only solvent constitutions having only advantages of each other but also high printing durability.

Examples of the binder resin having a siloxane skeleton include the following formulas (1-1) to (1-5), but the binder resins are not limited thereto (the lower right number is the degree of polymerization (molar ratio)). ) Represents).

[0044]

[Chemical 3]

[0045]

[Chemical 4]

Examples of the binder resin having a CF ₃ side chain include the following formulas (2-1) to (2-2), but the binder resin is not limited thereto (the lower right number indicates the degree of polymerization ( Molar ratio))).

[0047]

[Chemical 5]

In the binder resin of the charge transport layer in the present invention, in addition to a binder containing a siloxane and / or CF ₃ side chain, a binder resin excellent in durability and electrophotographic characteristics is blended to obtain the respective resin. It is possible to obtain an optimized structure of the charge transport layer, which takes advantage of the above characteristics.

Binder resins suitable for blending include polycarbonate and polyarylate, and these binders are known, and described in various materials such as JP-A-7-92703 and JP-A-10-20523. Has been done. Examples of constitutional units of these polycarbonates and polyarylates are shown below, but the present invention is not limited thereto. In addition, n and m in the examples represent the degree of polymerization (molar ratio).

[0050]

[Chemical 6]

[0051]

[Chemical 7]

Since cyclic ethers may be chemically unstable in a harsh environment or during long-term storage, stabilizers may be added to improve storage stability. When used as a coating liquid for the charge transport layer of the present invention, an antioxidant (AO agent) may be added as a stabilizer in the same manner. At that time, the antioxidant to be used is not particularly limited in chemical structure and the like as long as it does not adversely affect the electrophotographic characteristics. Examples of preferably used compounds include those having a hindered amine structural unit or a hindered phenol structural unit, or those having both, an organic phosphorus compound, an organic sulfur compound, a hydroquinone compound and a phenylamine compound. But
It is not limited to these.

(1) Examples of compounds having a hindered phenol structural unit

[0054]

[Chemical 8]

(2) Examples of compounds having a hindered amine structural unit

[0056]

[Chemical 9]

(3) Examples of organic phosphorus compounds

[0058]

[Chemical 10]

(4) Examples of organic sulfur compounds S (C ₂ H ₄ COOC ₁₂ H ₂₅ ) ₂ (5-8) S (C ₂ H ₄ COOC ₁₄ H ₂₉ ) ₂ (5-9)

(5) Examples of hydroquinone compounds ((5-
10) and derivatives)

[0061]

[Chemical 11]

Preferred antioxidants are those having a hindered phenol group in the molecule, which are advantageous from the viewpoints of stability of the coating solution composition, repetitive characteristics of the electrophotographic photosensitive member formed into a film, and stability of potential. And a heterogeneous mixture of antioxidants may be used.

The addition amount of the antioxidant is preferably 10 ppm to 1000 ppm with respect to the cyclic ether. If the addition amount is too small, the coating solution will deteriorate rapidly with time, and if the addition amount is too large, the electrophotographic characteristics will be adversely affected (deterioration of sensitivity). And increase in residual potential), so it is preferable to keep the addition amount as small as possible according to the desired liquid storage period.

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

The electrophotographic photoreceptor of the present invention is of a laminated type in which a charge transport layer and a charge generation layer are separated, and the surface layer is a charge transport layer so that the function can be exhibited more.

The support to be used may be any one having conductivity, and examples thereof include metals such as aluminum and stainless steel, metals provided with a conductive layer, paper, plastics, and the like, and the shape is a sheet shape or a cylindrical shape. Can be mentioned.

A conductive layer may be provided for the purpose of covering scratches on the support. This can be formed by dispersing a conductive powder such as carbon black or metal particles in a binder resin. The thickness of the conductive layer is preferably 5 to 40 μm, particularly preferably 10 to 30 μm.

An intermediate layer having an adhesive function is provided thereon. As the material of the intermediate layer, polyamide, polyvinyl alcohol, polyethylene oxide, ethyl cellulose,
Casein, polyurethane, polyether urethane and the like can be mentioned. These are dissolved in a suitable solvent and applied. The thickness of the intermediate layer is preferably 0.05 to 5 μm, and particularly preferably 0.3 to 1 μm.

A charge generation layer is formed on the intermediate layer.
The charge generation layer used in the present invention is formed by applying and drying a coating liquid in which a charge generation material and a binder resin are dispersed in a solvent. In the case of the function-separated type, the charge generation layer, together with the binder resin and the solvent, can be sufficiently processed by a homogenizer, ultrasonic dispersion, ball mill, vibrating ball mill, sand mill, attritor, roll mill or liquid collision type high speed disperser. Spread.

Examples of the charge generating material used here include pyrylium, thiapyrylium dye, phthalocyanine, anthanthrone, dibenzpyrenequinone, trisazo, cyanine, disazo, monoazo, indigo, quinacridone and asymmetric quinocyanine pigments.

As the binder resin, for example, polyester resin, polyacrylic resin, polyvinyl carbazole resin, phenoxy resin, polycarbonate resin, polystyrene resin, polyvinyl acetate resin, polysulfone resin, polyarylate resin, vinyldene chloride, polyvinyl benzal resin or poly Butyral resin and the like are mainly used. The ratio of pigment to binder resin is 1 /
0.1 to 1/10 is preferable, and more preferably 1/1 to
It is 3/1. The thickness of the charge generation layer formed by coating and drying the dispersion is preferably 5 μm or less, and particularly 0.1
˜2 μm is preferred.

The charge transport layer is formed mainly by coating / drying a coating solution in which a charge transport material and a binder resin are dissolved in the mixed solvent of the present invention. As the charge transport material used, triarylamine compounds, hydrazone compounds, stilbene compounds, pyrazoline compounds,
Examples thereof include low molecular weight compounds such as oxazole compounds, triarylmethane compounds and thiazole compounds.

As the binder resin for the charge transport layer,
Roxane skeleton and / or CF₃Binder with atomic groups
Are, for example, polycarbonate resin, polyaryle
Resin, polyacrylate resin, polyester resin,
Polystyrene resin, styrene-acrylonitrile copolymerization
Body resin, polymethacrylic acid ester resin or styrene-
Part of methacrylic acid ester copolymer resin, etc.
Skeleton and / or CF ₃It contains an atomic group
However, it is not limited to these. In addition, polycar
Bonate resin, polyarylate resin, polyacrylate
Resin, polyester resin, polystyrene resin, styrene
-Acrylonitrile copolymer resin, polymethacrylic acid
Stell resin or styrene-methacrylic acid copolymer
You may blend body resin etc. 0.5 ~ for charge transport materials
Combine with 2 times the amount of binder resin, coat, dry and charge.
Form a load transport layer. The thickness of the charge transport layer is 5 to 40 μm
Is preferable, and particularly 15 to 30 μm is preferable.

FIG. 1 shows a schematic structure of an electrophotographic apparatus provided with a process cartridge having the electrophotographic photosensitive member of the present invention.

In FIG. 1, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotationally driven around a shaft 2 in the direction of an arrow at a predetermined peripheral speed (process speed). The electrophotographic photosensitive member 1 is rotated by the primary charging means 3 during the rotation process.
The peripheral surface thereof is uniformly charged with a positive or negative predetermined potential, and then converted into a time-series electric digital image signal of the target image information output from exposure means (not shown) such as slit exposure or laser beam scanning exposure. Corresponding intensity-modulated exposure light 4 is received. In this way, electrostatic latent images corresponding to target image information are sequentially formed on the peripheral surface of the electrophotographic photosensitive member 1.

The formed electrostatic latent image is then developed by the developing means 5.
The image is visualized as a transferable particle image (toner image) by charged particles (toner) in the inside by normal development or reversal development, and an electrophotographic image is formed between the electrophotographic photosensitive member 1 and the transfer unit 6 from a sheet feeding unit (not shown). The toner image formed and carried on the surface of the electrophotographic photosensitive member 1 is sequentially transferred by the transfer unit 6 to the transfer material 7 that is taken out and fed in synchronization with the rotation of the photosensitive member 1.
At this time, a bias power source (not shown) applies a bias voltage having a polarity opposite to that of the charge held by the toner to the transfer unit.

The transfer material 7 to which the toner image has been transferred is separated from the surface of the electrophotographic photosensitive member and conveyed to the image fixing means 8 to be subjected to the fixing process of the toner image, whereby an image formed product (print, copy) is formed. Printed out.

After the transfer of the toner image, the surface of the electrophotographic photosensitive member 1 is cleaned by the cleaning means 9 to remove adhering substances such as transfer residual toner. In recent years, cleanerless systems have also been studied, and the transfer residual toner can be directly collected by a developing device or the like. Further, after the charge is removed by the pre-exposure light 10 from the pre-exposure means (not shown), it is repeatedly used for image formation. If the primary charging means 3 is a contact charging means using a charging roller or the like, pre-exposure is not always necessary.

In the present invention, among the above-mentioned electrophotographic photosensitive member 1, primary charging means 3, developing means 5, cleaning means 9 and the like, a plurality of components are housed in a container and integrally combined as a process cartridge. The process cartridge may be detachably attached to the main body of the electrophotographic apparatus such as a copying machine or a laser beam printer. For example, at least one of the primary charging unit 3, the developing unit 5, and the cleaning unit 9 is integrally supported together with the electrophotographic photosensitive member 1 to form a cartridge, and the cartridge is attached to and detached from the apparatus main body by using a guide unit 12 such as a rail of the apparatus main body. The process cartridge 11 can be freely used.

Further, when the electrophotographic apparatus is a copying machine or a printer, the exposure light 4 is reflected light or transmitted light from the document, or the document is read by a sensor, converted into a signal, and a laser is generated according to this signal. Beam scanning, LED
Light emitted by driving the array or driving the liquid crystal shutter array.

The electrophotographic photoreceptor of the present invention can be used not only in electrophotographic copying machines but also in laser beam printers,
It can be widely applied to electrophotographic application fields such as CRT printers, LED printers, FAX machines, liquid crystal printers, and laser plate making.

[0082]

EXAMPLES The present invention will be described in more detail with reference to specific examples. However, the embodiment of the present invention is not limited to these. In addition, "part" in an Example means a "mass part."

Example 1 30φ × 3 at room temperature / normal humidity
A 58 mm aluminum cylinder is used as a support, and a coating material composed of the following materials is applied to the support by a dipping method and heat-cured at 140 ° C. for 30 minutes to give a film thickness of 1
A conductive layer of 5 μm was formed.

Conductive pigment: SnO ₂ coat treated barium sulfate 10 parts Resistance adjusting pigment: titanium oxide 2 parts Binder resin: phenol resin 6 parts Leveling material: silicone oil 0.001 part Solvent: methanol / methoxypropanol (0.2 /0.8) 20 copies

Next, 3 parts of N-methoxymethylated polyamide and 3 parts of copolyamide were added to 65 parts of methanol.
A solution of 30 parts by weight / n-butanol in 30 parts was applied by a dipping method to form an intermediate layer having a film thickness of 0.5 μm.

Next, the Bragg angles (2θ ± 0.2 °) of CuKα characteristic X-ray diffraction are 9.0 °, 14.2 ° and 23.9.
4 parts of oxytitanyl phthalocyanine (TiOPc) having a strong peak at 2 ° and 27.1 °, 2 parts of polyvinyl butyral (trade name: S-REC BM2, manufactured by Sekisui Chemical Co., Ltd.) and 60 parts of cyclohexanone are 4 by a sand mill device using φ1 mm glass beads. After time-dispersed, 100 parts of ethyl acetate was added to prepare a charge generation layer coating solution. This was applied by a dipping method to form a charge generation layer having a film thickness of 0.2 μm.

Next, 10 parts of the charge transport material represented by the following formula:

[0088]

[Chemical 12] Further, 10 parts of the siloxane-modified polycarbonate resin of the formula (1-1) (viscosity average molecular weight (Mv) = 40,000) is dissolved in a mixed solvent of 30 parts of tetrahydrofuran / 50 parts of m-xylene to prepare a coating liquid for charge transport layer. And The coating solution was applied by a dipping method (constant coating speed) and dried at 140 ° C. for 30 minutes to form a charge transport layer having a film thickness of 28 μm (near the center).

The viscosity average molecular weight was calculated as follows. Dissolve 0.5 g of the sample in 100 ml of methylene chloride and use a modified Ubbelohde viscometer to measure 25 g.
Measure the specific viscosity at ° C. The intrinsic viscosity is obtained from this specific viscosity, and the average molecular weight is calculated by the Mark-Houwink viscosity formula. At this time, viscosity average molecular weight (Mv)
Is a polystyrene conversion value measured by GPC (gel permeation chromatography).

At this time, the following whitening, sagging, and bright part potential (Vl (potential at the time of overall exposure)) by an actual machine were measured, and in addition, a Taber abrasion test and a dissolution test were also performed. The results are shown in Table 2.
Shown in.

<Confirmation of whitening> The charge transport layer of the electrophotographic photosensitive member after production was observed with an optical microscope, and when a large number of micro bubbles were observed, it was evaluated as x, and when not observed, it was evaluated as o.

<Confirmation of sagging> The film thickness difference between the position of 180 mm (approximately the center of the electrophotographic photosensitive member) and the same position of 20 mm from the coating upper end (uncoated side) of the charge transport layer of the electrophotographic photosensitive member after fabrication was measured. Measured, ○ when the film thickness difference is less than 9 μm, 9 μ
The case of m or more was evaluated as x.

<Measurement of Bright Area Potential> Canon LBP-9
The electrophotographic photosensitive member produced by using 50 and its process cartridge (EP-72) is removed from the transfer roller under the environment of normal temperature and normal humidity (about 23 ° C./60% RH) in this apparatus and the potential probe is used. Bright part potential (V
1) was measured.

<Measurement of Taber Abrasion Test> The same charge transport layer coating solution as in this example was applied onto an aluminum sheet with a bar coater (drying conditions / film thickness are the same as in this example).
Then, the amount of mass reduction of this charge transport layer sheet (CT sheet) was measured with a Taber abrasion tester.

The Taber abrasion test method was as follows: Fuji Photo Film Co. # 2000 wrapping tape / weight 50
JIS K 7204 (199) with 0 g attached
According to No. 5) of Yasuda Seiki Seisakusho, No. 101 Tabe
The mass reduction amount of the charge transport layer was measured using a r Type Abrasion Tester (rotation speed: 1 rotation / second, 1000 rotations).

<Dissolution test> Same solvent composition as the charge transport layer (tetrahydrofuran 30 parts / m-xylene 50 parts)
In addition, 28 parts of the silicone-modified polycarbonate of the formula (1-2) (Mv = 40,000) was mixed and stirred, and the transparency of the solution after 24 hours was visually confirmed. When it was observed, it was evaluated as Δ, and when insoluble matter was observed, it was evaluated as x.

(Examples 2 to 5) Nos.
The solvent composition of the charge transport layer is 2 to 5, and BHT (2,6-di-tert-) of the formula (5-1) is used as an antioxidant.
Butyl-4-methylphenol), the drying temperature / hour is 110 ° C./hour, and the thickness of the charge transport layer is 2
An electrophotographic photosensitive member, a charge transport layer sheet, and a dissolution test solution were prepared in the same manner as in Example 1 except that the thickness was changed to 4 μm, and the whitening, sagging, bright part potential of the actual machine, Taber abrasion amount, and solution state were measured. It was evaluated and measured. The results are shown in Table 2.

[0098]

[Table 1]

[0099]

[Table 2]

(Comparative Examples 1 to 7) Nos.
The solvent composition of the charge transport layer is 1 to 5, and BHT (2,6-di-tert-) of the formula (5-1) is used as an antioxidant.
Butyl-4-methylphenol), the drying temperature / hour is 110 ° C./hour, and the thickness of the charge transport layer is 2
An electrophotographic photosensitive member, a charge transport layer sheet, and a dissolution test solution were prepared in the same manner as in Example 1 except that the thickness was changed to 4 μm, and the whitening, sagging, bright part potential of the actual machine, Taber abrasion amount, and solution state were measured. It was evaluated and measured. The results are shown in Table 4.

[0101]

[Table 3]

[0102]

[Table 4]

Example 6 A silicone-modified polycarbonate (M) of the formula (1-2) was used as a binder resin for the charge transport layer.
v = 40,000), and the solvent of the coating liquid for the charge transport layer was changed to No. BHT (2,6-di-tert-butyl-4-methylphenol) of the formula (5-1) was added to the composition described in 6 as an antioxidant, and the drying temperature / hour was 110 ° C./1 hour. In the same manner as in Example 1, except that the thickness of the charge transport layer was changed to 24 μm, an electrophotographic photosensitive member, a charge transport layer sheet, and a dissolution test solution were prepared, and whitening, sagging, and a bright part of an actual machine were performed. The potential, the amount of Taber abrasion and the solution state were evaluated and measured. The results are shown in Table 6.

Example 7 The silicone modified polyarylate (Mv) of the formula (1-5) was used as the binder resin of the charge transport layer.
= 40,000), the charge transport material was replaced with a compound represented by the following formula, and the solvent of the coating solution for the charge transport layer was No. 5 in Table 5. 7 has the structure of B of formula (5-1) as an antioxidant.
Example except that HT (2,6-di-tert-butyl-4-methylphenol) was added, the drying temperature / hour was changed to 110 ° C./1 hour, and the thickness of the charge transport layer was changed to 24 μm. An electrophotographic photoreceptor and a charge transport layer sheet and a solution for dissolution test were prepared in the same manner as in 1, and the whitening, sagging, bright part potential of an actual machine, Taber abrasion amount and solution state were evaluated and measured. The results are shown in Table 6.

[0105]

[Chemical 13]

Example 8 The silicone-modified polycarbonate (M) of the formula (1-2) was used as the binder resin for the charge transport layer.
v = 40,000 and 2 parts and the polycarbonate of the formula (3-3) (trade name: Z400, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) were replaced with 8 parts and a total of 10 parts, and a silicone powder lubricant (product) Name: Aron GS-101CP, manufactured by Toagosei Chemical Industry Co., Ltd., 0.1 part, and a fluorosurfactant (trade name: Aron GF-300, manufactured by Toagosei Chemical Industry Co., Ltd.) was added. No. 05 of Table 5 was added to the charge transport layer coating solution. 8, the drying temperature / hour is 110 ° C./hour, and the thickness of the charge transport layer is 2
An electrophotographic photoreceptor and a charge transport layer sheet and a solution for dissolution test {Formula (1-2): Formula (3-3) = 2: 8} were prepared in the same manner as in Example 1 except that the thickness was changed to 4 μm. Then, whitening, sagging, and light potential of the actual machine, Taber abrasion amount, and solution state were evaluated and measured. The results are shown in Table 6.

Example 9 The silicone modified polyarylate (Mv) of the formula (1-5) was used as the binder resin of the charge transport layer.
= 40,000) and 2 parts of the polyarylate of formula (4-2) (Mv
= 51,000) was changed to 8 parts for a total of 10 parts, and the solvent of the coating liquid for the charge transport layer was changed to No. 5 in Table 5. 9, the electrophotographic photoreceptor and the charge transport layer were formed in the same manner as in Example 1 except that the drying temperature / hour was changed to 120 ° C./1 hour and the thickness of the charge transport layer was changed to 24 μm. A sheet and a solution for dissolution test {Formula (1-5): Formula (4-2) = 2: 8} were prepared, and whitening, sagging, light portion potential of actual machine, Taber abrasion amount, and solution state were evaluated and measured. . The results are shown in Table 6.

Example 10 2 parts of a polycarbonate (Mv = 40,000) having a CF ₃ side chain of the formula (2-2) and a polyarylate of the formula (4-2) (Mv) were used as the binder resin of the charge transport layer. = 510,000) was replaced with a total of 10 copies of 8 copies,
The solvent of the coating liquid for the charge transport layer was set to No. 5 in Table 5. BHT of the formula (5-1) as an antioxidant in the constitution described in 10
(2,6-di-tert-butyl-4-methylphenol) was added and the drying temperature / hour was 120 ° C./1 hour,
An electrophotographic photoreceptor and a charge transport layer sheet and a solution for dissolution test (formula (2-2): formula (4-2)) in the same manner as in Example 1 except that the thickness of the charge transport layer was changed to 24 μm. =
2: 8} was prepared, and whitening, sagging, light portion potential of actual machine, Taber abrasion amount, and solution state were evaluated and measured. The results are shown in Table 6.

[0109]

[Table 5]

[0110]

[Table 6]

[0111]

As described above, the siloxane-containing skeleton and / or the C-containing skeleton are provided depending on the specific solvent composition of the charge transport layer of the present invention.
A non-halogen coating solvent is used to satisfactorily dissolve a binder resin having an F ₃ side chain, and to exhibit excellent film properties and shape when forming a charge transport layer and electrophotographic characteristics as an electrophotographic photoreceptor. The method for producing an electrophotographic photosensitive member capable of achieving an improvement in printing durability without changing the solid component constitution as a further effect, and the electrophotography obtained by the method. It has become possible to provide a photoconductor, a process cartridge having the electrophotographic photoconductor, and an electrophotographic apparatus.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus provided with a process cartridge having an electrophotographic photosensitive member of the present invention.

[Explanation of symbols]

1 Electrophotographic photoreceptor 2 axes 3 charging means 4 exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 guidance means

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Miki Tanabe             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Kazunari Nakamura             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Yamasaki             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Hirotoshi Uesugi             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation F term (reference) 2H068 AA13 BB25 BB27 BB31 BB33                       EA14

Claims (11)

[Claims] 1. A method of manufacturing an electrophotographic photosensitive member comprising a charge generation layer and a charge transport layer laminated on a conductive support,
Cyclic ethers having a boiling point of 90 ° C. or less under 1 atmosphere, aromatic hydrocarbon solvents having a substituent and siloxane skeleton, as constituents of the coating liquid constituting the charge transport layer.
A method for producing an electrophotographic photosensitive member, which comprises using a charge-transporting coating liquid containing a binder resin having one or both of CF ₃ side chains in combination. 2. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the cyclic ether having a boiling point of 90 ° C. or less under 1 atmosphere is tetrahydrofuran. 3. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the cyclic ether having a boiling point of 90 ° C. or less under 1 atmosphere is dioxolane. 4. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the cyclic ether having a boiling point of 90 ° C. or less under 1 atmosphere is oxane. 5. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the aromatic hydrocarbon solvent having a substituent is xylene or ethylbenzene. 6. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the binder resin having a siloxane skeleton is a polycarbonate or a polyarylate having a structure of the following formula (1). [Chemical 1] (In the formula, R ₁ and R ₂ each represent an alkyl group, an aryl group or an aralkyl group, and R ₁ and R ₂ may be the same or different. N represents an integer of 3 or more.) 7. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the binder resin having a CF ₃ side chain is polycarbonate or polyarylate having a structure of the following formula (2). 2] 8. The method for producing an electrophotographic photosensitive member according to claim 1, further comprising one or both of polycarbonate and polyarylate as a binder resin. 9. An electrophotographic photosensitive member manufactured by using the method for manufacturing an electrophotographic photosensitive member according to claim 1. 10. An electrophotographic photosensitive member manufactured by using the method for manufacturing an electrophotographic photosensitive member according to claim 1, a charging unit for charging the electrophotographic photosensitive member, and an electrostatic latent image. Of the electrophotographic photosensitive member thus formed with a toner and at least one unit selected from the group consisting of a cleaning unit for collecting the toner remaining on the electrophotographic photosensitive member after the transfer step. , A process cartridge which is detachable from the main body of the electrophotographic apparatus. 11. An electrophotographic photosensitive member manufactured by the method for manufacturing an electrophotographic photosensitive member according to claim 1, a charging unit for charging the electrophotographic photosensitive member, and a charged electrophotographic apparatus. An exposure unit that exposes the photosensitive member to form an electrostatic latent image, a developing unit that develops with an toner on the electrophotographic photosensitive member on which the electrostatic latent image is formed, and a toner image on the electrophotographic photosensitive member on a transfer material. An electrophotographic apparatus comprising a transfer means for transferring.